CN102019430A - Method for recovering copper from alkaline etching waste liquid and recycling alkaline etching liquid - Google Patents
Method for recovering copper from alkaline etching waste liquid and recycling alkaline etching liquid Download PDFInfo
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- CN102019430A CN102019430A CN2009101125253A CN200910112525A CN102019430A CN 102019430 A CN102019430 A CN 102019430A CN 2009101125253 A CN2009101125253 A CN 2009101125253A CN 200910112525 A CN200910112525 A CN 200910112525A CN 102019430 A CN102019430 A CN 102019430A
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Abstract
The invention discloses a method for recovering copper from alkaline etching waste liquid and recycling the alkaline etching liquid, comprising the step of adding a hydrazine hydrate reducing agent and a catalyst into the alkaline etching waste liquid to recover copper powder, wherein the alkaline etching waste liquid can be recycled after the copper powder is recovered. The invention has the optimum conditions of: placing the alkaline etching waste liquid into a reactor; adding hydrazine hydrate with mass percent concentration of 40 percent according to added quantity of 160-200mL/L; adding a solution of various salts of ruthenium, palladium, nickel and cobalt as the catalyst with added quantity of 0.01-0.2g/L (metered by the masses of the ruthenium, the palladium, the nickel and the cobalt), reacting for 30-35 minutes at temperature between 70DEG C and 100DEG C; and separating to obtain the copper powder. The invention has the beneficial effect that after the copper is recovered from the alkaline etching waste liquid, the alkaline etching waste liquid can be regenerated and recycled, therefore, various resources in the alkaline etching waste liquid can be used fully, and the etching cost of a printing plate and the discharge of pollutants can be reduced.
Description
Technical field:
The present invention relates to the recovery method that a kind of alkaline etching waste liquid for producing reclaims copper and alkaline etching liquid.
Background technology:
Contain cupric ammine complex, ammonium chloride and ammoniacal liquor in the alkaline etching waste liquid for producing, wherein copper content can reach 120-170g/L.If directly discharging can bring serious harm to environment.In PCB Production, need carry out circular regeneration to etching waste liquor, reach and make full use of resource, reduce cost, reduce pollutant emission.Etching waste liquor processing method commonly used at present mainly is neutralization (chemistry) precipitation method, flocculent precipitation, electrolysis etc.; It is simple that neutralization precipitation method and flocculent precipitation are handled alkaline etching waste liquid for producing technology, small investment, but can not be recycling to inorganic matter such as the ammonium salt in the waste liquid and organic matter; Electrolysis is handled the alkaline etching waste liquid for producing complex process, and investment is big.
Be that with the advantage of hydration hydrazine reductant the product of hydrazine hydrate after oxidized is the nitrogen G﹠W, do not bring other impurity.When generally reclaiming in the alkaline etching waste liquid for producing copper with hydrazine hydrate reduction, copper content is more than 100g/L in the alkaline etching waste liquid for producing after treatment, and efficient is low.
Summary of the invention:
The object of the invention provides the recovery method that a kind of alkaline etching waste liquid for producing reclaims copper and alkaline etching liquid, and its technology simple and stable, small investment, income height do not produce new pollutant in the processing procedure.Can when reclaiming copper, make alkaline etching waste liquid for producing obtain to recycle, can be back to the preparation alkaline etching liquid again, use as the PCB Production etching.
The present invention is implemented by the following technical programs: described a kind of alkaline etching waste liquid for producing reclaims the recovery method of copper and alkaline etching liquid, and its concrete steps are:
1) alkaline etching waste liquid for producing places reactor, is heated to 50～100 ℃, adds hydrazine hydrate, the solution of various salts that adds metal Ru, palladium, nickel, cobalt again is as catalyst, between 50～100 ℃ of the control reaction temperatures, the reaction time is 20～40 minutes, separates to obtain precipitation copper powder and filtrate.
2) above-mentioned steps 1) every liter of alkaline etching waste liquid for producing in, the addition of the solution of the two or more mixing in the various salts of a kind of solution in the various salts of metal Ru, palladium, nickel, cobalt or metal Ru, palladium, nickel, cobalt is 0.0001g/L～2g/L (in Metal Palladium, ruthenium, nickel, a cobalt quality), as: add palladium salt then the amount of palladium salt be quality in Metal Palladium.Optimal addn is 0.001g/L～0.2g/L (in Metal Palladium, ruthenium, nickel, a cobalt quality); In every liter of alkaline etching waste liquid for producing, its mass percent concentration of the hydrazine hydrate that is added is 30-80%, and addition is 73～256mL, and best hydrazine hydrate mass percent concentration is 40%, and optimal addn is 160～200mL; Range of reaction temperature is: 50～100 ℃, optimal reaction temperature is: 70～100 ℃; Reaction time is 20～40 minutes, and optimum reacting time is: 30～35 minutes.
