CN101209874A - Technique for processing and recovering disuse acidic copper etchant by metal aluminum - Google Patents
Technique for processing and recovering disuse acidic copper etchant by metal aluminum Download PDFInfo
- Publication number
- CN101209874A CN101209874A CNA2006101565974A CN200610156597A CN101209874A CN 101209874 A CN101209874 A CN 101209874A CN A2006101565974 A CNA2006101565974 A CN A2006101565974A CN 200610156597 A CN200610156597 A CN 200610156597A CN 101209874 A CN101209874 A CN 101209874A
- Authority
- CN
- China
- Prior art keywords
- technology
- aluminium
- handled
- copper etchant
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a technology for treating and recycling waste acid copper etchant with metal aluminum. The technology first controls variables such as temperature, copper concentration of waste acid copper etchant, etc. and then adopts one or more treating spouts filled with the metal aluminum to treat the copper etchant, and then copper is separated out as metal. The technology can be used in batch or continuous mode, the treating spouts applied are connected in series or in parallel or in series-parallel and heating or cooling is carried out to control the required temperature. The inside of the treating spouts can be optionally provided with an embedded separation mechanism so as to keep solid reaction product. The treated acid etchant contains dissolved aluminum salt and can be used as chemical product or raw material for waste treatment.
Description
Technical field
The present invention is about a kind of technology that reclaims copper etchant, more particularly, makes discarded acidic copper etchant separate out the treatment process of copper about a kind of metallic aluminium that utilizes, and utilizes this technology can not increase not wish the solubility or the insolubility byproduct that exist.
Background technology
As the part of manufacturing process, printed wire board industry uses acidic copper etchant to remove undesirable copper from printed-wiring board (PWB) usually.And employed acidic copper etchant generally all is the mixture that is made of hydrochloric acid, hydrogen peroxide and sodium-chlor.Also can be to use hypochlorous acid to receive or oxymuriate replaces hydrogen peroxide as oxygenant.Wherein the composition of acid ion and oxygenant will corrode copper, forms cupric chloride.In case formed the cupric chloride of capacity, when copper is in divalence (+2) copper state, can become a kind of active etchant, promptly, form cuprous chloride (+1) by cupric chloride corrosion and dissolution of metals copper.And cuprous salt can't be used as a kind of etching material, but cuprous salt can form active etchant or cupric form after utilizing hydrogen peroxide or clorox or oxymuriate to reoxidize.
Therefore such acidic copper etchant is widely used in the printed-wiring board (PWB) production plant very much.Though utilize the speed of this etchant etching very fast, include a large amount of copper in the solution after etching, the maximum normal contents of copper is every liter of 100-180 gram copper.And in a single day this solution contain copper, just will go out of use.Must remove institute's dissolved copper by processing, so that reclaim.
Proposed many useless etching reagent to be handled, so that the mode that copper is recycled for this reason.For example: a kind of direct electrolysis process that uses special electrode and cupric chloride etching reagent that Parikh etc. (United States Patent (USP) 3784455) propose.The direct electrolysis that Kucherenko etc. (United States Patent (USP) 4107011) propose, and the claimed produced simultaneously chlorine (co-produced chlorinegas) that utilizes is assisted oxidation univalent copper ion and recovery etching reagent.But the existence of chlorion makes direct electrolysis comparatively difficult.
In addition, great majority utilize electrolytic recovery method all to use membrane separation technique, perhaps use liquid ion exchange material, before carrying out electrolysis copper and muriate are separated.As: Edelstein (United States Patent (USP) 6375713) proposes and will mix with useless cupric chloride etching reagent by the sulfuric acid etchant solution of copper ore being handled acquisition, eliminate muriate and copper is transferred to sulphuric acid soln after concentrating by solvent extraction subsequently, carry out electrolytic deposition.A kind of similar technology that Hamby (United States Patent (USP) 3784455) proposes, wherein useless etching reagent is ammoniated copper etchant.A kind of porous separator that is used in the electrolytic cell that Naumov etc. (United States Patent (USP) 4604175) propose, by it iron(ic) chloride/cupric chloride etching reagent is handled, thereby the chlorine that makes anodizing produce can spread back cathode solution and be reoxidised into active ferric ion etching reagent with ferrous.A kind of similar technology that is used for cupric chloride or iron(ic) chloride that Mikami etc. (United States Patent (USP) 5393387) propose, but chlorine is communicated directly into another part of etching reagent, be used for reclaiming.
