CN106167250B - A kind of acid CuCl2Etching solution method of comprehensive utilization - Google Patents

A kind of acid CuCl2Etching solution method of comprehensive utilization Download PDF

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CN106167250B
CN106167250B CN201610530726.5A CN201610530726A CN106167250B CN 106167250 B CN106167250 B CN 106167250B CN 201610530726 A CN201610530726 A CN 201610530726A CN 106167250 B CN106167250 B CN 106167250B
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acid
solution
liquid
evaporation
comprehensive utilization
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CN106167250A (en
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王学文
王明玉
刘彪
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NINGBO FMR ENVIRON. & TECH. Co.,Ltd.
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • C01B7/07Purification ; Separation
    • C01B7/0706Purification ; Separation of hydrogen chloride
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/02Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00Compounds of copper
    • C01G3/02Oxides; Hydroxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

Abstract

A kind of acid CuCl2 etching solutions method of comprehensive utilization, it is characterised in that acidic etching liquid heating evaporation is first reclaimed into free HCl therein, the steam cooling being evaporated absorbs to obtain hydrochloric acid.Evaporation more than 80 DEG C of raffinate plus-minus filters to obtain liquid after cupric oxide filter cake and heavy copper after neutralizing.Cupric oxide filter cake is scrubbed again, obtains CuO products after drying.Liquid first adds sulfuric acid transition after heavy copper, then more than 100 DEG C double evaporation-cooling recovery hydrochloric acid, double evaporation-cooling raffinate room temperature crystallisation by cooling separate out niter cake NaHSO4·H2O crystal, make acid CuCl2Copper, chlorine in etching solution and sodium is efficiently separated and recycling, realize the zero-emission of technical process, mitigate copper acid etching technique pressure to caused by environment significantly.