Described catalyst is when adopting complex salt solution, described complex salt solution is selected from a kind of in the solution combined salting liquid of the solution of the solution of the solution of the solution of the solution of the solution of the solution of palladium salt and nickel salt or palladium salt and cobalt salt or ruthenium salt and nickel salt or ruthenium salt and cobalt salt, the ratio of two kinds of salt in the described complex salt solution corresponding with two kinds of salt the qualimetric ratio of corresponding two kinds of metals be 1: 1～1: 200, preferred 1: 10～1: 100.As: when complex salt solution is the solution of the solution of palladium salt and nickel salt when mixing, the ratio of its palladium salt and nickel salt is that the ratio in the quality of palladium, nickel is 1: 1～1: 200, and other is also in like manner.When adopting complex salt solution, mixing of the solution of the solution of preferred palladium salt of the present invention or ruthenium salt and the solution of nickel salt or cobalt salt, its effect is to improve the output of copper powder, also can reduce the catalyst cost, as long as because add the solution of a spot of palladium salt or ruthenium salt and the nickel salt of volume or cobalt salt solution mix the catalyst that is constituted, promptly can save energy the catalyst cost, can reach catalytic effect preferably again.
3) after reaction finishes, separate and obtain precipitation copper powder and filtrate, described precipitation copper powder can wash with ammonium chloride solution, the present invention adopts the ammonium chloride solution washing, the concentration of the ammonium chloride that adds suits and addition needs only an amount of, general concentration is 150 grams per liters～250 grams per liters, its objective is that the washing precipitation copper powder makes wherein stannous chloride sediment and chlorion form cuprous chloride complexation thing solution, removed the stannous chloride sediment, if (not removing the stannous chloride sediment can make precipitation copper powder variable color and purity not high, can influence the quality that reclaims copper), obtain purer precipitation copper powder and cleaning solution, the merging of the cleaning solution of acquisition and above-mentioned filtrate obtain filtrate A.Described filtrate can be back to the new etching solution of preparation, and mode is that filtrate A is prepared new etching solution as reuse preferably certainly, reaches the purpose of the abundant recovery of alkaline etching waste liquid for producing like this.
4) the purer precipitation copper powder of step 3) acquisition washs respectively with dilute sulfuric acid and water again, and drying obtains copper powder, obtains waste liquid B simultaneously.
5) the filtrate A that step 3) obtained add hydrogen peroxide or be placed in the air to oxidation-reduction potential be 220 ± 20mv (with respect to the silver-silver chloride reference electrode), regulating the pH value with ammoniacal liquor is 8.5～9, obtain alkaline etching liquid, is adjustment 40～55 ℃, just can by an injection apparatus with this liquid facing to copper thick be that the copper-clad plate of 18 μ m sprays, after 1～3 minute, the Copper Foil that is sprayed the position is all etched, proves that alkaline etching liquid can be recycled.
6) waste liquid B being delivered to waste water processing station handles.
The screening of catalyst system therefor of the present invention:
From present document as can be known, the reducing agent that can make copper ion be reduced to copper powder has many kinds, as: formaldehyde, ascorbic acid, dithionous acid salt, hypophosphite, hydrazine hydrate, boron hydride and metallic iron, magnesium, aluminium etc.Because after alkaline etching waste liquid for producing reclaimed copper powder, filtrate also will be reclaimed, and is mixed with alkaline etching liquid again, just do not wish in the chemical reaction of alkaline etching waste liquid for producing recovery copper powder, to introduce impurity, alkaline etching liquid is exerted an influence.Hydrazine hydrate in alkaline solution, is oxidized to the nitrogen G﹠W as reducing agent, does not bring impurity into, and is highly beneficial to the alkaline etching waste liquid for producing regeneration.
