DE1958949A1 - Process for the recovery of copper from insulated copper wire possibly contaminated with tin solder and / or tin - Google Patents

Description

Pennaylvenia ,. UEa.

"Process for the recovery of copper from isolated and optionally with tin solder or other? Meaning contaminated copper drab "

The invention relates in general to the recovery of copper, in particular with ia lectrQlyfckispfe2ainfe © it _? of insulated copper wire waste and in particular Ausschußcfeargen "d" h "games not appropriate the Horm quality bsi the manufacture of insulated KupferdrShten · To recover cL @ s copper is OCE worked up wire a & rhaokt * whereupon by air classification or · air blowout small Xsoliermaterialteilchen, which contain some copper »separates. The part of the initial material separated in this way is then processed further in a manner that is not of interest in the given context. The remaining wind sifting rope '! The AuegangsaiateriaLe is a treatment in an autoclave uateswosfea "oils the major £ ecause the invention forms · Hach the BefasutälCTig in Anto f'^{'^}i5r" IMET to d ^ i? atifsuar ^ fttszid® starting si £ t @ ü? ia ?. dab off una hetiU £ iiW ~ t ^ g; i. ^ eim ^ s? Se

BATH

shakes usd wfiseht with a surfactant, then, treated again in a hammer mill, rinsed and left bit Yasser, dried in a rotary dryer and then treated again if necessary in a hammer mill . Magn @ ttr @ nmmg subjected and noc & tt & ls windsichtet.

From some ÜSA-Pateatschriiten, like the USA-Latent 1 185 641, 1 8 * 2 970, 5 010 852, 1 726 633 » 2 077 785« ad 2 5 * 1 703 Üffilie & e process for re-drinking his iron copper are known, eachä & € & * This state of Secnnik recit is generally held, so that it is close to the specific knowledge of the invention, on the basis of which only a really advantageous, usable process cannot be inferred.

si & d _s wi® erfiadusigsgesiS was established, in particular ti © B & disgiiB ^ ea mi & fm ^ mseMmm ^ m & hm & a. during the treatment in the AntoluMvmL bow ± ® the dix-elct with this treatment level

¥ © rfahr # nsseliritt @ · The production or again

extraction of high-purity copper from insulated waste - * - was or AusschuSdraht, as already mentioned, tried earlier, but the belcannt & ti ¥ sr £ ahr 's were not satisfactory in terms of their speed un & Wirtachaftliehkeit and & © r quality of the recovered copper?.

B © 3? Srfisdimg therefore has the task of sugrunS®, a process ■ tfieä © ^ @ ffiimen'of high-purity .copper * from isolinahmrt@m.kupferdraht

'■ "ad fe.i! B © g © ther vcm copper adhering to Blefetrolytlsas £ © rqualitSt from kupit tin, Sinnlot and Xgplierstaterial, and in! © lyvi ^ lehlorid containing Isoiassmairarialien, make Βί &. Next® tasks and Ife ^ tsile of the

: * ■ *.:. 109823 / 07Ö4 _BÄD

are for the Fachaann avis the following description and the Claims apparent.

The invention relates to a process for recovering copper from isolated and optionally having adhered thereto tin solder and / or tin contaminated copper wire, which is characterized by ₁ to DAB

a) in an autoclave as starting material at most about 12.7 long pieces of insulated copper wire are used, provided that that the input material used au Höchetena about 15 wt .- # of insulating material, at most about 2 wt .- ^ of polyethylene and at least about 5 Sew .- # of polyvinyl chloride consists,

b) through the autoclave charging system, ^{circulate a distillate oil heated to at least 232 0} G, of which at least 10 % of the carbon atoms are bound in aromatic rings and at most 30% in paraffin chains ^:

c) the DistillatSl cools in the autoclave below its flash point, and

d) that which is still present after this treatment and through the treatment separates embrittled foreign material from the pieces of copper wire using mechanical cutting processes »

An important point in the process of the invention is the isolated DAB on-Buarbeitende wire is chopped into pieces of a certain length, and DAB are adhered to the conditions set out in the autoclave * In the erfindirngsgemSS for treating the autoclave charge B _used;:.: Tj.llatöl is it is a terrestrial