Also have a kind of being well known that to use scrap iron (scrap iron) that copper reduction is become the copper metal, this is a kind of submergence technology or cementation technology.What adopt usually in mining industry is to be sprayed at dissolved copper on the inferior quality ore through the sulphuric acid soln of dilution.Solution is pumped in the jar that has a scrap iron, and here copper precipitation takes place and sulfuric acid/ferrum sulfuricum oxydatum solutum is used again.Because the cost of batching is lower, therefore makes usually and handle the cupric chloride etching reagent in this way.But have sluggish and inadequate problem, resulting discarded iron(ic) chloride of being stained by copper must be abandoned.Treated solution is a kind of mixture that is made of iron, ferrous and iron(ic) chloride and copper metal.This mixture is very difficult to separate from the high copper of economic worth, and is difficult to flushing.Remaining molysite is to be worth low-down material, must be used as waste treatment usually.But this is a kind of slow relatively, with low cost very dirt and the technology that has environmental issue.(United States Patent (USP)s 3874940) such as Kausel etc. (United States Patent (USP) 4152143), Kellerwessel etc. (United States Patent (USP) 4119303) and Vera all described cementation copper on scrap iron, and improvements are that scrap iron is by make a return journey copper removal upper layer and manifest fresh iron of stirring highly ceaselessly.Vera etc. also propose, and iron is hundreds and thousands of with the ratio of the chemical equivalent of copper, so that make that reaction is the fastest.
(United States Patent (USP)s 6649131) such as Allies etc. (United States Patent (USP) 5560838) and Seo used etching reagent to precipitate cupric oxide simply, and cupric oxide still is a kind of low-value product, and remaining waste water is abandoned.Other technology relates to and heating, so that seethe with excitement in basic solution, has or do not have formaldehyde.
Hoboy etc. (United States Patent (USP) 6770249) use a kind of calcium chloride solution to convert refuse to copper, lead and other soluble metal ion, and they are higher than 6 o'clock precipitations in the pH value subsequently and separate out on zinc.Wallace (United States Patent (USP) 4008077 and 4082546) uses aluminium to precipitate from waste water, waste electroplating solution and photo fixing salt and separates out silver, copper and precious metal.Natural alumina surface coating layer has hindered this reaction, so aluminum component must be through the next disruptive oxidation aluminium lamination of mechanical workout, so that realize abundant immersion plating.
A in addition university paper (M.Shein, Reducing and Recycling HazardousMaterials) has been described some laboratory tests, and its middle school student can contrast and use iron, aluminum and zinc metal to precipitate copper from waste liquid.Explained aluminium and uneconomical (" using aluminium to reclaim copper will be very expensive ") in this part paper, and iron and zinc are preferred examples.
The amount of the spent acid etching reagent that is produced in the printed wire board industry is very big.Generally, the printed on both sides line material that every production is 7 to 10 square metres can produce one gallon useless etching reagent.Even between an in-between car, also can produce the useless etching reagent that surpasses 400,000 liters (100,000 gallons) every year.Because the amount of spent acid etching reagent is very big, and reclaim very complexity, therefore useless etching reagent needs to be handled and reclaim after the transportation at a distance.This extensive transportation of etching reagent is very expensive and dangerous, exists many Hazardous substancess that the chance of leaking takes place.
Aluminium successfully has been applied in the technology that ammoniated copper etchant is handled and reclaimed, and does not introduce detrimental impurity, need not to use expensive membrane separation apparatus and rectifier simultaneously.The efficient of this technology is higher, but thermal value is very high and be difficult to control, as the United States Patent (USP) 5524780 of Krulik.And the control to this technology improves, and more homogeneous and controlled speed of response (as: United States Patent (USP) 5556553 of Krulik) are provided.
Previous research and patent documentation all concentrate on and utilize aluminium to remove copper from the variable system of dig up mine treatment soln, waste water, electroplate rinsing liquid and other dilution and pH.These studies show that the natural alumina that is present in the aluminium surface has negative impact to speed of response and level of response.Adopted various schemes to try hard to improve speed of response and level of response, great majority all are to come the failure surface rete by aluminium is carried out mechanical friction.These researchs also show, when copper is deposited in the smooth relatively non-porous coating, with delayed response, unless denuded with physics mode.
