DD291317A5 - METHOD FOR SEPARATING COMPLEX-LINKED COPPERIONS AND COPPER DEPOSITS FROM USED GOODS AND OTHER WAESSRESS SOLUTIONS - Google Patents

Abstract

The invention relates to a method for the separation of complexed copper ions and copper abrasion from spent drawing agents and other aqueous solutions, which is preferably applicable in the field of non-ferrous metallurgy. According to the invention, the object is achieved by subjecting a solution of a pulling agent having a p H value between 8 and 10 to ultrafiltration, wherein metal abrasives, oils and organics are separated, hydrazine sulphate added to the filtrate with constant stirring and the precipitate after addition filtered from flocculants. It is also possible to add the filtrate to an electrolysis process. Separation; Copper ions, complex bound; p H value 8 to 10; Ultrafiltration; hydrazine sulfate; flocculants; filtration}

Description

Field of application of the invention

The invention relates to a process for the separation of complexed copper ions and copper abrasion from spent drawing agents and other aqueous solutions, which is preferably applicable in the field of non-ferrous metallurgy.

Characteristic of the known state of the art In wire drawing, the use of suitable drawing means to achieve high productivity is particularly important. These However, drawing agents are not unlimited use and must be renewed at certain intervals, wob the egg

used drawing agents are to be disposed of without damage. Most of the known drawing agents, either on mineral oil or on an aqueous basis, contain complexing agents in various concentrations. When pulling Kupferleg'orungsdraht therefore forms a stable copper complex in the drawing agent. In addition, a very fine copper abrasion with a

Grain size of 0.2-20pm, which can not be separated with the usual filter devices. In the known Drawing agents is present as a complexing agent mainly triethanolamine. Due to the complexing agent, the workup

and copper recovery considerably more difficult.

It is well known in the art to use spent mineral oil based make-up emulsions through the use of Process for vacuum evaporation, work up acid or salt cleavage. In the vacuum evaporation is obtained as an end product, an oil containing copper and organic substances and the Processing of the oil difficult. The application of vacuum evaporation is also very energy intensive. Acid cleavage gives an acidic oil which, in further processing, especially during combustion, Corrosion problems. The aqueous phase must then be treated further. For aqueous-based drawing agents and wastewater containing complexed copper ions, the vacuum evaporation

just a method to remove the large amount of water.

With the methods described so far no copper recovery took place. It is necessary to destroy the forming copper complex. For this purpose, the following methods are known:

- Elimination of the copper by precipitation with lime or other alkaline solutions (DD-PS 236720). Precipitation of the copper as hydroxide is not achieved due to the present pH in the drawing agent.

- Deposition of the copper by cementation, wherein a change in the pH in the acidic region is required.

- Precipitation by means of sodium dithiomite (DE-PS 2930110). No complete destruction of the complex is achieved; the residual copper levels are too high.

- Precipitation with sulfides

It is achieved a difficult filterable Niederschlug. The Siilfidüberschuß must be removed by the addition of Fe (II) salts again.

- Addition of Al or Fe powder (DE-PS 2917 597). The stable copper triethanolamine complex is not destroyed.

It is difficult to carry out all the precipitation processes described, since oils, organic substances and copper abrasion are present in the precipitated solutions.

- Carrying out a copper electrolysis

The implementation of an electrolysis is not possible in the original solutions. The deposited precipitate adheres poorly and the current efficiency is low.

Object of the invention

The aim of the invention is to limit exceedances of heavy metal ions, in particular copper from amine complexes, to prevent wastewater and recover the copper.

Explanation of the essence of the invention

The invention has for its object to work up spent oil-based, water-based and wastewater, which contain heavy metal complexes in the form of Kupvertriethanolaminkomplexes.

Eriindungsgemäß the object is achieved in that an aqueous alkaline Ziehmittellösung mi * is subjected to a pH between 8 and 10 ultrafiltration using a Zolluloseacetatmembran, wherein metal abrasion, oils and organic substances are separated and the filtrate is added with constant stirring Hydrazinsulf at , And the precipitate is filtered off after addition of flocculants. It is also possible to supply the filtrate to an electrolysis.

AusfQhrungsbelsplele The invention will be explained in more detail below with reference to two embodiments.

Bet game 1

With 40 liters of a spent aqueous-based draw solution, having a pH of between 8 and 9, becomes ultrafiltration

carried out.

Using a cellulose acetate membrane, copper debris and other interfering components are separated. The spent drawing agent has the following composition:

CU (, _t i4 "): 1.0 g / l CU (i, "i: 1.4 g / l org. ingredients: 3% PH value: 8th

The copper triethanolamine complex in the filtrate is further treated for copper recovery. To destroy the complex 80 g of hydrazine sulfate are added to this solution with constant stirring. The resulting precipitate is filtered off after addition of flocculation aids.

It is also possible to subject the filtrate to electrolysis. For the relatively low copper contents, a rolling-layer electrolysis cell is suitable for this purpose.

Example 2 E;) is a spent oil-based drawing agent which has the following composition:

01: 10% Cu (ie ,,, o: 1.6 g / l Cuiiut): 1.2 g / l PH value: 8th Amount: 1m ³

The work-up is carried out analogously to Example 1 in the following substeps:

- Dui the conduction of the ultrafiltration with a cellulose acetate membrane to separate the oil and chs Kupferabriebs. By recycling the solution can be concentrated to an oil content greater than 00%.

- Treatment of the filtrate with hydrazine sulfate. This takes place in a cylindrical container with internal stirring. The reaction time is max. 10min. Also in this case, the implementation of a copper electrolysis would be possible.

Claims (3)

A process for the separation of complexed copper ions and copper abrasion from spent drawing aids and other aqueous solutions, characterized in that an aqueous alkaline solution of a drawing agent having a pH of between 8 and 10 is subjected to ultrafiltration, whereby metal abrasion, oils and organic matter are separated Hydrazine sulfate are added to the filtrate with constant stirring and the precipitate is filtered off after addition of Rockungshilfsmitteln. 2. The method according to claim 1, characterized in that a Triethanolaminkomplex is constructed. 3. The method according to claim 1 and 2, characterized in that the filtrate is fed to an electrolysis.