CN1072218A

CN1072218A - The recovery of copper and copper alloy products lead-tin on face

Info

Publication number: CN1072218A
Application number: CN 91110457
Authority: CN
Inventors: 朱万良; 孙振坤
Original assignee: LUOYANG COPPER PROCESSING PLANT
Current assignee: LUOYANG COPPER PROCESSING PLANT
Priority date: 1991-11-09
Filing date: 1991-11-09
Publication date: 1993-05-19
Anticipated expiration: 2006-11-09
Also published as: CN1028773C

Abstract

The present invention relates to the recovery processing method of a kind of copper and copper alloy products lead-tin on face etc.The waste and old device that scribbles slicker solder (or lead or tin) on the surface soaks in fused salt, and the terne metal of fusing (or lead or tin) is cast ingot.Dissolved salt consist of sodium chloride-containing 20～80%, contain Repone K 20～80%.The temperature of fused salt is controlled at 690～850 ℃.The parts water flushing of the waste and old device of scalding through fused salt makes terne metal (or lead or tin) separate well with copper and copper alloy.The advantage of this processing method is operate continuously, and the fused salt loss is little, and wiping solder can directly reclaim and be re-used as scolder, and copper and copper alloy can directly be mixed with the alloy of the suitable trade mark.

Description

The recovery of copper and copper alloy products lead-tin on face

The present invention relates to scribble the processing method that reclaims wiping solder (or lead or tin) and copper and copper alloy the copper that contains wiping solder (or lead or tin) and the copper alloy scrap from the surface.

Exist in the society and be coated with tin in a large number, scribble the copper and the copper alloy scrap of wiping solder, automobile for example, the water tank of tractor, ice cream mould etc., scrap every year a lot, automobile particularly, the learies of the water tank of tractor is quite big, how reclaiming these waste materials is the problems that must solve. the existing recovery and treatment method of above-mentioned waste material is had two: first method is to scribble the waste material of wiping solder on the above-mentioned surface, place wall to hang with in the electric furnace of resistance wire heating, be heated to 600 °-750 ℃, make its lip-deep wiping solder fusing and drip to furnace bottom, reclaimed after compiling, the shortcoming of this method is under 600 °-750 ℃ high temperature, be coated in the wiping solder on copper and the copper alloy surface, when dripping to the furnace bottom recovery with liquid pearl attitude, the part slicker solder is oxidized, the oxide compound of its slicker solder still overlays on the surface of copper and copper alloy, can't remove, more be difficult to reclaim, and become the source of pollution that next step reclaims metallic copper and copper alloy again, make the recovery process complications of copper and copper alloy, reduced lead, the rate of recovery of tin and copper and copper alloy, the rate of recovery of slicker solder has only about 80%, second method is that copper and copper alloy scrap that the surface scribbles wiping solder are directly put into melting in the refining reverberatory furnace, plumbous, tin, metals such as zinc are all oxidized under 1200 °-1250 ℃ high temperature, and these oxide compound parts fly in the flue dust, another part slag making claws in stove and discards. and plumbous the flue dust, tin, the oxide compound of zinc recycles again. and the copper after refining forms big ear anode, again through being electrolyzed to produce cathode copper. the shortcoming of this method is expensive metallic tin, plumbous, metals such as zinc have all changed into their oxide compound, its part has entered flue dust, another part has entered in the slag, plumbous, metals such as tin can not directly reclaim with their form of metal, reduced the rate of recovery of these metals, make metallic lead, tin, the cost recovery of metals such as zinc is increased, and has reduced economic benefit widely.