Copper is with Cu (NH in alkaline etching waste liquid for producing
3)
4 2+Form exists, and the reaction that hydrazine hydrate and its reaction generate copper powder is that substep carries out.Cu (NH at first
3)
4 2+By hydrazine hydrate reduction is Cu (NH
3)
2 +:
Cu (NH then
3)
2 +Further be reduced to copper:
Hydrazine hydrate can also same Cu simultaneously
+Generate Cu (N
2H
4)
Y +Complex compound, Cu (N
2H
4)
Y +Complex compound is generating copper with the hydrazine hydrate reaction:
Because Cu (NH
3)
2 +And Cu (N
2H
4)
y +By hydrazine hydrate reduction is that the reaction speed of copper is very slow, and Cu (NH
3)
2 +Easily be oxidized to Cu (NH
3)
4 2+, need to seek catalyst for this reason and promote Cu (NH
3)
2 +And Cu (N
2H
4)
y +By hydrazine hydrate reduction is the chemical reaction of copper, reaches the consumption that reduces hydrazine hydrate, improves the yield of copper, thereby reduces cost.
Catalyst can induce chemical reaction to change, and chemical reaction is accelerated or slows down or carry out chemical reaction under lower temperature environment.Catalyst divides homogeneous catalyst and heterogeneous catalysis.Heterogeneous catalysis is presented on (for example: solid catalyst is in liquid hybrid reaction) in the out of phase reaction, and homogeneous catalyst then is the reaction (for example: liquid catalyst is in liquid hybrid reaction) that is presented on same phase.Catalyst has the selectivity (or selectivity) of height, a kind of catalyst is not that all chemical reactions are all had catalytic action, for example silver nitrate is catalytic action in the potassium permanganate at ammonium persulfate oxidation bivalent manganese, and other chemical reaction is just not necessarily had catalytic action.Some chemical reaction is not only in distress one catalyst, for example can play magnesia, iron oxide and cupric oxide or the like in addition of catalytic action in the potassium chlorate decomposes.Metallic element with catalytic action is the transition metal in the periodic table of elements mainly.The metallic element of catalyst all loads on the porous carrier usually, can load on as platinum, palladium etc. on the porous carriers such as molecular sieve, active carbon, aluminium oxide, if will load on palladium on the porous carrier as the catalyst of hydrazine hydrate reduction copper in the alkaline etching waste liquid for producing, then the copper of reduction generation can stop up hole, and catalyst is lost activity.As directly making then palladium surface coverage last layer copper of catalyst, make Metal Palladium lose catalytic activity equally with Metal Palladium.And catalyst and copper powder can mix, and the purity and the catalyst that then reduce copper powder are non-renewable, increase cost greatly, thereby simple metal is not very practical scheme as catalyst for purposes of the invention.In sum, key point of the present invention or creation point are exactly to seek some practical catalyst, and these catalyst can not only separate easily with the product copper that generates, and this catalyst can not exert an influence as alkaline etching liquid to the filtrate of having separated copper yet, and the filtrate of having separated copper is not needed to carry out comparatively complicated postprocessing working procedures, the thinking of screening catalyst below for the inventor again.
1) fewer for the catalyst of the metallic element of the oxidation reaction of hydrazine hydrate, platinum, palladium, ruthenium, iron, cobalt, nickel etc. have the self-catalysis activity, catalytically inactives such as metallic copper, silver, gold, tungsten, molybdenum, chromium, zinc, manganese, but the metallic element that has also has negative catalyst, as tin, the oxidation reaction of hydrazine hydrate is slowed down.
2) want to separate easily with the product copper that generates, this catalyst is the salt of solubility preferably, so emphasis of the present invention is to seek the soluble-salt that can make catalyst, Metal Palladium, ruthenium, cobalt, metallic salts such as nickel are the catalyst that the present invention filters out, prove Metal Palladium from following embodiment, ruthenium, cobalt, metallic salts such as nickel have catalytic action, these palladiums, ruthenium, cobalt, metallic salt catalyst such as nickel generate complex with the ammonia in the alkaline etching waste liquid for producing, reaction finishes the back palladium, ruthenium, cobalt, metallic salts such as nickel exist among the filtrate A with the complex form of ammonia, the effect (can use again when promptly add hydrazine hydrate reduction copper next time) that can have repetition catalysis, this catalytic action only has catalytic action to hydrazine hydrate reduction copper, have selectivity, and be present in the palladium among the filtrate A, ruthenium, cobalt, nickel ion does not exert an influence to the etching action of alkaline etching liquid.