Description

A kind of acid CuCl2Etching solution method of comprehensive utilization
Technical field
The invention belongs to chemical industry metallurgical field, and in particular to a kind of acid CuCl2Etching solution method of comprehensive utilization.
Background technology
Acid copper chloride etching liquid (HCl-CuCl2- NaCl) because its etching speed it is easy to control, molten amount of copper is big, and etching solution exists High etching quality can be reached under stable state, and be widely used in producing multiple-plate internal layer and printing-etched plate, and figure The etching of shape printed panel.The acidic etching processes of copper are with NaClO3Make oxidant, the dissolution agent of copper is made with hydrochloric acid and acidity is adjusted Agent is saved, product is CuCl2And NaCl.Therefore, with the progress of etching reaction, CuCl in etching solution2Concentration with NaCl can be gradual Rise.The etching speed of etching solution is with CuCl2The increase of concentration and reduce, when Cu concentration rises to 140-150g/L in solution, just It is difficult to be continuing with, so as to turn into acidic etching waste liquid.The acidic etching waste liquid discharged on production line has very high comprehensive profit With value.
Acidic etching waste liquid mainly reclaims copper therein at present, and its method mainly has electrolysis, solvent extraction, chemistry The precipitation method and crystallisation.Although electrolysis can reclaim to active ingredient therein, because electrolytic process discharges Cl2And make it Using being restricted.Solvent extraction is high because of etching liquid acidity, it is difficult to finds suitable extractant and still stagnates at present.Change Copper therein can only also be reclaimed by learning the precipitation method and crystallisation, wherein substantial amounts of Cl and Na can not be comprehensively utilized, to environmental protection Bring very big pressure.
The content of the invention
The present invention in view of the shortcomings of the prior art, proposes a kind of acid CuCl2Etching solution method of comprehensive utilization.
A kind of acid CuCl of the present invention2Etching solution method of comprehensive utilization, it is characterised in that comprise the following steps:
Step 1:Evaporation separation and recovery free hydrochloric acid
By acid CuCl2Etching solution is heated to being no more than 125 DEG C, evaporates free hydrochloric acid therein, the steam being evaporated Condensed absorbent obtains hydrochloric acid A, and evaporation raffinate is used for recovering copper;
Step 2:Precipitate recovering copper
In 80-125 DEG C, evaporation raffinate obtained by step 1 is mixed with sodium hydroxide, it is 6.5-13.5 to control terminal pH, Make Cu therein Precipitations in the form of cupric oxide, filter to obtain liquid after cupric oxide filter cake and heavy copper;Liquid divides again after heavy copper From recovery chlorine therein and sodium;Preferable mixing temperature is 90-115 DEG C, and preferable pH is 8.5-10.5;
Step 3:Make the transition separation and recovery of chlorine and sodium
Sulfuric acid is added in liquid after the heavy copper obtained to step 2, after the sodium in liquid after heavy copper is changed into niter cake, is added Heat makes Cl therein to 160 DEG C of evaporations are no more than-Volatilized in the form of HCl, the steam being evaporated is through BaCl2- HCl solution is washed After washing, condensed absorbent obtains hydrochloric acid B, and the cooling of evaporation raffinate or freezing and crystallizing separate out niter cake NaHSO4·H2O, filter to obtain sulfuric acid Hydrogen sodium crystal and its crystalline mother solution, liquid transition process is continuing with after crystalline mother solution then returns to heavy copper.
A kind of acid CuCl of the present invention2Etching solution method of comprehensive utilization, in step 1, acid CuCl2Etching solution is heated to When the 75-125 DEG C of concentration for being evaporated to free hydrochloric acid in solution is down to 0.5-0.05mol/L, stop evaporation;Evaporation is steamed selected from normal pressure Hair is evaporated under reduced pressure.