Summary of the invention
The object of the present invention is to provide a kind of technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed, when utilizing aluminium that the tart copper etchant is handled when making a return journey copper removal, need not to carry out abrasion, reaction fast and thoroughly.In technology of the present invention, only need high initial copper concentration, high chlorinity, high acidity and controlled high technology temperature are made up, just can disruptive oxidation easily aluminum membranous layer, the final fluffy and porous of copper that deposits is allowed fast, up hill and dale copper is removed.
The technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed among the present invention is passed through control suitable temperature and copper concentration, utilize one or more independently treatment trough that aluminium is housed that the spent acid copper etchant is handled again, make copper separate out as metal.
Technology among the present invention can make reaction carry out by the suitable control to temperature and copper concentration quick, thorough and basically harmlessly.Make aforesaid problem, promptly natural aluminum oxide rete can delay and disturbance reponse, is also successfully overcome.The finished product only are made up of the acidic solution of solid copper metal and aluminum chloride.This solution can be neutralized and be sold to the user of aluminium hydroxide.But more economical is the treated solution of direct marketing.Possible purposes comprises the liquor alumini chloridi that is used for drink water purifying and wastewater treatment and uses liquor alumini chloridi as the raw material of producing poly aluminium chloride and other products.Need not becomes key component of the present invention and is of value to economic benefit separating such as zinc or the so poisonous low value material of iron.
Technology among the present invention has fast, economy and the less advantage of toxicity.When with the operation of 40 to 80 ℃ predetermined temperature range, especially when with 50 to 70 ℃ predetermined temperature range operation, reaction fast and efficiently.Like this with regard to avoided the excessive problem of at high temperature runaway reaction and boiling and at low temperatures speed of response delay and the aluminum oxide rete stops the problem of reaction.It is highly important that at economic aspect the heat that has used the expection reduction reaction of cupric ion and aluminium to be produced uses outside heat that temperature is controlled so that utilize on a small quantity or not.Final economic benefits is that useless etching reagent need not before handling the pH value to be regulated.The another one economical advantage is that final treated etching reagent itself is a kind of valuable raw material, need not as waste treatment or abandons.Therefore, the value of aluminum metal is able to full remuneration by the form with generation heat and valuable aluminium salt.The copper metal is the unique solid that remains in the solution, and is easy to remove.
Technology is utilized metallic aluminium among the present invention in controlled reaction, allows useless etching reagent is handled or batch treatment continuously.This modification method promptly can keep speed of response fast with efficient based on making than some variable by accent based on following principle under the controlled temperature.These process variables comprise that the starting point concentration of copper, the surface area of aluminium, the weight of aluminium, type, proportion, temperature, acidity, chloride concentration and the liquid of aluminium chips add speed.In case relevant process variable is set, the acidic etchant treatment process can move easily automatically so.
By using a plurality of treatment troughs, can be controlled and be removed more up hill and dale copper better to technology.The thermopositive reaction that cupric ion and chlorine carry out can be used to remove most copper.The overflow that comes from first treatment trough can be sent in second treatment trough that includes heating component and high surface area aluminium of optional, so that up hill and dale copper is removed.Even under the batch treatment pattern, only use a treatment trough, combine with active temperature control by the interpolation of using control aluminium, also can efficiently and apace copper be removed, thermopositive reaction risk out of control can not appear.Can also in continuous processing, use higher flow velocity, in temperature control down, optionally a part of liquid stream is back to first treatment trough by by-pass conduit.As radiator and along with density loss, provide the longer time to make copper react more up hill and dale.
A plurality of treatment troughs can be arranged in any known configurations mode, so that more up hill and dale copper is removed in continuous mode.These treatment troughs can be arranged simply is the series connection form, and the outlet of a treatment trough is connected on the inlet of next treatment trough.In this distributing style, need not by-pass conduit.Described reaction will full out be carried out under the highest condition of copper concentration in first groove.Along with the removal of described reaction owing to institute's dissolved copper delays, the acidic etching solution that has used can be heated to any temperature required easily, impels the removal to copper to reach any required degree.This extra heating can utilize internal heater, immersion heater, sandwich-type well heater (jacketed heaters) or any other method to realize.They also can be arranged and be parallel form, perhaps according to useful engineering practice be arranged in any in batches, series connection and mixed form in parallel.
Another one advantage of the present invention is that the spent acid etching reagent can carry out site disposal at the production facility place easily.Treatment trough can use the recyclable container that is loaded with aluminum metal, when aluminium is depleted, only need change recyclable container simply.So just avoided the problem of peril of transportation refuse.Only need transportation safety through reclaiming the copper metal and being used for the liquor alumini chloridi of useful chemical purposes.