American documentation literature US2,967,769 have introduced the method for a kind of recovery than metals such as slicker solders on the infusible metallic surface, than the fusing point of infusible metal more than 1000 °F. this method has certainweight with title, be placed in the band foraminous basket by the waste and old device of making than refractory metal material (for example honeycomb scatterer centre portions of junked-auto) that has plumber's solder on the surface, band foraminous basket is put into the crucible that fills molten salt bath, melting salt in up-down vibration basket or the stirring crucible, and in molten salt bath, kept 5-10 minute, the temperature of molten salt bath is below 1000 °F, be preferably 750 °-900 °F, the magnesium chloride that consists of 38-65% of salt bath, the sodium-chlor of 30-53%, the zinc chloride of 3-15%, the metal collection such as slicker solder of fusing are in molten salt bath. scribble lead on the surface, after the waste and old device of making than the infusible metallic substance of metals such as tin soaks in salt bath and finishes, owing to being melted to remove, scolder falls apart, the parts of copper or copper alloy have been become, from molten salt bath, shift out basket, treat that fused salt drains from basket after, the parts of copper in the basket or copper alloy are shifted out from basket, in flowing water, wash, drying is weighed. fused salt poured out from crucible carefully at leisure, until being arranged, stay in the crucible in fused salt and scolder in a small amount, the scolder that will have fused salt again moves on in another container and dissolves except that desalting with flowing water, collected scolder is particulate state and little bulk, drying is weighed, metal such as slicker solder is separated with copper and copper alloy. this method is compared its advantage with two kinds of above-mentioned recovery methods and is: because be to place molten salt bath to heat by the waste and old device that constitutes than refractory metal that scribbles slicker solder on the surface, completely cut off air, avoided the oxidation of air to metals such as slicker solders, the rate of recovery of metals such as slicker solder is increased. but because device will be with the fused salt in the crucible carefully after soaking in fused salt, from crucible, pour out at leisure, make this technology become intermittent operation, the used time in each operational cycle extends greatly, and the wiping solder that will have fused salt is placed on its lip-deep fused salt of flush away in the flowing water, wiping solder is small-particle again, little bulk, operate careless slightly, easily washed away and lose; Surface at water washing process small particles, little blocky wiping solder is also easily oxidized. in addition, Magnesium Chloride Anhydrous price height, easily suction is difficult to obtain, sink to the Separation and Recovery that crucible bottom influences plumber's solder if in fused salt heat-processed, decomposite the magnesium oxide slag with hydrated magnesium chloride, fused salt can not be used continuously, carefully from crucible, pour out at leisure with Bi Bixu at every turn, the loss amount of fused salt is increased, the little blocky wiping solder of fine granularity is ingot casting again, and the fusing ingot casting has increased the loss of wiping solder again.

Purpose of the present invention just is to overcome above-mentioned existing shortcoming, work out a kind of recovery wiping solder (or lead or tin) of operate continuously and the processing method of copper and copper alloy, avoid generating in the fused salt MAGNESIUM METAL oxide precipitation, needn't remove fused salt at every turn, thereby reduce the loss of fused salt, shortened the time in each operational cycle again widely, the wiping solder that is melted state (or lead or tin) of recovery is directly discharged from crucible, cast wiping solder (or lead or tin) ingot, need not reprocess these wiping solders and just can use as scolder again, the copper of recovery and copper alloy can directly be mixed with the alloy of the red copper and the suitable trade mark.

Another object of the present invention is that research and design goes out from copper and copper alloy products surface recovery slicker solder the time, makes wiping solder (or lead or tin) can directly discharge a kind of special copple equipment of casting ingot from the crucible that fills fused salt.

The processing method that the lip-deep slicker solder of a kind of copper of the present invention and copper alloy products reclaims, fusing point is higher than on 850 ℃ the surface and scribbles the copper of slicker solder (or lead or tin) and the waste and old device of copper alloy system, place molten salt bath to soak 1-15 minute, stir fused salt or bob and weave and scribble the waste and old device of slicker solder (or lead or tin) in its surface, used molten salt bath consist of sodium chloride-containing 20-80%, contain Repone K 20-80%, the temperature of control molten salt bath is 690 °-850 ℃, the wiping solder (or lead or tin) that scribbles the molten state that the waste and old device of the copper of terne metal (or lead or tin) and copper alloy system separates from the surface sinks to the bottom of the container that fills fused salt, discharge from the weif orifice of container bottom lowest part, cast ingot. from fused salt, take out the copper of disintegration automatically and the parts of the waste and old device that copper closes system, above crucible, stop a moment slightly, making its surface go up adherent fused salt is dropped in the crucible, be placed in the water again and wash, thereby reach the isolating purpose of wiping solder (or lead or tin) and copper and copper alloy.

The lip-deep slicker solder of copper of the present invention and copper alloy products reclaims the special copple of processing method, it is a tubbiness, a weif orifice is arranged, block with a plug, the bottom surface of crucible tilts to the weif orifice place, the angle of its squint (being the bottom surface of crucible and the angle β of horizontal plane) is 10 °-15 °, weif orifice is positioned at the lowest part of crucible bottom side, so that make the wiping solder that sinks to crucible bottom (or lead or tin) of fusing collect in the weif orifice place, after treating that wiping solder (or lead or tin) gathers some amount, discharge, cast ingot.