A kind of acid CuCl of the present invention2Etching solution method of comprehensive utilization, in step 2, evaporation raffinate that step 1 is obtained After being heated to 80-125 DEG C, stirring thereto adds NaOH solids or temperature up to 80-125 DEG C of NaOH solution, makes mixed solution PH value rise to 6.5-13.5 after, maintain mixed solution temperature constant temperature between 80-125 DEG C, continue stir 0.5-2.5h; Or,
The evaporation raffinate stirring that step 1 obtains is added in the NaOH solution that temperature is 80-125 DEG C, makes the pH of solution After value drops to 13.5-6.5, solution temperature constant temperature between 80-125 DEG C is maintained, continues to stir 0.5-2.5h, filters black Color cupric oxide filter cake;The mass concentration of NaOH solution is 6-60%;
The cupric oxide filter cake being filtrated to get is added to OH-Ion concentration is 2-10mol/L, temperature 85-115 DEG C alkali lye in, stir 0.5-2.5h, filter to get filtrate while hot and filter residue, gained filtrate be stored at room temperature 16-24h, is filtered to remove The Fe (OH) wherein separated out3It is continuing with Deng washing procedure is returned after impurity, filter residue is washed with water to neutrality, 105-250 DEG C of drying 2-5h must aoxidize copper products;The solid-to-liquid ratio of cupric oxide filter cake and alkali lye is 1:1-6g/ml;Alkali in described alkali lye is selected from At least one of NaOH, KOH.
A kind of acid CuCl of the present invention2Etching solution method of comprehensive utilization, in step 3, changed into by the sodium in liquid after heavy copper After 1-5 times of niter cake stoichiometric number adds sulfuric acid, 75-160 DEG C of evaporation 0.2-2.0h is heated to;The matter of the sulfuric acid of addition Amount concentration is 40-98%;The niter cake crystal being filtrated to get directly makees product and sells or resaled after recrystallizing;Evaporation is selected from Atmospheric evaporation or reduction vaporization.
A kind of acid CuCl of the present invention2Etching solution method of comprehensive utilization, what the hydrochloric acid A that step 1 obtains obtained with step 3 Hydrochloric acid B returns to etching production line and is used to configure acidic etching liquid in the lump, or makees product sale, realizes acid CuCl2In etching solution The comprehensive utilization of Cl elements.
It is of the invention that there is advantages below and effect compared with existing technology:
The present invention dexterously using evaporation separation and recovery free hydrochloric acid-precipitation recovering copper-transition separation and recovery of chlorine and The PROCESS FOR TREATMENT of sodium contains CuCl2Acidic etching waste liquid, not only effectively reclaimed copper, and chlorine and sodium therein is also obtained Comprehensive utilization.In addition, the present invention is due to maintaining heavy process for copper Process liquor temperature to effectively prevent glue between 80-125 DEG C Shape Cu (OH)2The generation of precipitation, this not only significantly reduces the volume of copper sediment, improves the strainability of copper sediment, And significantly improve the purity of copper sediment, it is ensured that the purity of CuO products is up to more than 98.5%.Pass through present invention process It is overall to redesign, the mutual cooperation between each step, thus acid CuCl can be made2Copper, chlorine and sodium in etching solution obtain Efficiently separate and recycling, realize the zero-emission of technical process, mitigate copper acid etching technique significantly to caused by environment Pressure, also comply with the development trend of China's energy-conserving and emission-cutting technology transformation.
Embodiment
With reference to embodiment, the invention will be further described, following examples be intended to illustrate invention rather than it is right The further restriction of the present invention.
Embodiment 1
