DE2125095B2 - A method for separating the metal components from an aqueous medium by liquid / liquid extraction using an extractant of the hydroxyoyime type - Google Patents

Description

A-Cf = NOH) -R

used, in which R is an aliphatic radical and A is a cyclic organic radical represents which as a substituent at least

a) a hydroxyl group on a ring carbon atom in the 2-position to that ring carbon atom, to which the remainder -Q = NOH) -R is bound, and

b) at least one organic radical R 'and optionally

c) has at least one electrophilic residue.

2. The method according to claim 1, characterized in that one uses a hydroxyomin of the formula given above, in which the radical R is an alkyl radical having 5 to 20 carbon atoms.

3. The method according to claim 1, characterized in that there is a hydroxyoxime of the above used formula, in which the radical A is a substituted phenyl group.

4. The method according to claim 1, characterized in that there is a hydroxyoxime of the above given formula used, in which at least one organic substituent R '5 to 20 Has carbon atoms.

5. The method according to claim 1, characterized in that there is a hydroxyoxime of the above given formula is used in which at least one organic substituent R 'is an alkyl radical.

The extraction of the metal components from aqueous media is carried out according to numerous technical processes carried out with the aim of z. B. at least one particular metal component from more or less to isolate diluted solutions or at least to obtain them in enriched form. The main purpose Another method consists in the separation of unwanted metal ions from aqueous liquids. Selective extraction processes, which allow the separation of different metal components from one another, are of particular importance in the coal and steel industry, where the desired metal components often from aqueous solutions or suspensions of rather complicated mixtures of different Metal salts must be separated. In such cases the starting materials are generally derived from the ore leaching z. B. with water, acids, bases or saline solution is carried out after the raw ores by crushing, grinding, sieving and / or alluvial processing (flotation) into one appropriate shape. After the extraction, the metal components can be treated further, e.g. by washing out of the extract phase, precipitation, electrolysis and / or after pyrometallurgical Methods.

Thus, a method is known, according to which copper from aqueous media using extraction agents is extracted from the hydroxyoxime type. The hydroxyoxime compounds are either <x-hydroxy-substituted aliphatic ketone oximes or 2-hydroxybenzophenone oximes used e.g. B. 5,8-Diethyl-7-hydroxy dodecan-6-one oxime and / or 2-hydroxy-5-dodecylbenzophenone oxime. However, it was found that these known hydroxyoximes have certain disadvantages. The aliphatic <x-HycV <? Xyoxime need z. B. a relatively high pH (i.e. from above 3 to 4) in order to produce a sufficient extraction effect. However, a high pH is associated with associated with considerable consumption of alkali when a strongly acidic aqueous medium is extracted, such as it is generally obtained from copper leaching. The 2-hydroxybenzophenone oximes recommended in GB-PS 10 91354 on the other hand have a very good effectiveness at lower pH values, at their However, a rather long extraction time is required for use, which is important for the large-scale implementation is undesirable. To improve the aforementioned extraction process is also the Measure has been proposed to use a mixture of aliphatic and aromatic ketone oximes use without, however, the results were fully satisfactory.

The object of the invention was therefore to provide a new method of the type explained above to ask, be. which the extraction is carried out in a very short time and at very low pH values can be and in which no mixture of ketone oximes different to achieve good results Type is required.

The invention thus provides a process for separating the metal components from an aqueous one Medium by liquid / liquid extraction using a hydroxyoxime type extractant, wherein the aqueous medium is treated with an organic phase which is an organic, water-immiscible solvent and a hydroxyoxime as extractant e; '. holds, at least some of the metal components are converted into the organic phase and optionally from the organic phase Phase after their separation from the aqueous phase one (s) or more metal component (s) and / or Metal (s) isolated, which is characterized in that a hydroxyoxime of the general formula

Λ -C (NOH) R

used, in which R is an aliphatic radical and A is a cyclic organic radical, which as a substituent at least

a) a hydroxyl group on a ring carbon atom in the 2-position to that ring carbon atom, to which the radical -C (= NOH) -R is bound, and

b) at least one organic radical R 'and optionally

c) has at least one electrophilic residue.

Surprisingly, it has been shown that when using a hydroxyoxime of the general formula given as the extractant, a very high degree of extraction in a broad pH range extending into the extremely acidic area, e.g. B. at pH values of 0 to 2 or even below, can be achieved.