Embodiment
Although following description is detailed and concrete, described here technology only is used for illustration the present invention.Concerning person skilled in the art, all can adopt this design to obtain many technologies except that shown in these examples.
Useless etching reagent among the present invention comes from the spent acid copper etchant in industrial printed wiring workshop.It includes HCl and as the sodium chlorate of oxygenant.General analytical results is: the Cu:99.79 grams per liter, and Sp.Gr 1.210, and pH 0.25, free acid 0.31N.Other test utilizes similar acidic copper etchant to carry out, and includes the hydrogen peroxide that replaces sodium chlorate.
Example 1 to 3
One group of beaker that uses the spent acid copper etchant to test.Concentration is the copper of every liter 120 gram, is diluted to 50% and 25% in order to using.This time the purpose of test only is to study the speed of reaction.
The performance of test soln
| Acidic etchant | 25％ | 50％ | 100％ |
| PH | 0.42 | 0.05 | -0.24 |
| Equivalent concentration | 0.41 | 0.81 | 1.62 |
| Example 1 | Example 2 | Example 3 |
Example 1
This example has been used 200 milliliter 25% useless etching reagent, and the surface area that adds every gram with the fritter form is that 28.3 square centimeters aluminium matter is bored paper tinsel.
The table of example 1
| Time (second) | 0 | 155 | 295 | ＞1200 |
| Temperature (℃) | 26 | 48 | 63, coppery disappears | 63, still bubbling reacts with aluminium |
Example 2
This example has been used 200 milliliter 50% useless etching reagent, and the surface area that adds every gram with the fritter form is that 28.3 square centimeters aluminium matter is bored paper tinsel.
The table of example 2
| Time (second) | 0 | 35 | 37 | 50 | 50 | 77 | 198 | 295 |
| Temperature (℃) | 35 | 47 | 68 | 82 | 87 | 91 | 89 | 86 |
Obviously, the reaction of 50% solution is too violent, and 25% top temperature only is 63 ℃.In case solution reaches about 80 ℃, and uncontrolled reaction will take place, and utilizes in the test of the high slightly copper of concentration at other, can cause the solution boiling excessive.70 ℃ is the upper temperature limit of an environmental protection, and it shows is controlled.Be lower than 40 ℃, for the industrial application of the best, reacted slow.
Example 3
Use 100% useless etching reagent, but reaction is too violent,, also has some solution and take place to seethe with excitement excessive even add a spot of aluminium.
After copper was reduced, aluminium continued to react with free acid.This reaction is slower than very with the copper reduction reacting phase.The finished product will utilize aluminium that acid is thoroughly neutralized, along with the pH value obviously raises, and aluminum chloride generation hydrolysis, and aluminium hydroxide precipitates.For the waste treatment field, the acidic solution of aluminum chloride will be a kind of ideal product.It will be used to trade effluent is handled, tap water is carried out preliminary cleaning and precipitated solid from treated sanitary sewage.The tart liquor alumini chloridi can also be used as a kind of industrial raw material, for example is used to produce poly aluminium chloride, other waste treatment compound.This acidic solution can also be neutralized simply, and sells aluminium hydroxide.
Have been found that free acid is still very high after copper is reduced.This phenomenon is 20% or very obvious when higher in the concentration of useless etching reagent.So just show a kind of dynamic phenomenon, wherein with the reacting phase ratio of hydrogen with aluminium, the reaction of copper and aluminium is faster.This point all is useful in industry and reality, because the reduction rate of copper is fast more, equipment can be more little.
Example 4 to 6
Addition when this test is intended to study in the useless etching reagent that only thin aluminium matter brill paper tinsel is added to known quantity.Solution is 400 milliliter 25% spent acid copper etchant, and color is blue, contains every liter 30 copper about gram.If copper is all with CuCl
2Form exist, the reaction of the chemical equivalent of 0.189M copper and aluminium will consume 3.4 aluminium that restrain so.If some copper exists with the form of CuCl, the aluminium that is consumed can be still less so.Following table shows, has the cuprous chloride of the overwhelming majority, thereby the feasible 3 gram aluminium that only need be reduced into metal with regard to being enough to all cupric ions.Although reaction is violent, still can control top temperature is 67 ℃.