3) the present invention also tests as the catalytic action of hydrazine hydrate reduction copper platinum salt and molysite and sees embodiment 40～65, platinum salt and molysite also have catalytic action as can be known from embodiment, but result of the test illustrates the excellent catalytic effect of the catalytic effect of metal Ru, palladium, cobalt, nickel salt than chloroplatinic acid, frerrous chloride, can significantly cut down the consumption of energy, cost.Because the price of chloroplatinic acid doubles above than palladium salt and ruthenium salt price; Adopt palladium salt and ruthenium salt to reduce cost.Though the frerrous chloride price is low, but when frerrous chloride is catalyst, rust can appear in the copper powder that obtains, copper powder purity is lower, its reason is because frerrous chloride can produce gluey ferrous hydroxide precipitation in alkaline solution, and easy oxidized jellied ferric hydroxide precipitate, be difficult for being washed, contain gluey impurity such as ferric hydroxide precipitate among the filtrate A, etching action to alkaline etching liquid exerts an influence, as: the nozzle of alkaline etching machine is easily stopped up by colloidal iron hydroxide, causes the printed board etching inhomogeneous, effect is bad, easily produces waste product.
4) the present invention also to two kinds of complex salt solution or two or more complex salt solution as screening of catalyst, the present invention is after the test of having made one-component salting liquid catalyst, find that two or more combination of salting liquid with catalysis also has catalytic action, see embodiment 13-14 for details, embodiment 21-28, the test of embodiment 29-33, from the above embodiments test, also can find out the use cost that can reduce catalyst in large quantities, and catalytic effect does not weaken, as everyone knows, metal Ru, its excellent catalytic effect of the salt of palladium, but it costs an arm and a leg, relatively large use no doubt can be recovered to copper from alkaline etching waste liquid for producing, but not very good from economy, thereby the salt that can use single as an alternative metal Ru of complex salt solution or palladium is as catalyst, be another characteristics of the present invention, the present invention selects metal Ru salt or palladium salt and price lower nickel salt or cobalt salt and mixes, by this thinking of evidence is feasible, and can mix with relatively large nickel salt or cobalt salt with a spot of ruthenium salt or palladium salt, if carry out the mixed catalytic effect too with a large amount of ruthenium salt or palladium salt with more a spot of nickel salt or cobalt salt certainly, this tests verified feasible, but do not reach the purpose that reduces the catalyst cost, innovative point of the present invention is that proposition is a kind of more practical, price is lower and can reach the complex salt solution catalyst of equal effect again, reach the utilization rate that has improved hydrazine hydrate, make under the equal conditions (filtrate A copper content reaches the following and copper powder purity of 60g/L and all is higher than 99%) hydrazine hydrate consumption obviously reduce, and improve reaction speed.Following experiment has proved that all the ratio of the limit of ruthenium salt in the complex salt solution of the present invention or palladium salt and nickel salt or cobalt salt is 1: 200, promptly in the complex salt solution as long as a ruthenium salt or palladium salt mix the catalytic effect that can reach 201 portions of simple ruthenium salt or palladium salt with 200 parts nickel salt or cobalt salt.
The present invention has following advantage: 1, a kind of solution in the various salts of employing metal Ru, palladium, nickel, cobalt is as catalyst, or adopt solution that two or more the mixing in the various salts of metal Ru, palladium, nickel, cobalt obtains as catalyst, reach the utilization rate that has improved hydrazine hydrate.2, adopt hydrazine hydrate as reducing agent, reacted product is the nitrogen G﹠W, do not bring other impurity into, filtrate behind the filtering-depositing copper can be back to the new etching solution of preparation, its etch effect is good as can be known in experiment, make full use of the various resources in the alkaline etching waste liquid for producing, reached the effect of zero-emission, realized cleaner production.3, the precipitation copper powder purity that obtains all is higher than 99%, can be used for preparing stannous chloride etc.4, the present invention adopts hydrazine hydrate and ruthenium, palladium, nickel, the catalyst of one of salting liquid of cobalt or two or more cooperations carries out alkaline etching waste liquid for producing and reclaims copper and reclaim the alkaline etching liquid test, by experimental result as can be known its reaction speed obviously to reclaim the reaction speed of copper fast than merely carrying out alkaline etching waste liquid for producing with hydrazine hydrate, and under the same conditions, with above-mentioned catalyst than above-mentioned catalyst useless, its output that reclaims copper powder obviously improves, copper content obviously reduces among the filtrate A, reach the hydrazine hydrate of same amount, producing the copper rate improves, promptly produce same copper, the hydrazine hydrate consumption is less, and the cost of hydrazine hydrate is very high, and available complex salt makees catalyst, has reduced rare ruthenium salt or palladium salt use amount, save scarce resource, thereby improved actual application value of the present invention.5, behind the copper in reclaiming alkaline etching waste liquid for producing, alkaline etching waste liquid for producing is renewable recycling, reaches the various resources that make full use of in the alkaline etching waste liquid for producing, reduces the etching cost of printed board, reduces the discharging of pollutant.