Examples of aliphatic radicals R in the general formula are alkyl, alkenyl or alkapolyenyl radicals. The radical R can be branched or unbranched and contain substituents and / or heteroatoms. Unbranched In general, radicals are very suitable. The number of carbon atoms in the radical R can, for. B. 1 to 20 and is preferably 5 to 20, in particular 7 to 11. Alkyl radicals are preferred as R radicals Specific examples of suitable alkyl radicals are methyl, ethyl, n-pentyl, n-heptyl, n-octyl, n-nonyl, n-undecyl, n-tridecyl and n-heptadecyl groups.

The cyclic radical A in the general formula can be a carbocyclic or heterocyclic radical; this radical may contain one or more double bonds. Specific examples of cyclic Residues from which the radicals A are derived by substitution are the cyclopentyl, cyclohexyl, cycloheptyl, Phenyl and naphthyl group. Aromatic radicals are preferred, in particular the phenyl group.

Examples of organic radicals R 'suitable as substituents are alkyl, alkaryl, alkenyl, alkapolyenyl, Alkoxy, alkylthio and alkoxycarbonyl radicals. This (r) organic radical (s) can (can) be unbranched or be branched as well as substituents and / or heteroatoms exhibit. The number of carbon atoms of such radicals R 'can, for. B. 1 to 20 amount / τ and is preferably 5 to 20, in particular 7 to 14. Preference is given to those compounds in which R 'or at least one of the radicals R 'is an alkyl radical, such as a sec-alkyl radical, is specific examples of suitable ones Alkyl radicals are the methyl, sec-hexyl, sec-heptyl, sec-octyl, sec-nonyl, sec-undecyl and sec-pentadecyl groups. The cyclic radical A preferably has only one radical R 'as a substituent. The total number of C atoms in the radicals R and R 'is expediently 10 to 25, preferably about 14 to about 18. The number the carbon atoms of the radicals R and R 'are also preferably approximately the same.

Specific examples of hydroxyoximes that are very suitable according to the invention are

(5-sec-heptyl-2-hydroxyphenyl) -n-heptyl-

ketone oxime,
(S-sec.-octyl ^ -hydroxyphenylJ-n-octyl-

ketone oxime,
(5-sec-nonyl-2-hydroxyphenyl) -n-nonylketone-

oxime and
(5-sec-heptyl-2-hydroxyphenyl) -n-nonyl-

ketone oxime.
Other suitable hydroxyoximes are

(2-hydroxy-5-methylphenyl) -n-tridecyl-

keiono.xim,
(2-hydroxy-5-sec.-heptylphenyl) -methyl-

ketone oxime,
(2-hydroxy-5-sec-dodecylphenyl) -ethyl-

ketone oxime,
(2-hydroxy-5-sec-undecylphenyl) -n-pentyl-

ketone oxime,
(2-hydroxy-5-sec-hexylphenyl) -n-undecyl-

ketone oxime,

(2-hydroxy-5-sec-pentadecylphenyI) -n-heptyl-

ketone oxime,
(2-Hydroxy-5-selc-octylphenyl) -n-undecyl-

ketone oxime and

(2-Hydroxy-5-sec-octylphenyl) -n-heptadecylketone oxime.

The hydroxyoximes used in the process of the invention are new compounds. they have themselves

ίο to be very effective for the extraction of metal components from aqueous media over a wide pH range, generally down to one Extends value of about 1, proved. If, however, components from media with an even higher

is acidity, i.e. with. pH values below about 1, are to be extracted, the effectiveness of the extraction is often considerably reduced using media such a high acidity can, for. B. from the leaching of copper-containing ores with strong acids. It should It should also be borne in mind that the pH of the aqueous phase during the extraction with a hydroxyoxime decreases as a result of the formation of an equivalent amount of hydrogen ions. Best possible extraction a desired metal component can be obtained even in the aforementioned cases, e.g. B. by carrying out or carrying out the extraction in several successive stages Addition of a base which increases the pH in a suitable manner.

jo Surprisingly, however, it was found that a highly efficient extraction even using a single step over a wide pH range, which is particularly in the extremely acidic area (e.g. down to values from 0 to 1 or even below)

Jj extends, can be done if that as Hydroxyoxime of the general formula given in the cyclic radical A used as extraction agent apart from the hydroxyl group and the radical (s) R ', there is at least one electrophilic rust

Examples of such electrophilic radicals are the halogen atoms, in particular the chlorine, bromine and Fluorine atom, the nitro and cyano group and alkoxycarbonyl radicals of the general formula below

