CN100467671C - Method for recovering hydrochloric acid and copper sulfate from acidic etching liquid - Google Patents
Method for recovering hydrochloric acid and copper sulfate from acidic etching liquid Download PDFInfo
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- CN100467671C CN100467671C CNB2006100380805A CN200610038080A CN100467671C CN 100467671 C CN100467671 C CN 100467671C CN B2006100380805 A CNB2006100380805 A CN B2006100380805A CN 200610038080 A CN200610038080 A CN 200610038080A CN 100467671 C CN100467671 C CN 100467671C
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- hydrochloric acid
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Abstract
This invention is a method of recovering chlorhydric acid and copper sulfate from acid etching solution. The procedures are that (1) recovering chlorhydric acid. The acid etching waste solution is filled in acid resistant distillation plant, then concentrated sulfuric acid is added, then they are heated to boiling state and the chlorhydric acid is recovered through distillation, the concentration of the concentrated sulfuric acid is 98% or more than 98%. The adding on is more than 5-15% than that based on the theoretical value of copper ion fully reacted with sulfuric acid in the distillation. (2) Recovering copper sulfate. First, the residue in chlorhydric acid recovery is watering dissolved to thoroughly decompose the copper sulfate in the residue; the adding quantity of the water is 30-70% volume of acid etching waste solution. Secondly, copper sulfate is seed out through the changing of high temperature to low temperature; the temperature change is controlled between 40 to 60 degrees centigrade. Thirdly, copper sulfate is got after the copper sulfate crystalline is filtrated and washed. The simplest method is used to recover the useful resource in etching waste liquor in this invention. The technique equipment is simple, operation is convenient, and there is no environment pollution, so it has wide using value.
Description
Technical field
The present invention relates to from industrial effluent, reclaim the method for useful resources, be specifically related to a kind of method that from acidic etching waste liquid, reclaims hydrochloric acid and copper sulfate.
Background technology
Over past ten years, steady-state growth along with world's electronic industry, China's printed circuit board is to surpass 20% speedup fast development. and will produce a large amount of acidic etching waste liquids every year, its main component is cupric chloride and hydrochloric acid, copper content is at 130～180g/L, concentration of hydrochloric acid is about 10%. and the processing of waste liquid has not only solved the pollution problem of waste liquid from environmental angle, main is to make limited resources obtain reclaiming and utilizing, and has obvious social and economic benefit.
In the recovery of etching solution and aspect utilizing many kinds of methods were arranged in the past. first kind is to add copper powder in etching solution, hydrochloric acid reaction in heating back copper powder and the etching solution, by the hydrochloric acid in this reaction removal etching solution, and then by reaction generation copper sulfate. owing to can produce a large amount of poisonous gases in the reaction process, the words of directly discharging if this gas is not handled, with the severe contamination atmosphere, human body is caused very big injury. second kind is to add cupric oxide to come neutralizing acid in etching solution, thereby the hydrochloric acid in the removal etching solution, and then by reaction generation copper sulfate. but the market price of cupric oxide is very high, so consider from economic benefit, this method also is unadvisable. the third is to adopt a large amount of alkali (such as ammoniacal liquor) neutralizing acid, thereby the hydrochloric acid in the removal etching solution, yet and then by reaction generation copper sulfate. this method economic benefit is poorer.
By above introduction as can be known, the deficiency that prior art exists is: 1, reclaim(ed) sulfuric acid copper from acidic etching liquid only, and abandoned recovery to hydrochloric acid; 2, existing method is not to have severe contamination, is exactly the cost height, deficiency in economic performance.Therefore, recoverying and utilizing method how to explore a kind of not only simple economy but also environmental protection is the problem that those skilled in the art pay close attention to always.
Summary of the invention
The invention provides a kind of method that from acidic etching liquid, reclaims hydrochloric acid and copper sulfate, its objective is that will solve prior art exists problems such as deficiency in economic performance and environment protection.
For achieving the above object, the technical solution used in the present invention is: a kind of method that reclaims hydrochloric acid and copper sulfate from acidic etching liquid comprises following steps successively:
(1), reclaims hydrochloric acid
Acidic etching waste liquid is contained in the acid proof water distilling apparatus, adds the vitriol oil then, be heated to boiling state and reclaim hydrochloric acid by distillation, wherein, the concentration of the vitriol oil is more than 98% or 98%; The add-on of the vitriol oil increases by 5～15% again based on content of copper ion in the water distilling apparatus and the required theoretical value of sulfuric acid complete reaction;
(2), copper sulfate is received in the field
1., remaining residual looking into after reclaiming hydrochloric acid is dissolved in water, the copper sulfate in residual the looking into is fully dissolved, the add-on of water is controlled at and adds 30～70% of acidic etching waste liquid volume;
2., utilize high temperature by cooling cupric sulphate crystal to be separated out to cryogenic temperature variation, the temperature difference of temperature variation is controlled at 50 ± 10 ℃ of scopes;
3., the cupric sulphate crystal body is filtered and washing obtains copper sulfate.