The table of example 4-6
| 1 gram aluminium | 2 gram aluminium | 3 gram aluminium | |
| Outlet temperature (℃) | 43 | 54 | 67 |
| Dissolve the time (second) that all aluminium consumes | 65 | 83 | 98 |
| Color | Dark green | Dark green | Colourless |
| Example 4 | Example 5 | Example 6 |
Example 7-10
The spent acid copper etchant contains the copper of 123 grams per liters, the muriate of 6.79N and the acidity of 1.86N.In order to make muriatic effect stdn, used a kind of NaCl and reference solution of making of the HCl of 2N by 230 grams per liters.
Four kinds of test solns are prepared to 5%, 10%, 20% and 40% spent acid copper etchant respectively.The dosing of every kind of solution all is tart muriate reference solutions, and be not in all other examples for water.Therefore, for all tests, ionic strength, acidity and chlorinity are all identical.Test soln is 100 milliliters, so copper content is shown in the following table.
| Dilution | 5％ | 10％ | 20％ | 40％ |
| Copper (gram) | 0.615 | 1.23 | 2.46 | 4.92 |
| Finish the required aluminium of copper reduction (gram) | 0.173 | 0.346 | 0.69 | 1.38 |
| The aluminium foil (gram) that adds | 1.5 | 1.5 | 1.5 | 1.5+1.5 |
| Finish the required time of reaction (minute) | 3 | ＜3 | 1.66 | ＜1；＜1 |
| Top temperature (℃) | 63 | 70 | 90 | 93；100 |
| Example 7 | Example 8 | Example 9 | Example 10 |
The detail as a result that is used for example 7-10
Example 7: carried out fast in 1-2 minute before being reflected at, color fades away.Temperature is increased to 63 ℃, and begins to descend when continuing bubbling.Show that being reflected in 3 minutes of copper finish.After the copper reduction reaction finished, aluminium continued to react with free acid, because can see the generation of bubble.In the time of the 5th minute, temperature is still 62 ℃.
Example 8: be reflected at first few minutes and carry out fast, be similar to example 1.Temperature is increased to 73 ℃ maximum, descends subsequently.Bubble still produces in the time of the 5th minute, and temperature is 70 ℃, shows to continue to react with acid.
Example 9: temperature is increased to 90 ℃ in the time of 1 minute and 40 seconds.See that the copper metal is abundant.Like concentration best and that be easy to manage most this moment well.
Example 10: temperature is increased to 93 ℃ in the time of 1 minute, shows solution and goes out to seethe with excitement in aluminum metal.This reaction is too violent.Stop when being reflected at 1 minute, because aluminium is depleted.Also there are some white depositions.Add the aluminium of 1.5 grams once more.React very violent, and temperature is increased to more than 100 ℃.The outer beaker that overflows of most of solution boilings.Remain many aluminium.
Example 11
This is a kind of actual test.Reactive tank is 200 liters.
The spent acid etching reagent is the useless etching reagent of generality that comes from industrial printed wiring workshop, and it comprises HCl and as the sodium chlorate of oxygenant.Analytical results is:
Copper: 99.79 grams per liters
Sp.Gr 1.210
PH 0.25
Free acid: 0.31N
In groove, add about 50 liters useless etching reagent, utilize tap water to be diluted to 200 liters.Have a recycle pump, a compartment that is connected the lid on the acid mist washer and is used for the titanium basketry is placed solution in the groove.Fill the thin aluminium matter that is cut into fritter of different amounts in the titanium basketry and bored paper tinsel, the aluminium sheet of 1 cm thick perhaps in bulk.Analytical results to initial testing solution is: copper 25.47 grams per liters, free acid are 0.09N.The temperature of solution is 30.6 ℃.Temperature utilizes hand-held IR thermometer to measure.The surface area of aluminium foil is 28.3 square centimeters of every grams with the ratio of weight.Therefore each titanium basketry all has 0.5 kilogram aluminium foil, has about 14000 square centimeters surface reaction area.
Reaction is carried out fast and reposefully.
Just begin: the aluminium matter of about 3 centimetres of 2 cm x of 0.5 kilogram of filling is bored paper tinsel in small-sized titanium basketry.When this titanium basketry was placed reactive tank, reaction began immediately.
The 7th minute: the temperature in the reaction basketry was 70 ℃, and the temperature of solution is 43 ℃.Two other basketry that 0.5 kilogram of aluminium matter brill paper tinsel is housed is put into test trough successively.Temperature raises and is in controlled range.