Place molten salt bath to soak the waste and old device that scribbles slicker solder on its surface, the time of its immersion is between 1-15 minute. and the time of immersion is too short, it is isolating not exclusively to be coated in lip-deep wiping solder (or lead or tin) tip-off, the rate of recovery of wiping solder (or lead or tin) reduces, and do not scald the terne metal that gets off on copper and the copper alloy surface and still be attached on copper and the copper alloy surface, the recovery that influences copper and copper alloy is used. the overlong time of immersion, prolonged the time of technological process, waste energy, can not improve the rate of recovery of slicker solder, so the time of soaking was good with 5-10 minute in molten salt bath.

The waste and old device that scribbles the copper of plumber's solder (or lead or tin) and copper alloy system on the said surface is copper and the copper alloy scrap that scribbles slicker solder, wiping solder on all surfaces such as the waste water tank of automobile, tractor, useless ice cream mould, refrigerator radiator tube. introducing domestic automobile, the used tubular type water tank of tractor, pipe according to data is H90 brass, sheet is the T2 red copper, is welded with No. 10 or No. 20 wiping solders.

On with its surface, scribble in the waste and old copper of wiping solder (or lead or tin) and the process that copper alloy device is immersed in fused salt, wiping solder (or lead or tin) and fused salt be react with not, fusing point is low (to be about about 200 °-300 ℃, it is 183 ℃ that the eutectic temperature of slicker solder has only). be coated in the wiping solder (or lead or tin) that has on copper and the copper alloy surface be melted separate after, because wiping solder (or lead or tin) differs greatly with the proportion of fused salt (proportion of wiping solder is about 4-5 times of fused salt proportion), so the terne metal that melts (or lead or tin) sinks to the bottom of crucible very soon and collects in the weif orifice place and obtain recovery. because wiping solder (or lead or tin) all is immersed in the fused salt, avoided and the contacting of air, wiping solder (or lead or tin) can be not oxidized, copper and copper alloy also not with the fused salt react with, and its fusing point is all more than 850 ℃, for example the fusing point of red copper is 1083 ℃, the fusing point of H90 brass is about 1050 ℃, the fusing point of H62 brass is about about 900 ℃, so wiping solder (or lead or tin) can well be separated with copper and copper alloy.

Molten salt bath consist of sodium chloride-containing 20-80%, contain Repone K 20-80%, the fusing point of sodium-chlor is that the fusing point of 803 ℃ of Repone K is 775 ℃, and the fusing point of the sodium-chlor of 50% Repone K and 50% is about 660 ℃, so the composition of molten salt bath is to contain the sodium-chlor of 50-70%, the Repone K that contains 30-50% is good.

The temperature of control molten salt bath is 690 °-850 ℃, the temperature of molten salt bath is too low, the viscosity of fused salt increases when being lower than 690 ℃, mobile variation. when from molten salt bath, taking out the parts of the copper that disintegrated and the waste and old device of copper alloy, adherent fused salt amount increases on its face, the salt crust that next step cleaning is removed on copper and the copper alloy surface has increased difficulty, and the speed that the loss amount that has increased fused salt makes the terne metal that melts sink at the bottom of the crucible simultaneously is also slack-off; The temperature height of fused salt, its good fluidity, viscosity is little, the time of soaking can suitably reduce, and can reduce the loss of fused salt again, and the speed that the wiping solder that melts is sunk at the bottom of the crucible accelerates, the Separation and Recovery that helps wiping solder. still, the temperature of molten salt bath is too high, is higher than 850 ℃, and Repone K has a small amount of volatilization loss, polluted environment, energy expenditure is big, and operation is also inconvenient, so the temperature of molten salt bath is to be controlled at 700 °-760 ℃ for good.

The processing method that slicker solder of the present invention reclaims, be that the sodium-chlor and the Repone K mixing salt that will prepare put into the fusing of crucible internal heating, the method of heating is coal gas heating or coal-fired heating, preferably big chamber and burner hearth are separated during coal-fired the heating, when treating that the fused salt temperature reaches 690 °-850 ℃, the mesh screen basket that scribbles the waste and old device of slicker solder on its surface will be filled, be dipped in 690 °-850 ℃ the molten salt bath, in immersion process, stir the fused salt or the mesh screen basket of bobbing and weaving, make the terne metal (or lead or tin) that is coated on copper and the waste and old device of copper alloy, being subjected to that terne metal (or lead or tin) that washing away of fused salt make tip-off hightails copper material surface and the bottom that sinks to crucible. soak time is 1-15 minute, preferably 5-10 minute, basket is proposed, above crucible, stop a moment slightly, putting in advance, the ready tank that fills water washes, wash the fused salt that adheres on its surface off. through the surface cleaning of the copper material after the flushing, can be used for preparation according to the trade mark of alloy and produce corresponding alloy. the waste and old water tank of automobile after soaking for example, radiating pipe and radiator element are thrown off automatically, separate through picking again, deliver to the ingot casting of the corresponding alloy designations of melting between alloy car. also can prepare leaded brass or tin leaded brass such as 59-1,58-2 etc. with copper that reclaims and copper alloy.