-COOR "

in which R "is expediently an alkyl radical having 1 to 20 carbon atoms. Examples of preferred radicals of these Formula are the methoxycarbonyl and ethoxycarbonyl group. The halogen atoms, especially the chlorine ίο atom, are preferred as electrophilic residues. Excellent results are achieved with the invention. Hydroximes achieved which have only one electrophilic radical on the cyclic radical A. Possibly however, there are 2 or more such radicals)> present, which are identical or different from one another could be. These radicals are particularly effective when the cyclic organic radical A to which they are attached are bonded, is an aromatic radical, in particular the phenyl group.

ho If the electrophilic residue is simultaneously one represents organic radical R ', as it is e.g. B. is the case with an alkoxycarbonyl radical does not have to be at the same time another radical R 'may be present. In these cases it is generally advantageous to add the total number to h) carbon atoms of one or more of these electrophilic Residues of the aliphatic radical R and - if present - additional radicals R '10 to 25, is preferably 14-18.

Favorable positions of the electrophilic residue (s) in the cyclic radical A are generally those positions which correspond to the hydroxyl group in 2-position confer increased acidity. If the cyclic radical A is a phenyl group, the 3- and / or 5-position is most preferred, with the 2-position is occupied by a hydroxyl group. B. with the 3-chloro-2-hydroxyphenyl compounds the hydroximes of the general formula obtained The organic radical (s) R 'can (Can) generally assume any of the remaining positions of the cyclic radical A. Compounds suitable according to the invention are, for. B. those which have a in the 5-position of a phenyl group Radical R ', preferably an alkyl radical.

Hydroxyoximes are thus further examples of extraction agents which are very suitable according to the invention the given general formula, in which the radicals A and R are the following groups:

is hydrolyzed, or condensed with a carboxylic acid R-COOH in the presence of boron trifluoride, and the obtained ketone is then converted into the oxime. As starting materials for the foregoing The respective processes are suitable - generally by alkylating phenol with a «-Olefin obtained - 4-alkylphenoie, which before the Acylation can optionally be chlorinated in the 2-position. The corresponding hydroxyoximes can z. B. be prepared according to the following reaction scheme:

5-sec-heptyl-3-chloro-2-hydroxy-

phenyl n-heptyl

S-sec ^ Octyl-S-chloro ^ -hydroxy-

phenyl n-octyl

S-sec.-Nonyl ^ -chlor ^ -hydroxy-

phenyl n-nonyl

5-sec-heptyl-3-chloro-2-hydroxy-

phenyl n-nonyl

S-sec.-octyl-S-chloro ^ -hydroxy-

phenyl n-nonyl

5-methyl-3-chloro-2-hydroxyphenyl n-tridecyl

5-sec-heptyl-3-chloro-2-hydroxy-

phenyl methyl

S-sec.-DodecylO-chloro ^ -hydroxy-

phenyl ethyl

5-sec-undecyl-3-chloro-2-hydroxy-

pheny! n-pentyl

S-sec-hexyl-S-chloro ^ -hydroxy-

phenyl n-undecyl

5-sec-pentadecyl-3-chloro-2-hy-

droxyphenyl n-heptyl

S-sec.-octyl-S-chloro ^ -hydroxy-

phenyl n-undecyl

S-sec.-octyl-S-chloro ^ -hydroxy-

phenyl n-heptadecyl

Excellent results are achieved in particular when using (S-sec.-Octyl-S-chloro ^ -hydroxyphenyl) -n-nonylketonoxir. achieved.

In the process of the invention, mixtures of 2 or more hydroxyoximes of the specified general formula can be used. Simultaneously with one or more of the invention Hydroxyoximes can also use other suitable extractants, e.g. B. Hydroxyoximes of a different type, be used.

The hydroxyoximes of the general formula given are easy to prepare, e.g. B. by oximation of the corresponding ketones. According to a preferred process for the preparation of hydroxyoximes which Have a substituted phenyl group A, is an alkylphenol, which is optionally substituted in the nucleus by a electrophilic radical, such as a chlorine atom, is substituted with an acid moride R-COCI or with a Trichloralkane R - CCI3 in the presence of aluminum chloride, the product obtained in the latter case

O λ C-R

(Cl)

OH

NOH

However, the halogenation can also be carried out in a later process stage, for example on the ketone before it is converted into the oxime. Specific examples of commercially available 4-Alkylphenoie, which can be used in the aforementioned processes, are 4-heptyl-, 4-octyl- and 4-nonylphenol.

For oximation, the respective alkylphenyl ketones can be refluxed with a hydroxylamine salt Implementation. For this purpose, the reaction components in z. B. an alcohol, like Ethanol, as well as in the presence of a base such as pyridine, refluxed. The base is used for Binding of the acid component added to the hydroxylamine. The hydroxylamine salt, e.g. B. the hydrochloride or hydrogen sulfate, is preferably used in excess in the aforementioned process.