The 20th minute: sampling was analyzed, and find that copper has reduced 50% and reached 13.25 grams per liters, and free acid was 0.18N.Temperature of reaction in the titanium basketry is 68 ℃, and the temperature of solution is 58 ℃ in the groove, shows that temperature is able to good control.
The 28th minute: the temperature of reaction in the titanium basketry was 70 ℃, and the temperature of solution is 65 ℃ in the groove.
The 37th minute: sampling was analyzed, and find that copper has reduced 94% and reached 1.51 grams per liters, and free acid was 0.6N.Temperature of reaction in the titanium basketry is 72 ℃, and the temperature of solution is 68 ℃ in the groove, shows that temperature is able to good control.
The 45th minute: find that by range estimation similar all copper all disappears, solution was the copper brown, stems from very small copper particle.These copper are easy to be removed by filteration or centrifugation, form the limpid liquid that contains copper hardly.Take out three basketrys.Preceding two basketrys do not have the residual of aluminium.The 3rd basketry still contains a spot of aluminium foil.Institute's dissolved copper is 1.1 grams per liters, shows that in quick single stage reaction 96% copper is removed.
Solution is discharged from and takes out copper.The outward appearance of copper is very good, and is easy to scoop out.
The table of example 11
| Time | The aluminium basketry | Total surface area | Copper (grams per liter) | Acid (N) | Temperature of reaction | Solution temperature |
| Just begin | 1 basketry that has 0.5 kilogram of aluminium foil | 14000 square centimeters | 25.74 | 0.09 | 30.6 | |
| The 7th minute | 70 | 43 | ||||
| The 20th minute | Increase by two basketrys | 42000 square centimeters | 13.25 | 0.18 | 68 | 58 |
| The 28th minute | 70 | 65 | ||||
| The 37th minute | 1.51 | 0.6 | 72 | 68 | ||
| The 45th minute | 1.1 |
Example 12
Groove is washed, and pour into 150 liters of solution again through handling in the preceding example.This solution contains the copper of 1.1 grams per liters and the free acid of 0.6N.Also include the aluminum chloride that produces by previous reaction.The purpose of this test is whether institute's dissolved aluminium can produce any negative impact to reaction, whether make chlorinity and acidity be higher than the example 11 of dilute with water, and whether research can use 1 cm thick aluminium sheet in bulk.Each titanium basketry all uses one group of five aluminium sheet, 1 centimetre of 20 cm x, 25 cm x.Because the heat of previous reaction remnants in 150 liters of reusable solution, the temperature when just beginning is 53 ℃.Initial copper concentration is 22 grams per liters.The surface area of aluminium sheet is approximately 0.76 square centimeter of every gram.The aluminium that each basketry splendid attire is about 6.6 kilograms, surface area are about 5000 square centimeters.Because the surface area of aluminium foil is 28.3 square centimeters of every grams, so the surface area of aluminium foil is 37 times of aluminium sheet.Owing to added the aluminium of Different Weight, therefore to compare with example 11, example 12 has been equivalent to utilize 12% of aluminium foil surface area.By adding aluminium sheet, this ratio is increased to 24%, and by adding aluminium foil continuously, this ratio is increased to 57% and 90% subsequently.
Just begin: add a titanium basketry that has aluminium sheet.These aluminium sheets have thicker aluminium oxide passivation rete relatively.Owing to micro-bubble occurs, show that reaction begins immediately, but reaction seems comparatively slow, because the surface area of every gram aluminium is less, and alumina layer is thicker.In last test, temperature begins to raise, but speed is slow.
The 16th minute, add second titanium basketry that has 5 aluminium sheets, amount to 10 blocks of aluminium sheets.Temperature near the aluminium sheet place in the titanium basketry is 75-80 ℃, and solution temperature is 60 ℃.
The 27th minute: the temperature near the aluminium sheet place was 84 ℃, and solution temperature is 76 ℃.
The 34th minute: the 3rd titanium basketry that has aluminium foil is added into reactive tank.Temperature in the titanium basketry is 76 ℃, and solution temperature is 73 ℃.
The 36th minute: the 4th titanium basketry that has aluminium foil is added into reactive tank.Temperature in the titanium basketry is 86 ℃, and solution temperature is 75 ℃.
The 45th minute: find all aluminium foils all dissolvings in the basketry.
The 54th minute: two aluminium foil basketrys were empty.Temperature in the basketry is 75 ℃, and solution temperature is 74 ℃.
Solution presents the copper brown once more, and finds that copper content is 1.17 grams per liters.