The temperature of the used water of fused salt on the flush away copper material surface in tank, there is not strict restriction, generally get final product with cold water, the tap water of room temperature for example, needn't heat in addition or cool off. the time of washing in water depends primarily on the situation of cleaning, generally about 1-15 minute. have only with two, three minutes. in tank, wash the water of copper material, when wherein saliniferous concentration reaches certain value, can also recycle.

The crucible that the lip-deep slicker solder of copper and copper alloy products reclaims the technology special use is a tubbiness, the shape of bucket can be a drum shape, oval barrel-shaped, square barrel-shaped, the bucket of rectangular barrel-shaped a kind of shape wherein, but being with drum shape. the volume of crucible is decided on the scale of production. for the ease of the carrying and installation of crucible equipment, around suitable for reading, a flange is installed near crucible, three hangers are installed on flange. if crucible is a drum shape, flange is circular then three positions of hanger on flange, with the angle between two hangers is 90 °, it is good that angle between two hangers of another hanger and this becomes 135 ° of angles respectively, used special copple can cylinder iron be cast or be welded with steel plate, the plug of weif orifice can cylinder iron be cast or become with the round steel car. for example pull the crucible that is welded into drum shape with the steel of 10 mm thick, used basket can be decided according to the shape of crucible, can make drum shape or rectangular different shape such as barrel-shaped, its method for making is that the steel bar with diameter 8 millimeter is welded, the size of basket with each side around the basket apart from 150 millimeters left sides of crucible inwall in being advisable. processing method of the present invention also is applicable to the recovery of the useless tinware spare of scrap lead word etc.

Processing method of the present invention, also has the following advantages outside the various advantages such as rate of recovery height of 967,769 wiping solders that had (or lead or tin) except having american documentation literature US2, and they are:

(1) processing method operate continuously of the present invention, its fused salt composition is that sodium-chlor adds Repone K, american documentation literature US2,969, the 769 fused salt compositions of being introduced are 38-65% magnesium oxide, the sodium-chlor of 30-53%, the zinc chloride of 3-15%, avoided the magnesium chloride in fused salt to resolve into the magnesium oxide precipitation slagging in the high-temperature lower part branch, on sinking at the bottom of the crucible, influence the shortcoming that terne metal (or lead or tin) reclaims, be beneficial to the recovery of terne metal (or lead or tin) again, the loss amount of fused salt is little, the time in each operational cycle shortens widely, can add needed mixing salt at any time again, the terne metal (or lead or tin) that reclaims can directly be emitted from crucible and be cast alloy pig, directly use or according to user's needs as scolder, with it is that the basis is allocated an amount of lead or tin into, be mixed with new scolder, copper that reclaims and copper alloy be the raw material of the copper alloy of the suitable trade mark of conduct preparation directly, needn't be again through being smelted into operations such as big ear anode production electrolytic copper, make the copper and the copper alloy of recovery obtain directly rationally using, so processing method of the present invention is simple, cost is low, good in economic efficiency, copper, copper alloy, the rate of recovery height of wiping solder (or lead or tin), for example wiping solder becomes the rate of recovery behind the ingot all up to more than 92%.

2. the crucible device structure of technology special use of the present invention is simple, and is easy to use effective.

Fig. 1 slicker solder of the present invention reclaims the facade view of technology special copple

(1) be that crucible (2) is that weif orifice (4) is a hanger for sidewall of crucible (3)

Fig. 2 slicker solder of the present invention reclaims the vertical view of technology special copple

Fig. 3 contains the mesh screen basket synoptic diagram of the waste and old device that the surface scribbles slicker solder

More specifically describes the present invention with following indefiniteness embodiment, will help understanding, and not as the qualification to protection domain of the present invention, protection scope of the present invention is determined by claims the present invention and advantage thereof.