Related content in the technique scheme is explained as follows:
1, in the such scheme, the control of described vitriol oil add-on is extremely important. and vitriol oil add-on is many more, and the HCl concentration that steams is big more, but influential to the crystallization that goes on foot copper sulfate down, promptly can reduce the growing amount of copper sulfate; Vitriol oil add-on is very few, then can influence the quality of copper sulfate. so the add-on of the vitriol oil will be according to what of content of copper ion in the used waste liquid, by reaction equation Cu
2++ H
2SO
4=CuSO
4+ 2H
+Calculate. owing to also contain a small amount of other metal in the waste liquid, also on theoretical calculated value, increase by 5～15%. so add the amount of the vitriol oil
2, in the such scheme, reclaiming the hydrochloric acid process, because the solution in the water distilling apparatus is steamed gradually, vitriol (mainly being copper sulfate) concentration increases gradually, easily cause the bumping of jumping. in order to prevent the liquid bumping of jumping in the distillation, can keep the slight boiling condition distillation to reclaim hydrochloric acid. simultaneously, also can utilize agitator set in the water distilling apparatus, hydrochloric acid is reclaimed in distillation on one side under slight boiling condition, stir on one side.
3, in the such scheme, when being dissolved in water copper sulfate, the add-on of water is controlled at and adds the 40～60% preferable of acidic etching waste liquid volume, be controlled at 50% for best. because the add-on of water is too many, it is just few to separate out crystal, solution needs reconcentration to increase the crystalline amount, and therefore operation steps has increased; The add-on of water is very few, and crystallisate is many, but crystalline form, color difference, if the cupric sulphate crystal quality obviously descends. copper sulfate is dissolving fully, also can help dissolving by heating.
4, in the such scheme, copper sulfate can add a small amount of copper sulfate crystal in order to improve crystallization velocity, with the accelerate crystallisation process in process of cooling when crystallization.
5, in the such scheme, in order further to economize on resources, mother liquor after filtering in the reclaim(ed) sulfuric acid copper and washing can be sent into the reuse of reclaim(ed) sulfuric acid copper step next time in reclaiming hydrochloric acid and copper sulfate. but mother liquor reuse number of times can not be many, reclaim 1～2 time, the available iron filings exchange column of mother liquor for the third time (this moment, the pH value just was the top condition of iron displacement copper), exchange back and forth with pump and to carry out replacement(metathesis)reaction, copper is cemented out, until qualified discharge, obtain the copper sponge (copper that cements out with iron) more than 95%. also can collect concentrated recrystallize (referring to remaining copper sulfate recrystallize in the mother liquor).
6, in the such scheme, the simplest method of reclaim(ed) sulfuric acid copper is: utilize the field to receive the remaining residual heat of looking into self behind the hydrochloric acid, add normal-temperature water and dissolve copper sulfate by stirring; Naturally cooling to room temperature then in air separates out cupric sulphate crystal.
7, the present invention reclaims principle and is:
(1), reclaims hydrochloric acid
Reaction formula: CuCl
2+ H
2SO
4=CuSO
4+
2HCl
In the acidic etching waste liquid that contains cupric chloride and hydrochloric acid, add sulfuric acid, sulfuric acid and cupric chloride reaction generate copper sulfate and hydrochloric acid, because the sulfuric acid boiling point than hydrochloric acid height, reclaims so can adopt distillation method that hydrochloric acid is steamed.
(2), reclaim(ed) sulfuric acid copper
Reaction formula: CuSO
4+ 5H
2O=CuSO
45H2O
Remaining residual looking into (mainly being copper sulfate) is dissolved in water after will reclaiming hydrochloric acid, utilize then copper sulfate under high temperature and low-temperature condition solubleness poor (copper sulfate solubleness is big during high temperature, solubleness is little during low temperature), make the dissolved cupric sulphate crystal become CuSO by cooling
45H
2O separates out.
Because the technique scheme utilization, the simplest distillation method of the present invention's employing reclaims hydrochloric acid and the copper sulfate in the etching waste liquor. this method processing unit is simple, and is easy and simple to handle, free from environmental pollution, and instant effect has wide practical value.