The method used in each case for the preparation of the extractant used according to the invention depends on the respective compounds used as starting materials or on the effectiveness of the relevant process when using such starting materials.

For a selective extraction according to the invention Process, such an organic solvent is chosen that the organic phase is not or dissolves only very slightly in the aqueous medium and vice versa. The mutual miscibility of the two Phases should preferably be at most 5 percent by volume, in particular less than 1 percent by volume. Examples of suitable solvents are halogen-containing solvents such as chloroform, 1,2-dichloroethane, 1,2-dichloropropane or di- (2-chloroethyl) ether, as well as in particular hydrocarbons such as kerosene, toluene or the xylenes.

The organic phase can also contain other components, e.g. B. an additive for prevention the formation of emulsions or the breaking of Emulsions formed during the extraction of the aqueous medium, in the course of which vigorous stirring to ensure good contact / wipe the two phases emD is not recommended. have formed

can. A long chain is generally used for this aliphatic alcohol used.

The method of the invention is very suitable for the separation of, for example, copper, iron. Nickel and / or cobalt (optionally together with other metal components). A special meaning possesses the process according to the invention for the selective separation from solutions which contain at least 2 Metal components included. The raw materials subjected to extraction are often derived /. B. from ore leaching, for example with acids or with a base such as ammonia (under pressure) is carried out after the raw ores are in a appropriate shape.

When copper (II) components of iron (III) and / or other metal components. like nickel or Cobalt to be separated, low pH values are preferred, in particular pH values from 0 to 2. If, on the other hand, nickel components are to be separated from cobalt components,> can be assumed from an aqueous ammoniacal medium, the cobalt components if necessary previously converted into the trivalent form by oxidation, in which the nickel components keep the bivalent form. For the oxidation, for. B. Oxygen or a free one Oxygen containing gas. preferably air is used.

In order to successfully carry out the selective extraction of copper components according to the method of the invention, the aqueous medium, such as a solution derived from ore leaching, should preferably have a pH of at most 2.0. especially from 0 to 1.5. exhibit. Hydroxvoximes of the general formula given, which have an electrophilic radical in the cyclic radical A, generally have a particularly low effectiveness in the pH range from 0 to 0.8, while the other hydroxyoximes used according to the invention are highly advantageous at a somewhat crude pH can be used. _: preferably in the pH range from 1 to 1.5. Surprisingly, it has been found that the copper can easily be extracted from aqueous media which contain both iron and copper components when the aforementioned pH ranges are used, while the iron remains. If necessary, the aqueous solutions from the leaching plant are adjusted to the desired pH value by adding acid, such as sulfuric acid.

The concentrates of the metal components in -, .. aqueous medium can lie within wide ranges and are generally 0.01 to 1 mol / liter, preferably 0.05 to 0.5 mol / liter.

According to the invention, the selective extraction is preferably carried out continuously. It is ν expedient to promote the contact between the two phases by vigorous stirring and that Continue stirring until a state of equilibrium is established between the two phases shark. Generally after 1 to 5 minutes this will be the t, r. Case. It is expedient to have a volume ratio of the organic phase to the aqueous medium of 1: 3 to 3: 1 applied.

The extracted (n) metal component (s) may (can), with advantage from the organic phase, which in _t ~ - represents aligemeinen a solution of a complex of the respective hydroxy-oxime and the relevant metal in a suitable solvent such as kerosene.

by washing this phase after it has been separated from the aqueous phase with an aqueous solution of a strong acid, preferably sulfuric or nitric acid, are separated.

The metal component (s), such as copper, is (are) transferred into the washing solution in the form of the corresponding salts, such as the sulfates. From this they can then by conventional methods, for. B. be separated in the form of salts by evaporation of the water and / or crystallization, or as metals by direct electrolysis. The organic phase, which contains the released extraction agent, is advantageously used for further extractions. However, it is often advisable to use a base such as ammonia for the aforementioned washing, since the desired metal component ( e.g. Ni) can then in many cases become precipitated by evaporation of the ammonia.

In other cases it may be useful to use a metal component directly from that component to separate enriched organic phase by hydrogenation of the phase. This method allows it often, “read the metal in question in powder form obtain.

The examples illustrate the invention.