Take 151.3g/L containing Cu, HCl 2mol/L, NaCl 52.6g/L etching solution 2.5m3, 95 DEG C of reduction vaporizations 0.5h, HCl concentration therein is set to be down to 0.25mol/L, the steam cooling absorption evaporated obtains HCl contents up to 10.5% Hydrochloric acid.Evaporation residue stir while hot add temperature be 85 DEG C of concentration up to 20% NaOH solution, when the pH of solution rises to 9.5 stop plus alkali, and 105 DEG C are continued to stir 0.5h, filter to obtain liquid after cupric oxide filter cake and heavy copper.Cupric oxide filter cake presses solid-liquid Than 1:3g/ml mixes with 4mol/L NaOH solution, 95 DEG C of agitator treating 1h, filters to obtain liquid after alkali cleaning cupric oxide and alkali cleaning.Alkali Wash rear liquid and be stored at room temperature 20h, filter off except after the red precipitate wherein separated out, return cupric oxide filter cake caustic wash process continues to make With.Alkali cleaning cupric oxide filter cake is first eluted 3 times with clear water, then by solid-to-liquid ratio 1:1g/ml is stirred with distilled water wash 2 times after, 155 DEG C drying 2.5h obtains purity up to 98.7% CuO products, and the rate of recovery of technical process copper is up to 99.7%.Liquid is converted by sodium therein after heavy copper 4.5 times into niter cake theoretical amount add the sulfuric acid transition that concentration is 98%, and 130 DEG C of atmospheric evaporation 0.5h of liquid, are waved after transition The steam issued is through BaCl2After the washing of-HCl solution, cooling, which absorbs, obtains HCl contents up to 25.1% hydrochloric acid, evaporates raffinate Room temperature crystallisation by cooling separates out purity up to 99.1% niter cake NaHSO4·H2O crystal, niter cake crystalline mother solution return to heavy copper Liquid transition process is continuing with afterwards, and gained hydrochloric acid returns to production line and prepares etching solution.
Embodiment 2
Take 153.2g/L containing Cu, HCl 1.8mol/L, NaCl 54.1g/L etching solution 2L, 106 DEG C of atmospheric evaporations 45min, HCl concentration therein is set to be down to 0.12mol/L, the steam cooling absorption evaporated obtains HCl contents up to 9.1% Hydrochloric acid.Evaporation residue stir while hot add temperature be 90 DEG C, the KOH solution that concentration is 8mol/L, when the pH of solution rises to 8.5 stop plus alkali, 103 DEG C of solution continue to stir 1.5h, filter to obtain liquid after cupric oxide filter cake and heavy copper.Cupric oxide filter cake is pressed Solid-to-liquid ratio 1:3g/ml adds liquid after the alkali cleaning that embodiment 1 obtains, and stirring is filtered after boiling 0.5h, and alkali cleaning cupric oxide is again through distillation The CuO products that purity is 99.1% are obtained after water rinsing, drying.Liquid by volume 1 after heavy copper:The sulfuric acid that 3 addition embodiments 1 obtain Hydrogen sodium crystalline mother solution makes the transition, 115 DEG C of atmospheric evaporation 1h of liquid after transition, and the steam cooling absorption evaporated obtains HCl contents and reached 22.8% hydrochloric acid, evaporation raffinate room temperature crystallisation by cooling separate out purity up to 99.3% niter cake NaHSO4·H2O crystal.
Embodiment 3
Take 153.2g/L containing Cu, HCl 1.8mol/L, NaCl 54.1g/L etching solution 2L, 106 DEG C of atmospheric evaporations 45min, HCl concentration therein is set to be down to 0.12mol/L, the steam cooling absorption evaporated obtains HCl contents up to 9.1% Hydrochloric acid.Evaporation residue stirs while hot adds the cupric oxide tune pH to 3.6 that embodiment 1 obtains, filtering, and filtrate is then added to In the NaOH solution that 500mL temperature is 105 DEG C, concentration is 50%, continue to stir 1.5h after solution mixing, filter to obtain black oxidation Liquid after copper filter cake and heavy copper.Cupric oxide filter cake obtains the CuO products that purity is 99.4% after distilled water is rinsed, dried.After heavy copper Liquid by volume 1:The niter cake crystalline mother solution transition that 3 addition embodiments 1 obtain, 120 DEG C of atmospheric evaporation 1h of liquid, are waved after transition The steam cooling issued, which absorbs, obtains HCl contents up to 21.7% hydrochloric acid, and evaporation raffinate room temperature crystallisation by cooling separates out purity and reached 99.3% niter cake NaHSO4·H2O crystal.