1 π ■ - ^i? 7 3 / π 7 ß U, BADOBtölNAi,

"IdeetiiXat * Me ölfceaperatur betsÄgt vorsugswaiee to au 260 ⁰ C, The Hag used · the · © Bsalrtetueke amounts etva 6.35 to 42.7 sau vein of Folyviaylcliloridgeiielt: dee into the autoclave eingesetsten Aesgangsmaterials insufficient 1st d" h "as Veniger It is at least 5 0 "f" - #, so that the raw material is treated with the light oil, further polyvinyl chloride sugeaetst · Before the autoclave opens, it is rinsed with cold oil to avoid soaking. IKLe treatment »» duration The autoclave is 3 hours before yesterday's inspection *. The nacSi of Sbtneosen of euf seuarb "it © nd # ii Auagangamateriale still Bit the Kiapferdrs & tetöcken vermisch tea Preadstoffβ are brittle and adhere who schvaca as copper, eo that they dnroh a Polge of pSsjsiScÄlisohön showers and Brecbwrgängen such treatment in a hammer mill, Hütteln on a »vibration sieve and Vindsioh * th, as well as Haednea, degreasing tuad rinsing, can be removed, which can be used in the term ^ echanieohe separation" susaBmenfaseen *

As audga & eematerial for the method of the invention, before * suggireise hopscotch used, which ait certain Kengen Anfeaftenäes Sense solder and tin is contaminated. The way and together » Aetsyng of the Xsoüersmaterials can be different · With the is the method of the invention to be used as the starting material insulated plucked wire, the insulating material usually consists of The structure is based on Fol ^ rvlnyl chlorid, but others can also Isolation materials be present, a. E rubber, jfjrlon, P0I7-tetrafltiörethylene, Textile and paper «I've already mentioned may, however, as starting material in the autoclave aserhaekte insulated wire bsw. its insulating material

109823/0784

Contain only a certain maximum amount of polyethylene, expressed as a percentage of the raw material used.

The Eupfer wire to be processed is chopped up and sieved so that at least the vast majority of the pieces have a length of 6.55 XB & 12.7 ram · The exact © percentage of pieces with this length is aa and not critical in itself, but should be almost no Brahtatüekchen be longer than 12.7 mm. The chopped up raw material is placed in baskets and placed in an autoclave, which is then sealed. It has been found _t that when aan the wire easily rolled placed in the basket, the Heibe oil can not sufficiently penetrate the material to be treated to cause a corresponding treatment of the insulating material, so that it can not be achieved in this Heise the desired success · It was also found that it is advantageous to wind the chopped up raw material or blow it out with Imtfs. · The air classification can be carried out in a conventional air classification device. The critical point in this pretreatment is that the starting material used in the autoclave should preferably not contain more than about 10% of plastics likewise inadequate, since the plastics have an adhesive effect. The starting material used in the autoclave must therefore contain no more than about 12.7 mm long pieces and have a Kmetstoffgahalt of at most about 10 #

1Q3823 / 0784. BATH

- «■ - · 1358949

# can contain polyethylene · A higher reserves as PsIyätSiylen su rapid Yersagen the process veer because the polyethylene tends to treat _s - like stringing machine mentioned, may the off ·· gangeBateriel h3eb "t" n3 2 percent "used in the autoclave Bring used estilat oil from gelling su. It should therefore wesig mögliefest Polyethylene be voriwinden, d * h "that ssan the hot BestÜlatöi * before it can be eveetat Stus, vSmo lisger iHElaufen laeotft JEKCOX _1, the lower the proaentuale Jbateil to Polyätbyleii ix into the autoclave eingesetsten At" gangB "atea ? ial is ·

Another important factor is the ^ s ^ asBensetstiag of the Auegengsaatex-ia! Used in the autoclave (s is, as already ssw§! Int _s t »e» of the Hiadestge & alis of polyvinyl chloride. It was found that δ & Β? Vmm Uab Am5gang0m & material no or veniger

as äi # «e ^ iii & eer ^ essie $ m £ m§ € <m% m. 5 Se ¥ _e -ie polyethylene 'contains * fias% @ i @ia «i ^! 'beetiaaal? ^, leliandlimgsteiaperatiir and Bes autoclaves released or embrittled Isola- ?' - hv is much more beneficial than with a working method.

WeiTex & ls was found ü & B is shown below a low PVC content of the Atiegangsmaterials inserted into the autoclave by adding

PVCM3tiiökch @ can iateheb8n, and that if _t Sas entire insulation material contained in the inserted into the autoclave "Aiisfpaggaaterial from P ¥ 0 is low and zwecklst, & · Sat © '' kB ?? The total content of these raw materials as P7C is up to about 10 tea- $. / ■

WesatLi <äi © Äsesseaheit of PW sioh has such a favorable effect, is -not o "Bs is assumed that there are several 109823/07 * 04 BAD ₀ RiGlNAU

toren aft & giving are * During the treatment with the hot oil doesn’t form see hydrochloric acid, which is believed to be included in "method of the invention plays an important role, especially in the formation of EU and tin salsa on the solder and tin adhering to the wire to be treated. Furthermore, in the presence of FVG available an exothermic reaction takes place, which sn the places »where one Particularly high carving is desired, β * h * directly on the Surface of the ZJtrahtetüoke asu a typical local elevation leads*