The table of example 12
| Time | The aluminium group | Total surface area | Copper (grams per liter) | Acid (N) | Temperature of reaction | Solution temperature |
| Just begin | 1 group of 5 aluminium sheet | 5000 square centimeters | 22 | 53 | ||
| The 16th minute | Increase by one group of aluminium sheet | 10000 square centimeters | 75-80 | 60 | ||
| The 27th minute | 84 | 76 | ||||
| The 34th minute | Increase an aluminium foil basketry | 24000 square centimeters | 76 | 73 | ||
| The 45th minute | Increase an aluminium foil basketry | 38000 square centimeters | 86 | 75 | ||
| The 54th minute | 1.17 | 75 | 74 |
Be coated with copper on the aluminium sheet, but be different from the throw out of mentioning in the patent formerly, this throw out porous, and can be used in copper is reduced.At preceding 34 minutes, the surface area in the example 12 only had 1/4th in the example 11 to play a role.Then, surface area increases to 90% of example 11, and reaction has reached identical degree (copper content is 1.1 grams per liters) in a similar time.Obviously, using the useless etching reagent of high density under comparatively high temps, comprise muriate, is that copper react successfully, key fast and completely.
Claims (19)
1. a technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed is at first controlled various process variables, utilizes one or more independently treatment trough that aluminium is housed that the spent acid copper etchant is handled again, makes copper separate out as metal.
2. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1, it is characterized in that described process variable comprises that the starting point concentration of copper, the surface area of aluminium, the weight of aluminium, type, proportion, temperature, acidity, chloride concentration and the liquid of aluminium chips add speed.
3. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1 is characterized in that described treatment trough is kept for handling the technological temperature of described etching reagent by heating or cooling.
4. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1 is characterized in that described technological temperature is maintained between 35 to 80 ℃.
5. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 4 is characterized in that described technological temperature is maintained between 50 to 70 ℃.
6. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1 is characterized in that the copper starting point concentration in the described technology is set to smaller or equal to 60 grams per liters.
7. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 6 is characterized in that the copper starting point concentration in the described technology is set to 20 to 40 grams per liters.
8. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1, it is characterized in that, the main treatment trough that described treatment trough comprises, this main treatment trough can be used for removing copper from described etching reagent at least one other treatment trough feed that includes aluminium.
9. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 8 is characterized in that described treatment trough is designed to portable, is used for replenishing aluminium in the different location and taking out reaction product.
10. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 8 is characterized in that described treatment trough is not of portable form, and is used for replenishing aluminium in the appointed place and taking out reaction product.
11. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 8 is characterized in that described main treatment trough is to a plurality of treatment trough feed that are the configured in series form.
12. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 8 is characterized in that described main treatment trough is to a plurality of treatment trough feed that are collocation form in parallel.
13. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 8 is characterized in that described main treatment trough is to a plurality of treatment trough feed that are series-parallel connection combining and configuring form.
14. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1 is characterized in that described treatment trough utilizes filteration to remove solid from described etching reagent.
15. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1 is characterized in that described treatment trough utilizes centrifugation to remove solid from described etching reagent.
16. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1 is characterized in that described treatment trough utilizes sedimentation to remove solid from described etching reagent.
17. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1 is characterized in that described treated useless etching reagent is used as a kind of aluminum salt solution that is used to carry out waste treatment.
18. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1 is characterized in that, described treated useless etching reagent is used as a kind of aluminum salt solution that chemical feedstocks is produced that is used for.