Economic and Efficiency Analysis of the present invention is as follows:
Suppose acidic etching liquid and ammonia etching solution mixed in certain proportion and produce copper sulfate. because the amount of acidic etching liquid is greatly more than the ammonia etching solution, so unnecessary acidic etching liquid will be with in 20% the ammoniacal liquor and back regeneration product copper sulfate.
Known: acidic etching liquid density: 1.247 * 10
3Kg/m
3
20.1% dilute hydrochloric acid density: 1.120 * 10
3Kg/m
3, market price is: 250 yuan/ton;
20% ammoniacal liquor market price is: 600 yuan/ton;
Rule of thumb value is produced 1 ton of copper sulfate, if having only acidic etching liquid, need consume 3.6 tons of acidic etching liquids so, also need consume 2.33 tons of 20% ammoniacal liquor, and the price that promptly need consume ammoniacal liquor is: 2.33 * 600=1398 (unit).
Adopt the inventive method, in the lab scale of laboratory, every 100ml etching solution distillation will obtain 90ml dilute hydrochloric acid at most, and the volume that promptly obtains dilute hydrochloric acid is for adding 90%. of etching solution volume
Acidic etching liquid is calculated as follows with the economic benefit that distillation method reclaims hydrochloric acid and copper sulfate acquisition:
Produce 1 ton of copper sulfate, need to use the etching solution volume: V=3.6 ÷ 1.247=2.887 (m
3)
Obtain hydrochloric acid volume: V (HCl)=2.887 * 90%=2.598 (m
3)
Hydrochloric acid quality: m (HCl)=2.598 * 1.120 * 10
3=2.910 (tons)
Economic benefit is: 2.910 * 250=727.5 (unit)
If dilute hydrochloric acid is distilled again, can obtain the concentrated hydrochloric acid of SILVER REAGENT, economic benefit is higher.
In sum, adopting distillation method to produce 1 ton of copper sulfate will increase economic benefit and be: 727.5+1398=2125.5 (unit) (promptly reclaiming the economic benefit of the economic benefit+saving ammoniacal liquor of hydrochloric acid).
Then economic benefit was by producing 15 tons of copper sulfate calculating in one day:
2125.5 * 15=31882.5 (unit)
The economic benefit that obtains was by calculating in 25 days in one month:
31882.5 * 25=797062.5 (unit)
Description of drawings
Accompanying drawing 1 is process flow sheet of the present invention.
Accompanying drawing 2 is the embodiment of the invention one a water distilling apparatus synoptic diagram.
In the above accompanying drawing, 1, adjustable electric furnace; 2, matrass; 3, condensation-water drain water; 4, receiving bottle; 5, distillate conduit.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: a kind of method (laboratory lab scale) that reclaims hydrochloric acid and copper sulfate from acidic etching liquid
One, main agents and instrument
1, the vitriol oil 98% AR level
2, the full glass distiller of 500ml (500ml matrass, the spiral condenser that 20cm is long)
3, the adjustable electric furnace of 600W or 800W
4,100ml graduated cylinder
5, WFX-130 atomic absorption spectrophotometer is used to measure foreign matter contents such as iron, lead, chlorion
6, water distilling apparatus is as shown in the figure:
Two, reclaimer operation
1, distillation. get the 100ml cupric and be 139g/L, hydrochloric be in about 10% the full glass matrass of acidic etching liquid impouring, add the 14ml vitriol oil again and several granulated glass spherees prevent the liquid bumping. by shown in Figure 2, install water distilling apparatus, beginning to add thermal distillation. the distillate volume is about 90ml, the standard caustic soda solution titration of gained hydrochloric acid, calculating concentration of hydrochloric acid is 21%.
2, dissolving crystallized. in matrass, add 50ml distilled water while hot, dissolve sulfur hydrochlorate (mainly being copper sulfate), again with in the solution impouring beaker, cooling, and (not adding copper sulfate crystal in theory also can separate out to add several copper sulfate crystals, but can improve crystallization velocity after adding), slowly allow cupric sulphate crystal.
3, bleed filtration, washing. with the crystalline sulfuric acid copper solutions impouring suction filtration in the B of bleeding, with the depleted copper sulfate solution washing for several times, drain, be placed on air drying and get finished product copper sulfate CuSO
45H
2O.