The specific embodiment:
The present invention is described in detail below in conjunction with embodiment:
The used alkaline etching liquid of following embodiment is provided by Fujian Fuqiang Accurate PCB Co., Ltd..
Embodiment 1:
1,1 liter of alkaline etching liquid waste liquid is placed reaction vessel, be heated to 100 ℃, drip 175 milliliters of 40% hydrazine hydrates, add 1.0 milliliters and include the palladium chloride solution that Metal Palladium is 1mg/mL, keep 100 ℃ of reaction temperatures, the reaction time is 35 minutes.
2, reaction finishes back filtration fast, obtains precipitation and filtrate.This is precipitated as the copper powder precipitation, and purity is 99.2%, and the filtrate copper content that obtains is that 40g/L, pH are 8.5, and filtrate can be back to the new etching solution of preparation.
Embodiment 1-1:
1,1 liter of alkaline etching liquid waste liquid is placed reaction vessel, be heated to 100 ℃, drip 175 milliliters of 40% hydrazine hydrates, add 1.0 milliliters and include the palladium chloride solution that Metal Palladium is 1mg/mL, keep 100 ℃ of reaction temperatures, the reaction time is 35 minutes.
2, reaction finishes back filtration fast, obtains precipitation and filtrate.To precipitate with a small amount of 200g/L ammonium chloride solution washed twice and obtain copper powder precipitation and cleaning solution, merging filtrate and cleaning solution obtain filtrate A.
3, copper powder precipitation uses 2% dilute sulfuric acid and water washing clean again, in 105 ℃ of dryings, obtains the 115g copper powder, obtains liquor B simultaneously.Hydrazine hydrate consumption (in every gram copper powder) is: 1.52ml/g
4, the filtrate A copper content that obtains is that 40g/L, pH are 8.0, oxidation-reduction potential is-240mv (with respect to the silver-silver chloride reference electrode), filtrate A added 30% hydrogen peroxide or be placed in the air to oxidation-reduction potential be 220mv, regulating the pH value with ammoniacal liquor is 9, adjustment is 40～55 ℃, by an injection apparatus with this solution facing to copper thick be that the copper-clad plate of 18 μ m sprays, 2.5 after minute, Copper Foil by the spray position is all etched, proves that alkaline etching liquid can be recycled.
Embodiment 2:
1,1 liter of alkaline etching liquid waste liquid is placed reaction vessel, be heated to 100 ℃, drip 175 milliliters of 40% hydrazine hydrates, add 10.0 milliliters and include the palladium chloride solution that Metal Palladium is 1mg/mL, keep 100 ℃ of reaction temperatures, the reaction time is 35 minutes.
2, reaction finishes back filtration fast, obtains precipitation and filtrate.To precipitate with a small amount of 200g/L ammonium chloride solution washed twice and obtain copper powder precipitation and cleaning solution, merging filtrate and cleaning solution obtain filtrate A.
3, copper powder precipitation uses 2% dilute sulfuric acid and water washing clean again, in 105 ℃ of dryings, obtains the 118g copper powder, obtains liquor B simultaneously.Hydrazine hydrate consumption (in every gram copper powder) is: 1.48ml/g.
4, the filtrate A copper content that obtains is that 39g/L, pH are 8.0, oxidation-reduction potential is-235mv (with respect to the silver-silver chloride reference electrode), filtrate A added 27.5% hydrogen peroxide or be placed in the air to oxidation-reduction potential be 220mv, regulating the pH value with ammoniacal liquor is 8.5～9, adjustment is 40～55 ℃, by an injection apparatus with this solution facing to copper thick be that the copper-clad plate of 18 μ m sprays, 2.5 after minute, Copper Foil by the spray position is all etched, proves that alkaline etching liquid can be recycled.
Embodiment 3:
1,1 liter of alkaline etching liquid waste liquid is placed reaction vessel, be heated to 100 ℃, drip 175 milliliters of 40% hydrazine hydrates, add 30.0 milliliters and include the palladium chloride solution that Metal Palladium is 1mg/mL, keep 100 ℃ of reaction temperatures, the reaction time is 35 minutes.
2, reaction finishes back filtration fast, obtains precipitation and filtrate.To precipitate with a small amount of 200g/L ammonium chloride solution washed twice and obtain copper powder precipitation and cleaning solution, merging filtrate and cleaning solution obtain filtrate A.