Embodiment 1

Take by weighing a certain amount of waste and old water tank of automobile and place drum shape mesh screen basket through water flushing after drying, operate by above-mentioned formality and equipment, in fused salt, soaked 3 minutes, in immersion process, make mesh screen basket constantly bob and weave (also can stir fused salt), make the wiping solder that has melted sink to crucible bottom rapidly, used molten salt bath consist of sodium chloride-containing 75%, contain Repone K 25%, heat fused salt with coal gas, the temperature of control molten salt bath is 830 ℃ ± 5 ℃, being pooled to a certain amount of wiping solder discharges from the crucible weif orifice, cast the wiping solder ingot, weigh, from molten salt bath, mesh screen basket is proposed, above crucible, stop a moment, from mesh screen basket, take out the parts of the junked-auto water tank that has disintegrated, putting into the tank that fills water immediately washes, water temperature in the tank is a room temperature, washed 7 minutes, flush away sticks in the salt on the junked-auto tank parts that scatters, weigh after the drying, the alloy of the corresponding trade mark of melting between alloy car is separately delivered in picking, the rate of recovery of the wiping solder behind the ingot casting is 94%, leaded 82.47% stanniferous 15.24% in the wiping solder, cupric 99% in the red copper, in the brass cupric 90%. both can make H62 and H59-1 copper alloy respectively. wiping solder can directly be made scolder.

Embodiment 2

Its working method and equipment used are substantially with embodiment 1, only different is to soak 7 minutes in fused salt, molten salt bath consist of sodium chloride-containing 65%, contain Repone K 35%, the temperature of control molten salt bath is 790 ℃ ± 5 ℃, flushing is 12 minutes in tank, the rate of recovery of the wiping solder behind the ingot casting is 93.9%, in the wiping solder leaded 35.42%, stanniferous 37.66%, cupric 99% in the red copper, in the brass cupric 90%. both can make H62, H59-1 alloy respectively. wiping solder can directly be made scolder.

Embodiment 3

Its working method and equipment used are substantially with embodiment 1, only different is soaked 5 minutes in fused salt, molten salt bath consist of sodium chloride-containing 50%, contain Repone K 50%, the temperature of control molten salt bath is 720 ℃ ± 5 ℃, flushing is 10 minutes in tank, and the rate of recovery of the wiping solder behind the ingot casting is 92%, in the wiping solder leaded 90%, stanniferous 1.65%, cupric 99% in the red copper, in the brass cupric 90%. both can make H62, H59-1 alloy respectively. wiping solder can directly be made scolder.

Embodiment 4

Its working method and equipment used be substantially with embodiment 1, and only different is to soak 10 minutes in fused salt, molten salt bath consist of sodium chloride-containing 35%, contain Repone K 65%, the temperature of control molten salt bath is 760 ℃ ± 5 ℃, flushing is 12 minutes in tank.

Embodiment 5

Its working method and equipment used be substantially with embodiment 1, and only different is to soak 15 minutes in fused salt, molten salt bath consist of sodium chloride-containing 25%, contain Repone K 75%, the temperature of control molten salt bath is 810 ℃ ± 5 ℃, flushing is 15 minutes in tank.

Claims

1, the processing method of the lip-deep slicker solder recovery of a kind of copper and copper alloy products, fusing point is higher than 850 ℃, scribble the copper of terne metal (or lead or tin) and the waste and old device of copper alloy system on the surface, place molten salt bath to soak 1-15 minute, stir fused salt or bob and weave and scribble the waste and old device of terne metal (or lead or tin) in its surface, from molten salt bath, take out the parts of the waste and old device of the copper of disintegration automatically and copper alloy system, in water, wash, feature of the present invention is

1) used fused salt consist of sodium chloride-containing 20-80%, contain Repone K 20-80%,

2) temperature of control molten salt bath is 690 ℃-850 ℃,

3) scribble the copper of terne metal (or lead or tin) and copper alloy system from the surface, the wiping solder of the molten state that separates on the waste and old device (or lead or tin) sinks to the bottom of the container that fills fused salt, discharge from the weif orifice of the lowest part of its container bottom, cast ingot.

2, the processing method that reclaims according to the slicker solder of claim 1 is characterized in that, fused salt consist of sodium chloride-containing 50-70%, contain Repone K 30-50%.

3, the processing method that reclaims according to the slicker solder of claim 1 is characterized in that, the temperature of control fused salt is 700 °-760 ℃.

4, the lip-deep slicker solder of a kind of copper and copper alloy products reclaims the special copple of technology, feature of the present invention is, it is a tubbiness, one weif orifice is arranged, block with a plug, the bottom surface of crucible tilts to the weif orifice place, and the angle of its inclination is 10 °-15 °, and weif orifice is positioned at the lowest part of crucible bottom side.

5, according to the special copple of claim 4, it is characterized in that, around suitable for reading, a flange is installed near crucible.

6, according to the special copple of claim 5, it is characterized in that, three hangers are installed on flange.

According to the special copple of claim 5, it is characterized in that 7, crucible is a round barrel shape, flange is circular, and three hangers are that two angles between the hanger are 90 ° in the position on the flange, becomes 135 ° of angles respectively between two hangers of another hanger and this.