The autoclave is closed, whereupon oil is continuously circulated through the baskets containing the pieces of wire at a temperature between 232 and 260 ° C. The circulation of the oil is important so that the substances to be separated from the copper are flushed away. It has been found that at temperatures below about 252 ° C., irrespective of the duration of the treatment, the success aimed at in the process of the invention is not achieved. The upper limit of the oil temperature depends primarily on the flash point and the decomposition point of the oil used Oils have flash points of over 260 ^° C., but it is known that flames can also occur below the flash point. It has been found that the _{contents of the autoclave>} before opening the autoclave * should cool down to at least 95 ₄ 3 ° ^{C in} order to rule out the possibility of inflammation, although this temperature is well below the flash point of the detilled oil used * The reason that inflammation occur below the expected flash point, is not fully understood * Saher is si * cherheitshalber rinsed with cool oil before opening the autoclave and the iPeaperatur characterized at most about 95.3 ⁰ C overall

109823/0784

- * -; 1958349

e The imaginary maximum treatment temperature iron

260 ⁰ O does not represent a sharp and critical temperature limit * but is simply about the upper limit value of the difficulties arising from the decomposition and ignition of the oil and due to the economic problem that the UL has to be cooled further before the autoclave is opened , is preferably not exceeded. In addition, it was found that "by increasing the treatment temperature to over 260 ⁰ O no acceleration is achieved so considerable that the disadvantages described would be compensated for" as can be seen from the limit values given above for the composition of the deetillatole used as the treatment medium in the autoclave , these are crude oil fractions with a relatively high aromatic content and a relatively low paraffin content. If an oil is used that does not meet the stated conditions, i.e. if the percentages of aromatically or paraffinically bound carbon atoms are outside the stated limit values, the process can easily become clogged due to increased Schlaraa formation.If the conditions are insufficient Oil can therefore not be recycled or recycled back into the process as often as the oils to be used according to the teaching of the invention, and moreover leads to greater corrosion of the device used *

S ¹ Oils suitable for the purposes of the invention are sold under the trade names Sun Oil 310 (oil B) and Sun Oil Circo Light (oil A) These oils are petroleum distillates with the following properties or characteristics:

10982 3/07

TiBkosity, SÜS at sight, ⁰ AH at 15.56 ° 0 YlaniBpun & t ■ O Pot »Point, ⁰ C ⁰ O

oil A

150

162.8 -40

68.9 0 * 886

19 40 41

Oil B

110

-42.8

75.6

0.865

11 43

46

In the table above, Q _n means ge »

bonded carbon atoms, 0 _Ά in Saphtliensingen

C-Atoasi and CL in

0_

Pareffin chains linked O atoms. Although the deep geate applicable treatment temperature of 232 ° 0 below the Melting point of pure tin and dioate at the scfeffielspa ^ rt? by Zicnlot lies, sense and tin solder are removed in the oil bath of the Eupfar « These metals appear in the oil bath as tin-II and lead-salts Salt formation is an exothermic reaction and the resulting local reaction the heat generated on the head surface is increased? the Qe * Effective action of the litigation «During this 3ehan.dlimgS8chrit ~ tea also creates other chemical

Vie already mentioned, daa in this Behandlmigsstiife used · oil during the treatment, the reprocessed Axi $ gangsm & - terimls in 4utol: 3Laven i®n # r wiedar attributed looks wan Sm Kreisla ^ -. ^ ia & a l? os? ratB «uad rather Bauart voa *, in d & m. the twri der

in the

formed visual substances can settle * Bas in the autoclave fed in * oil is heated up ia elaes WSxseatuitaueeher * 9a « Of course, the same oil losses have occurred since the beginning of the year by adding fresh oil. During this stage of treatment ersseugte (carrion «earth blown off»

Hacadem sow the Semperatcop Is autoclave by rinsing with cold "oil at about i21 ° G or venigear geseakt h t _t nlisict nan the irarde the Braatstiieke enthalteadexi Körb" r.ue dea Autokl & irish Herati and IABT to drain * Ea gefuadeR that saßtlicii © yet on the leftover freiadstoff® epröd \ ιηά are friable see 809it leieat by the name? ? as "mechanical separation process Behandlimgesehritte designated ⁸ E ATF can first * What and how" - are vlele such Behandlusgesohritte specifically applied, can voe $ all m drop - ereKihieden Ain · TjplBzh for Abtrennuzg iron ¥ @ £ i8 |> r8 &# dough Ifetes 'iai s§i ^r ö1i®Ä.? »·? # Μιι5 scher iSrennverfahren is f oigfade B @ ih © by