3, copper powder precipitation uses 2% dilute sulfuric acid and water washing clean again, in 105 ℃ of dryings, obtains the 116g copper powder, obtains liquor B simultaneously.Hydrazine hydrate consumes (in every gram copper powder): 1.51ml/g.
4, the filtrate A copper content that obtains is that 38g/L, pH are 8.0, oxidation-reduction potential is-235mv (with respect to the silver-silver chloride reference electrode), filtrate A added 27.5% hydrogen peroxide or be placed in the air to oxidation-reduction potential be 220mv, regulating the pH value with ammoniacal liquor is 8.5, adjustment is 40～55 ℃, by an injection apparatus with this solution facing to copper thick be that the copper-clad plate of 18 μ m sprays, 2.5 after minute, Copper Foil by the spray position is all etched, proves that alkaline etching liquid can be recycled.
Embodiment 4:
1,1 liter of alkaline etching liquid waste liquid is placed reaction vessel, be heated to 100 ℃, drip 175 milliliters of 40% hydrazine hydrates, add 1.0 milliliters and include the ruthenic chloride solution that metal Ru is 1mg/mL, keep 100 ℃ of reaction temperatures, the reaction time is 35 minutes.
2, reaction finishes back filtration fast, obtains precipitation and filtrate.To precipitate with a small amount of 200g/L ammonium chloride solution washed twice and obtain copper powder precipitation and cleaning solution, merging filtrate and cleaning solution obtain filtrate A.
3, copper powder precipitation uses 2% dilute sulfuric acid and water washing clean again, in 105 ℃ of dryings, obtains the 113g copper powder, obtains liquor B simultaneously.Hydrazine hydrate consumption (in every gram copper powder) is: 1.55ml/g.
4, the filtrate A copper content that obtains is that 44g/L, pH are 8.0, oxidation-reduction potential is-240mv (with respect to the silver-silver chloride reference electrode), filtrate A added 27.5% hydrogen peroxide or be placed in the air to oxidation-reduction potential be 220mv, regulating the pH value with ammoniacal liquor is 8.8, adjustment is 40～55 ℃, by an injection apparatus with this solution facing to copper thick be that the copper-clad plate of 18 μ m sprays, 2.5 after minute, Copper Foil by the spray position is all etched, proves that alkaline etching liquid can be recycled.
Embodiment 5:
1,1 liter of alkaline etching liquid waste liquid is placed reaction vessel, be heated to 100 ℃, drip 175 milliliters of 40% hydrazine hydrates, add 10.0 milliliters and include the ruthenic chloride solution that metal Ru is 1mg/mL, keep 100 ℃ of reaction temperatures, the reaction time is 35 minutes.
2, reaction finishes back filtration fast, obtains precipitation and filtrate.To precipitate with a small amount of 200g/L ammonium chloride solution washed twice and obtain copper powder precipitation and cleaning solution, merging filtrate and cleaning solution obtain filtrate A.
3, copper powder precipitation uses 2% dilute sulfuric acid and water washing clean again, in 105 ℃ of dryings, obtains the 115g copper powder, obtains liquor B simultaneously.Hydrazine hydrate consumption (in every gram copper powder) is: 1.52ml/g.
4, the filtrate A copper content that obtains is that 42g/L, pH are 8.0, oxidation-reduction potential is-235mv (with respect to the silver-silver chloride reference electrode), filtrate A added 27.5% hydrogen peroxide or be placed in the air to oxidation-reduction potential be 220mv, regulating the pH value with ammoniacal liquor is 8.5～9, adjustment is 40～55 ℃, by an injection apparatus with this solution facing to copper thick be that the copper-clad plate of 18 μ m sprays, 2.5 after minute, Copper Foil by the spray position is all etched, proves that alkaline etching liquid can be recycled.
Embodiment 6:
1,1 liter of alkaline etching liquid waste liquid is placed reaction vessel, be heated to 100 ℃, drip 175 milliliters of 40% hydrazine hydrates, add 30.0 milliliters and include the ruthenic chloride solution that metal Ru is 1mg/mL, keep 100 ℃ of reaction temperatures, the reaction time is 35 minutes.
2, reaction finishes back filtration fast, obtains precipitation and filtrate.To precipitate with a small amount of 200g/L ammonium chloride solution washed twice and obtain copper powder precipitation and cleaning solution, merging filtrate and cleaning solution obtain filtrate A.