By analysis, the result is as follows:
| The mensuration project | CuSO 4·5H 2O | As | C1- | Pb | Fe |
| Analytical unit | ％ | mg/kg | mg/kg | mg/kg | mg/kg |
| Measuring method | Iodimetry,iodometry | The siliver diethyldithiocarbamate colorimetry | Silver nitrate turbidimetry method | Atomic absorption method | Atomic absorption method |
| Measurement result | 98.2 | 0.07 | 680 | Do not detect | Do not detect |
In order to understand the changing conditions of gained concentration of hydrochloric acid in the distillation, a certain amount of hydrochloric acid of our Fractional Collections and measure its concentration in the test, the result is as shown in the table:
| Number of times | Stepwise distillation volume (ml) | Concentration of hydrochloric acid (%) |
| The 1st time | 20 | 16.0 |
| The 2nd time | 20 | 19.2 |
| The 3rd time | 20 | 21.3 |
| The 4th | 20 | 24.0 |
| The 5th (the 4th adds 15ml distilled water continuation distillation after finishing) | 20 | 27.0 |
1. as can be seen from the above table, more to the distillation later stage, its concentration is high more for concentration of hydrochloric acid, and is equal difference and increases progressively trend.
2. liquor capacity is more little in the matrass, and concentration of hydrochloric acid is high more, and the amount that cupric chloride converts copper sulfate to is many more. and obtain adding 15ml water continuation distillation again after 80ml slips out liquid in order to reduce chloride ion content in the product, to be preferably in, drive chlorion as far as possible away.
Embodiment two: a kind of method (being applicable to suitability for industrialized production) that reclaims hydrochloric acid and copper sulfate from acidic etching liquid
One, still kettle
The still kettle of available enamelled or rigid polyvinyl chloride. pipeline can be used the graphite pipeline. and for easy to operate, still kettle can be inserted three pipelines, is respectively applied for logical steam, adds the vitriol oil and adding distil water.
Two, reclaim hydrochloric acid
Acid etching degree liquid is contained in the acid proof still kettle, adds the vitriol oil then, be heated to slight boiling condition, on one side the turn on agitator stirring, hydrochloric acid is reclaimed in distillation on one side.
The concentration of the vitriol oil is 98%, after adding the vitriol oil in the acidic etching waste liquid, the temperature of reactor reaches degree more than 40 in winter, can reach degree more than 60 summer. therefore, waste liquid has just seethed with excitement behind the hot a little 2min, begins to have distillate to flow out. and keep the about 15min of slight boiling condition distillation to finish. used vapour heating in the actually operating. solution is steamed gradually in reactor, and vitriol increases gradually, easily cause and jump, prevent the liquid bumping by stirring.
The add-on of the vitriol oil is based on content of copper ion in the water distilling apparatus and the required theoretical value of sulfuric acid complete reaction, and the add-on that increases by 15%. vitriol oils again is calculated as follows:
Known: the molecular weight of copper is 63.55, and the vitriolic molecular weight is 98
If: institute gets that copper content is x (g) in the etching solution, and the theoretical value of sulfuric acid quality is y (g), and the actual value of sulfuric acid quality is Y (g)
According to reaction formula: Cu
2++ H
2SO
4=CuSO
4+ 2H
+
Then need quality y (the g)=x/0.6355 (g) of 98% vitriol oil
After the vitriol oil added 15% again, actual vitriol oil Y (g)=x/0.6355 (1+15%) (g) for need
Actual volume V=m/ ρ=1.15 x/0.6355/1.83 (ml) that add the vitriol oil
Three, reclaim(ed) sulfuric acid copper
1, remaining residual looking into behind the receipts hydrochloric acid of field is dissolved in water, the copper sulfate in residual the looking into fully is dissolved in the solution, the add-on of water is controlled at and adds 30～70% of acidic etching waste liquid volume, and span of control is 40～60% preferably, and the best is 50%.
2, utilize high temperature by cooling cupric sulphate crystal to be separated out to cryogenic temperature variation, the temperature difference of temperature variation is controlled at 50 ± 10 ℃ of scopes. and the simplest way is a remaining residual heat of looking into self behind the utilization recovery hydrochloric acid, add normal-temperature water and dissolve copper sulfate by stirring, if vitriol is dissolving fully not, also can help dissolving by heating. in air, naturally cool to room temperature then cupric sulphate crystal is separated out.A small amount of copper sulfate crystal can be added in order to improve crystallization velocity in process of cooling, with the accelerate crystallisation process.