Claims (9)

  1. A kind of 1. acid CuCl2Etching solution method of comprehensive utilization, it is characterised in that comprise the following steps:
    Step 1:Evaporation separation and recovery free hydrochloric acid
    By acid CuCl2Etching solution is heated to 75-125 DEG C, evaporates free hydrochloric acid therein, is evaporated to free hydrochloric acid in solution When concentration is down to 0.5-0.05 mol/L, stop evaporation, the steam condensed absorbent being evaporated obtains hydrochloric acid A, and evaporation raffinate is used for Recovering copper;
    Step 2:Precipitate recovering copper
    In 80-125 DEG C, evaporation raffinate obtained by step 1 is mixed with sodium hydroxide, it is 6.5-13.5 to control terminal pH, is made wherein Cu in the form of cupric oxide Precipitation, filter to obtain liquid after cupric oxide filter cake and heavy copper;Liquid separates and recovers again after heavy copper Chlorine and sodium therein;
    Step 3:Make the transition separation and recovery of chlorine and sodium
    Sulfuric acid is added in liquid after the heavy copper obtained to step 2, after the sodium in liquid after heavy copper is changed into niter cake, is heated to No more than 160 DEG C evaporations, make Cl therein-Volatilized in the form of HCl, the steam being evaporated is through BaCl2- HCl solution washs Afterwards, condensed absorbent obtains hydrochloric acid B, and the cooling of evaporation raffinate or freezing and crystallizing separate out niter cake NaHSO4·H2O, filter to obtain hydrogen sulfate Sodium crystal and its crystalline mother solution, liquid transition process is continuing with after crystalline mother solution then returns to heavy copper;Hydrochloric acid A that step 1 obtains with Hydrochloric acid B returns to etching production line and is used to configure acidic etching liquid in the lump.
  2. A kind of 2. acid CuCl according to claim 12Etching solution method of comprehensive utilization, it is characterised in that:In step 2, After the evaporation raffinate that step 1 obtains is heated into 80-125 DEG C, stirring adds NaOH solids thereto or temperature reaches 80-125 DEG C NaOH solution, after the pH value of mixed solution is risen to 6.5-13.5, constant temperature, at least stir 0.5h;Or,
    The evaporation raffinate stirring that step 1 obtains is added in the NaOH solution that temperature is 80-125 DEG C, made under the pH value of solution After dropping to 13.5-6.5, constant temperature, 0.5h is at least stirred, filter to obtain cupric oxide filter cake.
  3. A kind of 3. acid CuCl according to claim 22Etching solution method of comprehensive utilization, it is characterised in that:NaOH solution Mass concentration be 6-60%.
  4. A kind of 4. acid CuCl according to claim 32Etching solution method of comprehensive utilization, it is characterised in that:It will be filtrated to get Cupric oxide filter cake be added to OH-In the alkali lye that ion concentration is 2-10mol/L, temperature is 85-115 DEG C, 0.5- is stirred 2.5h, filters to get filtrate while hot and filter residue, gained filtrate are stored at room temperature 16-24h, is returned after being filtered to remove the impurity wherein separated out Washing procedure is continuing with, and filter residue, which is washed with water to neutrality, 105-250 DEG C of drying 2-5h, must aoxidize copper products;Cupric oxide is filtered The solid-to-liquid ratio of cake and alkali lye is 1:1-6 g/ml.
  5. A kind of 5. acid CuCl according to claim 42Etching solution method of comprehensive utilization, it is characterised in that described alkali lye In alkali be selected from least one of NaOH, KOH.
  6. A kind of 6. acid CuCl according to claim 12Etching solution method of comprehensive utilization, it is characterised in that:In step 3, By the sodium in liquid after heavy copper change into 1-5 times of niter cake stoichiometric number add sulfuric acid after, be heated to 75-160 DEG C of evaporation 0.2-2.0h;The mass concentration of the sulfuric acid of addition is 40-98%.
  7. A kind of 7. acid CuCl according to claim 62Etching solution method of comprehensive utilization, it is characterised in that:It is filtrated to get Niter cake crystal directly makees product and sells or resaled after recrystallizing.
  8. A kind of 8. acid CuCl according to claim 1 or 62Etching solution method of comprehensive utilization, it is characterised in that:The steaming Hair is selected from atmospheric evaporation or reduction vaporization.
  9. A kind of 9. acid CuCl according to claim 1-7 any one2Etching solution method of comprehensive utilization, it is characterised in that: The hydrochloric acid B that the hydrochloric acid A that step 1 obtains obtains with step 3 makees product sale in the lump, realizes acid CuCl2Cl members in etching solution The comprehensive utilization of element.
CN201610530726.5A 2016-07-07 2016-07-07 A kind of acid CuCl2Etching solution method of comprehensive utilization Active CN106167250B (en)

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CN107354461A (en) * 2017-09-13 2017-11-17 田成 A kind of printed circuit board acidic etching waste liquor process for regenerating, recovering and reutilizing
CN111333099B (en) * 2020-03-06 2022-04-08 合肥工业大学 Method for preparing nano copper hydroxide from acidic copper chloride etching waste liquid

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CN100484878C (en) * 2005-09-16 2009-05-06 上海应用技术学院 Method for preparing cuprous chloride using printed circuit board etching waste liquid
CN102303892B (en) * 2011-08-15 2013-04-24 昆山德阳新材料科技有限公司 Method for preparing copper oxide based on acidic etching liquid as raw material
CN103966607A (en) * 2013-01-31 2014-08-06 西安瑞凯电力科技有限公司 Method for recovering copper and hydrochloric acid from acid etching solution

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