3, copper powder precipitation uses 2% dilute sulfuric acid and water washing clean again, in 105 ℃ of dryings, obtains the 117g copper powder, obtains liquor B simultaneously.Hydrazine hydrate consumption (in every gram copper powder) is: 1.50ml/g.
4, the filtrate A copper content that obtains is that 40g/L, pH are 8.0, oxidation-reduction potential is-235mv (with respect to the silver-silver chloride reference electrode), filtrate A added 27.5% hydrogen peroxide or be placed in the air to oxidation-reduction potential be 220mv, regulating the pH value with ammoniacal liquor is 8.5～9, adjustment is 40～55 ℃, by an injection apparatus with this solution facing to copper thick be that the copper-clad plate of 18 μ m sprays, 2.5 after minute, Copper Foil by the spray position is all etched, proves that alkaline etching liquid can be recycled.
Embodiment 7～12:
Method by embodiment 1-1 is implemented, and the condition of pressing in the table 1 is implemented.The effect of embodiment 7～12 sees Table 2.
Table 1
Table 2
Embodiment 13～14:
Method by embodiment 1-1 is implemented, and the condition of pressing in the table 3 is implemented.The effect of embodiment 13～14 sees Table 4.
Table 3
Table 4
Embodiment 15～20:
Method by embodiment 1-1 is implemented, and the condition of pressing in the table 5 is implemented.The effect of embodiment 15～20 sees Table 6.
Table 5
Table 6
Embodiment 21～28:
Method by embodiment 1-1 is implemented, and the condition of pressing in the table 7 is implemented.The effect of embodiment 31～38 sees Table 8.
Table 9
Table 10
Embodiment 29～33:
Method by embodiment 1-1 is implemented, and the condition of pressing in the table 9 is implemented.The effect of embodiment 29～33 sees Table 10.
Table 9
Table 10
Embodiment 34～39:
Method by embodiment 1-1 is implemented, and the condition of pressing in the table 11 is implemented, and does not promptly add catalyst in implementation process.The effect of embodiment 34～39 sees Table 12.
Table 11
Table 12
Embodiment 40～65:
Method by embodiment 1-1 is implemented, and the condition of pressing in the table 13 is implemented, and promptly adds chloroplatinic acid, frerrous chloride catalyst in implementation process.The effect of embodiment 40～65 sees Table 14.
Table 13:
Table 14:
By above embodiment 1～39 as can be known, the present invention adopts hydrazine hydrate and ruthenium, palladium, nickel, the catalyst of one of salting liquid of cobalt or two or more complex salt carries out alkaline etching waste liquid for producing and reclaims copper and reclaim the alkaline etching liquid test, by experimental result as can be known its reaction speed obviously to reclaim the reaction speed of copper fast than merely carrying out alkaline etching waste liquid for producing with hydrazine hydrate, and under identical hydrazine hydrate reduction agent condition, with above-mentioned catalyst than above-mentioned catalyst useless, its output that reclaims copper powder obviously improves, copper content obviously reduces among the filtrate A, reach the copper powder of being measured equally, the minimizing of hydrazine hydrate consumption.And the alkaline etching liquid that obtains that reclaims, its circulation etching result of use is good.
Contrasted under the condition in same reaction temperature, reaction time with embodiment 40～65 by embodiment 1～33, embodiment 1～33 has descended 5～10% than embodiment 40～65 hydrazine hydrate consumptions (in every gram copper powder).Add under the catalyst same, embodiment 1～33 than 40～65 reaction time of embodiment reduce 5 minutes, reaction temperature descends 10 ℃, the excellent catalytic effect of the catalytic effect of metal Ru, palladium, cobalt, nickel salt than chloroplatinic acid, frerrous chloride is described, can significantly cuts down the consumption of energy, cost.Because the price of chloroplatinic acid doubles above than palladium salt and ruthenium salt price; Adopt palladium salt and ruthenium salt to reduce cost.Though the frerrous chloride price is low, when frerrous chloride was catalyst, rust can appear in the copper powder that obtains, copper powder purity is lower, be owing to frerrous chloride can produce gluey ferrous hydroxide precipitation in alkaline solution, and easy oxidized jellied ferric hydroxide precipitate, be difficult for being washed, contain impurity such as iron among the filtrate A, the nozzle of alkaline etching machine is easily stopped up by iron hydroxide, causes when the printed board etching, and etching is inhomogeneous, etch effect is bad, easily produces waste product.