3, the cupric sulphate crystal body is carried out suction filtration and washing obtains copper sulfate. after the copper sulfate crystal filtering separation, the dilute solution washing (the copper sulfate dilute solution can be prepared with copper sulfate) of available copper sulfate, can reduce copper sulfate impurity and free acid. the mother liquor after filtering and washing can be sent into the reuse of reclaim(ed) sulfuric acid copper step next time in reclaiming hydrochloric acid and copper sulfate. but mother liquor reuse number of times can not be many, reclaim 1～2 time, the available iron filings exchange column of mother liquor for the third time (this moment, the pH value just was the top condition of iron displacement copper), exchange back and forth with pump and to carry out replacement(metathesis)reaction, copper is cemented out, until qualified discharge, obtain the copper sponge (copper that cements out with iron) more than 95%. also can collect concentrated recrystallize (referring to remaining copper sulfate recrystallize in the mother liquor).
The foregoing description only is explanation technical conceive of the present invention and characteristics; its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this; can not limit protection scope of the present invention with this. all equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (6)
1, a kind of method that reclaims hydrochloric acid and copper sulfate from acidic etching liquid is characterized in that comprising successively following steps:
(1), reclaims hydrochloric acid
Acidic etching waste liquid is contained in the acid proof water distilling apparatus, adds the vitriol oil then, be heated to the slight boiling condition distillation and reclaim hydrochloric acid; Wherein, the concentration of the vitriol oil is more than 98% or 98%; The add-on of the vitriol oil increases by 5～15% again based on content of copper ion in the water distilling apparatus and the required theoretical value of sulfuric acid complete reaction;
(2), reclaim(ed) sulfuric acid copper
1., remaining residue after reclaiming hydrochloric acid is dissolved in water, the copper sulfate in the residue is fully dissolved, the add-on of water be controlled at add acid etching degree liquid long-pending 40～60%;
2., utilize high temperature by cooling cupric sulphate crystal to be separated out to cryogenic temperature variation, the temperature difference of temperature variation is controlled at 50 ± 10 ℃ of scopes;
3., the cupric sulphate crystal body is filtered and washing obtains copper sulfate.
2, method according to claim 1 is characterized in that: be provided with agitator in the described water distilling apparatus, hydrochloric acid is reclaimed in distillation on one side under slight boiling condition, stir on one side.
3, method according to claim 1 is characterized in that: the add-on of water is controlled at and adds 50%. of acidic etching waste liquid volume
4, method according to claim 1 is characterized in that: in reclaim(ed) sulfuric acid copper step, when by cooling cupric sulphate crystal being separated out, add copper sulfate crystal.
5, method according to claim 1 is characterized in that: in reclaim(ed) sulfuric acid copper step, the mother liquor after filtering and washing is sent into the reuse of reclaim(ed) sulfuric acid copper step next time in reclaiming hydrochloric acid and copper sulfate.
6, method according to claim 1 is characterized in that: in reclaim(ed) sulfuric acid copper step, and the heat of remaining residue self behind the utilization recovery hydrochloric acid, adding normal-temperature water and road are crossed to stir and are dissolved copper sulfate; Naturally cooling to room temperature then in air separates out cupric sulphate crystal.
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|---|---|---|---|
| CNB2006100380805A CN100467671C (en) | 2006-01-24 | 2006-01-24 | Method for recovering hydrochloric acid and copper sulfate from acidic etching liquid |
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|---|---|---|---|
| CNB2006100380805A CN100467671C (en) | 2006-01-24 | 2006-01-24 | Method for recovering hydrochloric acid and copper sulfate from acidic etching liquid |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100385025C (en) * | 2006-09-07 | 2008-04-30 | 惠州市奥美特净水工程有限公司 | Method of coproducing modified polyiron from copper extracted PCB acid etching waste liquid |
| CN101125719B (en) * | 2007-07-13 | 2011-02-09 | 深圳市中冠环保科技有限公司 | Method for reclaiming hydrochloric acid and metal copper from printed circuit acidic etching waste liquid |
| CN101391800B (en) * | 2007-09-20 | 2011-06-15 | 深圳市东江环保股份有限公司 | Method for producing basic copper chloride, cupric sulfate pentahydrate from copper-containing etching waste liquid |
| 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 |
| CN104085911B (en) * | 2014-06-28 | 2015-09-23 | 南通久信石墨科技开发有限公司 | Copper etchant solution displacement generates the process unit of copper sulfate |
| CN107099802A (en) * | 2017-06-16 | 2017-08-29 | 深圳市新锐思环保科技有限公司 | A kind of novel acid etching solution resource recycling method and recycling system |
| CN113336259A (en) * | 2021-08-06 | 2021-09-03 | 清大国华环境集团股份有限公司 | Method for recycling acidic copper sulfate waste liquid |
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2006
- 2006-01-24 CN CNB2006100380805A patent/CN100467671C/en not_active Expired - Fee Related
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