19. the technology of utilizing metallic aluminium that discarded acidic copper etchant is handled and reclaimed according to claim 1 is characterized in that described treated useless etching reagent can be neutralized, and is used to reclaim solid aluminium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101565974A CN101209874B (en) | 2006-12-31 | 2006-12-31 | Technique for processing and recovering disuse acidic copper etchant by metal aluminum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101565974A CN101209874B (en) | 2006-12-31 | 2006-12-31 | Technique for processing and recovering disuse acidic copper etchant by metal aluminum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101209874A true CN101209874A (en) | 2008-07-02 |
| CN101209874B CN101209874B (en) | 2011-09-14 |
Family
ID=39610153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101565974A Expired - Fee Related CN101209874B (en) | 2006-12-31 | 2006-12-31 | Technique for processing and recovering disuse acidic copper etchant by metal aluminum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101209874B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451916A (en) * | 2010-10-28 | 2012-05-16 | 华固实业股份有限公司 | Method for transforming aqueous solution containing copper chloride into copper powder and polyaluminum chloride (PAC) |
| CN103803737A (en) * | 2012-11-06 | 2014-05-21 | 重庆龙健金属制造有限公司 | Treatment method of copper-containing etching liquid |
| CN104818385A (en) * | 2015-04-10 | 2015-08-05 | 吴江市松陵镇氧化铜厂 | Energy-saving, environmental-protection and zero-discharge technology of acidic waste etching solution resource recycling treatment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5524780A (en) * | 1995-01-31 | 1996-06-11 | Applied Electroless Concepts Inc. | Control of regeneration of ammoniacal copper etchant |
| US5556553A (en) * | 1995-05-23 | 1996-09-17 | Applied Electroless Concepts, Inc. | Recycle process for regeneration of ammoniacal copper etchant |
| CN1854343A (en) * | 2005-04-26 | 2006-11-01 | 李德良 | Copper etching liquid and its circulative usage |
-
2006
- 2006-12-31 CN CN2006101565974A patent/CN101209874B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451916A (en) * | 2010-10-28 | 2012-05-16 | 华固实业股份有限公司 | Method for transforming aqueous solution containing copper chloride into copper powder and polyaluminum chloride (PAC) |
| CN103803737A (en) * | 2012-11-06 | 2014-05-21 | 重庆龙健金属制造有限公司 | Treatment method of copper-containing etching liquid |
| CN103803737B (en) * | 2012-11-06 | 2015-10-28 | 重庆龙健金属制造有限公司 | A kind for the treatment of process containing copper etchant solution |
| CN104818385A (en) * | 2015-04-10 | 2015-08-05 | 吴江市松陵镇氧化铜厂 | Energy-saving, environmental-protection and zero-discharge technology of acidic waste etching solution resource recycling treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101209874B (en) | 2011-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102021595B (en) | Surface pre-treatment system combining four aluminum alloy working grooves into whole for full recovery of medicament and zero emission of wastewater | |
| CN103936081B (en) | Method and system for preparing ferric chloride, electrodeposited copper and copper powder from copper-containing hydrochloric acid waste liquid | |
| US3953306A (en) | Metal recovery from waste treatment sludges | |
| CN104310647A (en) | Recycling method for treating stainless steel pickling acid pickle and wastewater | |
| Diban et al. | Zinc recovery and waste sludge minimization from chromium passivation baths | |
| CN101619463B (en) | Method for on-line pickling solution treatment and system thereof | |
| CN218810653U (en) | Contain processing apparatus of nitrate radical waste liquid | |
| CN101338365B (en) | Synthesizing method for molybdenum-nickel ore | |
| CN101492186A (en) | Method and device for circulation and regeneration of acidic waste etching liquid | |
| CN101209874B (en) | Technique for processing and recovering disuse acidic copper etchant by metal aluminum | |
| CN106319519A (en) | Method for cyclically preparing tin stripping solution and electroplated tin by utilizing waste tin stripping solution | |
| CN100510188C (en) | Method of recovering copper metal from waste printed circuit board and copper containing waste liquid and device thereof | |
| KR101247941B1 (en) | Refining Method of Copper Chloride Etching Waste Fluid And Refined Copper Chloride Solution | |
| Keskitalo et al. | Analysis of key patents of the regeneration of acidic cupric chloride etchant waste and tin stripping waste | |
| CN102732725B (en) | Method for circularly removing impurity chlorine in zinc sulfate solution by using cuprous salt | |
| CN108193052A (en) | Resource utilization prepares the method without ammonium fluxing agent using low acid waste water containing zinc | |
| CN210314493U (en) | Novel molten tin stripping water recycling system | |
| CN202626296U (en) | Recycling device of waste tin-stripping liquid | |
| JP5808132B2 (en) | Treatment and recovery method for copper-containing acidic waste liquid and equipment therefor | |
| CN103422087A (en) | Surface phosphating treatment technology | |
| JP4295352B1 (en) | Wastewater treatment equipment for reusing water in surface treatment of trivalent chromate and wastewater treatment method for reusing water | |
| US5524780A (en) | Control of regeneration of ammoniacal copper etchant | |
| CN208562480U (en) | A kind of recovery system of cupric silicon powder | |
| CN1982505A (en) | Method for recovering and reutilizing copper etching agent containing amino-soda by metal aluminum | |
| CN109112546B (en) | Oxidation line system and process for recovering aluminum hydroxide and sodium sulfate from mold-stewing liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110914 Termination date: 20121231 |