Claims (8)
1. an alkaline etching waste liquid for producing reclaims the recovery method of copper and alkaline etching liquid, it is characterized in that: in alkaline etching waste liquid for producing, add the hydrazine hydrate reduction agent, add catalyst again, in reaction temperature is under 50～100 ℃, reacted 20～40 minutes, and separated obtaining precipitation copper powder and filtrate, have a kind of solution that is selected from palladium salt, ruthenium salt, nickel salt, cobalt salt in the described catalyst at least.
2. reclaim the recovery method of copper and alkaline etching liquid according to the described a kind of alkaline etching waste liquid for producing of claim 1, it is characterized in that: in every liter of alkaline etching waste liquid for producing, its mass percent concentration of the hydrazine hydrate that is added is 30-80%, and addition is 73～256mL.
3. according to the recovery method of claim 1 or 2 described a kind of alkaline etching waste liquid for producing recovery copper and alkaline etching liquid, it is characterized in that: the addition of described catalyst is palladium salt or ruthenium salt or nickel salt or the cobalt salt that correspondingly contains 0.001～2 gram in every liter of alkaline etching waste liquid for producing in the quality of palladium or ruthenium or nickel or cobalt.
4. reclaim the recovery method of copper and alkaline etching liquid according to the described a kind of alkaline etching waste liquid for producing of claim 3, it is characterized in that: described catalyst adopts complex salt solution, described complex salt solution is selected from a kind of in the formed complex salt solution of solution of the solution of the solution of the solution of the solution of the solution of the solution of the solution of palladium salt and nickel salt or palladium salt and cobalt salt or ruthenium salt and nickel salt or ruthenium salt and cobalt salt, the ratio of two kinds of salt in the described complex salt solution corresponding with two kinds of salt the qualimetric ratio of corresponding two kinds of metals be 1: 1～1: 100.
5. reclaim the recovery method of copper and alkaline etching liquid according to the described a kind of alkaline etching waste liquid for producing of claim 4, it is characterized in that: the precipitation copper powder that described separation obtains washs with ammonium chloride solution, obtain purer precipitation copper powder and cleaning solution, the cleaning solution of acquisition obtains filtrate A with the filtrate that is obtained merging; The purer precipitation copper powder of above-mentioned acquisition washs respectively with dilute sulfuric acid and water again, and drying obtains copper powder.
6. reclaim the recovery method of copper and alkaline etching liquid according to the described a kind of alkaline etching waste liquid for producing of claim 5, it is characterized in that: the filtrate A that obtains is added hydrogen peroxide or be placed in the air to the oxidation-reduction potential with respect to the silver-silver chloride reference electrode be 220 ± 20mv, regulating the pH value with ammoniacal liquor is 8.5～9, obtains alkaline etching liquid.
7. reclaim the recovery method of copper and alkaline etching liquid according to the described a kind of alkaline etching waste liquid for producing of claim 4, it is characterized in that: the complex salt solution that mixes formation of the solution that described catalyst adopts palladium salt or ruthenium salt and the solution of the solution of nickel salt or cobalt salt.
8. reclaim the recovery method of copper and alkaline etching liquid according to the described a kind of alkaline etching waste liquid for producing of claim 7, it is characterized in that: the solution of the solution of palladium salt or ruthenium salt and the solution of nickel salt or cobalt salt mixes by 1: 10～100 proportioning with the mass metrology of metal.
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| CN102560500A (en) * | 2012-02-03 | 2012-07-11 | 昆山市洁驰环保科技发展有限公司 | Method for producing nanometer copper powder by use of waste alkaline etching solution which can be regenerated and apparatus thereof |
| CN103397341A (en) * | 2013-07-29 | 2013-11-20 | 陈飙 | Method for recycling copper from basic waste etching liquid |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3324450A1 (en) * | 1983-07-07 | 1985-01-17 | ELO-CHEM Ätztechnik GmbH, 7758 Meersburg | AMMONIUM SULFATE-CONTAINING ETCH SOLUTION AND METHOD FOR REGENERATING THE ETCH SOLUTION |
| KR19980040479A (en) * | 1996-11-29 | 1998-08-17 | 안덕기 | Copper waste treatment method |
| DE102004030924A1 (en) * | 2004-06-25 | 2006-01-19 | Elo-Chem-Csm Gmbh | Electrolytically regenerable etching solution |
| DE102006036888A1 (en) * | 2005-11-10 | 2007-05-16 | Eve Recycling Sarl | Regenerable etching solution |
-
2009
- 2009-09-18 CN CN200910112525A patent/CN102019430B/en not_active Expired - Fee Related
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