The material to be treated is first treated in a hammer mill after the oil has dripped off, then in a vibrating trough with an alkali-free washing and degreasing agent, s * B, which is available from the Firaa Wyandott © Ohesii © axs under ^ βτ designation " Crystal Soap "marketed product, treated in a wide hammer mill, rinsed in a swivel pan with water, dried in a botation dryer, again in a SsULag mill finally a £ tf © it @ g. Hai winnowed · The three-letatfesssMten Behandlunge "" Mfagm. Ale is sometimes "BicherheitsheX '& ss ¹ * 2i? © e ®aiig ®r- ₉ w ä? End it in other cases not <£££ orderlieft siad"Aa-'ifäffite;#gp tfeechens with detergents or bmSmtqt rinsing « and

10982 ^ / 078 ^ BADORfGiNAL

For example, a solvent can also be removed from the process Apply feeding using OJriehlorethylene «

As has been established, the treatment time in the autoclave should preferably be at least 1 1/2 hours ₄ - (however, a treatment time of more than 3 hours is not necessary so * has never been found, a treatment duration of about 2 hours is particularly favorable «

If post-oxidizing gas atmospheres or other than the specified liquid media are used as treatment media $ z * B ». Water, are obtained, as stated, no satisfactory results, as in the method of the OF INVENTION & Raigo The gate members obtained by the retracts, the invention _v z "3ο that! Obtained as product copper, which can be used without further purification _t and that the Effort in skilled work is very low _r need not due to any minor parts. z * B * Income from air pollution »to be bought *

Below are the characteristics and results' various Experiments listed in a table

The oils 0 and I) listed in the "Oil used" column are trade products that are sold under the designation ^a Sun ßundex 53 "or" Sun Sundex 170 ". *

109823/0784

attempt

, 2 3 4 5 6

Aiff pklaveneins atsiOTt (wire)

isolation

10.0

.2.4

12.0

2.1

5 7

Pl

0 0 O approx. 0.1

^M 0.2 ♦ ».

# PVC (including quantities to be set)

ca <

•1

• Λ Ii

10

5 7

Isolation

PTO ,. PX 2e2Ctil

PVO ₅

_t textile

0.2

IPVO ^ BVQi Pl

PVC,

PVO,

oil »rap ⁰ O

260

232 232 232 260 260 246

Treatment time i «Auto * klav ^ n

2 2

2.5

AWAY

oil

Sn "after autoclave treatment

Pb after autoclave

Sn according to mecban, 3? Γθε * tion

Fb to mechan, !Separation

.3-

5 6

0.070 O ₅ OS? 0.080

O ₄ OO ^ S

0.0097

0.0042

<0.025 0.011 O ₅ OIO 0.012

<Ο.Ο25 ¹

< 0.025

< O ₅ O25

<0.003 δ.028 _{0.0035 O 5} OOI 3

<0.003

<0.003

< 0.003

In the table above, P1 means polyethylene * The autoclave feedstock is about copper wire ₉ which is contaminated with the tin and solder that usually adheres to the industrial selector wires »The specified oil temperatures and treatment times are only approximate values ) "are just the insulating material! an indicated by type and quantity "omissions in columns mean that corresponding values were not available." In all tests, the average ratio of the amount of copper wire used to the oil used for treatment was about 62.6 kg / 3.79 Iitr

109823/0784

Claims (3)

1) Procedure for recovering copper from isolated land possibly with tin solder and / or tin contaminated copper wire * thereby g e k e η η - a) in an autoclave el »starting material at most about 12.7 * nm long pieces of. insulated stomper wire is used, with the proviso that the starting material used is too at most about 15 wt. ~ # of insulating material, at most about 2% by weight of polyethylene and at least about 5% by weight consists of polyvinyl chloride, b) A distillate oil heated ^{to at least 232 0} O circulates through the autoclave for at least one hour, ₉ of whose carbon atoms at least 10 % are bound in aromatic chains and at most 50% in paraffin chains c) the distillate oil cools down in the autoclave below its flash point, and d) that which is still present after this treatment and through di © Treatment of embrittled foreign material by means of mechanical Burning process of the copper wire pieces " 2) Method according to claim 1, characterized in that the temperature of Bestillatols used to treat more than 260 ⁰ C and the treatment time is at most 3 hours in an autoclave ", and that the Beetillatö'l in the autoclave after the treatment at least 109823/0784 , is cooled down to about 121 ⁰ C before opening the autoclave 3) Method according to claim 1 or 2, characterized in that the starting material used is insulated copper wire, the insulation of which contains polyethylene and / or polyvinyl chloride and / or textile material or consists of it and adheres to the tin and / or tin solder, this wire in at most 12.7 now long pieces minced, the lighter separated from the wire eerbackten Leuchen by wind sifting or blowing out with air, the Auegangsoaterial thus obtained, if necessary, as far as polyvinyl chloride is added to _t that of the P ¥ ~ G content is at least 5 parts by weight ίί and then Claim Λ or 2 processed further. 109823/0784