A. Manufacture .i.ng of hydroxyoximes of the specified
general formula

a) Preparation of (2-hydroxy-5-methylphen \ I) -n-tridecylketone oxime

228 g (IMoI) synthetic acid and 238 g (2MoI) thionyl chloride are in a thermometer. Combined 2 liter flask equipped with a stirrer and reflux condenser. The mixture is gradually heated with stirring and then refluxed for 150 minutes. The excess thionyl chloride is distilled off under reduced pressure. The residue obtained is 246.5 g (1 mol) of myrstinic acid chloride, which is added dropwise into a second 2-liter three-necked flask, which is also equipped with a thermometer. Stirrer and reflux condenser is equipped and in which 108 g (1 mol) of p-cre ^ ol are presented. The mixture obtained in the second flask is ^{stirred at 80 °} C. until the evolution of hydrogen chloride has ceased. The aforementioned mixture is then poured into water and the aqueous mixture is stirred at 80 ° C. The organic layer is extracted with diethyl ether and the extract is washed successively with water, aqueous sodium bicarbonate solution and finally again with water and then dried over sodium sulfate. After distilling off of the ether at reduced pressure, 302 g of the crude p-cresyl myristic acid are obtained, which are treated further without purification The temperature is increased to 90 to 115 ^° C. and the mixture is stirred until foaming, after which it is stirred for about 150 minutes, the warm mixture is then poured into excess 6 η hydrochloric acid the mixture is extracted with diethyl ether and the ether extract is nachei nander with water, aqueous sodium bicarbonate solution and washed again with water, and finally over

Dried sodium sulfate. In this case 56.8 is obtained 283 g of colorless crystals of 2-myristoyl-5-methyl phenol; mp. 57.1 to ⁰ C. Finally, 270.3 g (0.85 mol) of the above Ketophenols, 70.9 g (1 , 02MoI) hydroxylamine hydrochloride and 312 g (3MoI) sodium acetate trihydrate and 1 liter of ethanol are placed in a 2-liter three-necked flask equipped in the usual way, and the mixture is heated for 4 hours. After driving off the alcohol on a steam bath, the residue obtained is taken up in diethyl ether and the ethereal solution is washed successively with water, aqueous sodium bicarbonate solution and again with water and finally dried over sodium sulfate. After separating off the ether, 310 g of crude (2-hydroxy-5-methylphenyl) -n-tridecyl ketone oxime are obtained, which is contaminated with 2 to 3% of the ketophenol used as the starting compound. After recrystallization of this oxime from an ether / ethanol mixture, aqueous white crystals with a melting point of 98.5 to 100.3 ° C. are obtained which are very readily soluble in ether and kerosene and moderately soluble in ethanol.

b) Preparation of (2-hydroxy-5-sec-dodecylphenyl) ethyl ketone oxime

92.5 g (IMoI) propionyl chloride and 262 g (IMoI) p-sec-dodecylphenol (obtained by alkylating phenol with tetrameric propylene) are combined in a 2 liter three-necked flask equipped with a thermometer, stirrer and reflux condenser. The mixture obtained is gradually heated with stirring and then refluxed for at least t hour. The mixture is then poured into water and the aqueous mixture is stirred at 60 ° C. to decompose the excess propionyl chloride. It is extracted with pentane and this extract is washed successively with water, aqueous sodium bicarbonate solution and again with water and finally dried over sodium sulfate. The pentane is then distilled off, after which 298.4 g of crude p-dodecylphenyl propionate are obtained. The total amount of this ester, along with 140 g (1.05 mol) of aluminum chloride, is placed in a 2 liter three-necked flask equipped in the conventional manner. The temperature is gradually increased until the foaming has stopped. The mixture is then stirred for about 1 hour at 12O ⁰ C. The warm mixture is then poured into excess 6 η HCl and the resulting mixture is extracted with diethyl ether. The ether extract is washed successively with water, aqueous sodium bicarbonate solution and again with water and finally dried over sodium sulfate. This gives 308.4 g of crude (2-hydroxy-5-sec-dodecylphenyl) ethyl ketone.

298.9 g (0.94 mol) of the aforementioned ketone, 70.9 g (1.02MoI) hydroxylamine hydrochloride, 312 g (3MoI) Sodium acetate trihydrate and 1 liter of ethanol are supplied in a conventional manner Given a 2 liter three-necked flask. After about three hours of heating and evaporation of the ethanol in one Steam bath, the residue obtained is taken up in diethyl ether, and the ethereal solution is with Water, aqueous sodium bicarbonate solution and washed again with water and finally over Dried nairium sulfate Ether at reduced pressure gives 333 g (1 mol) of crude (2-hydroxy-5-sec-dodecylphenyl) ethyl ketone oxime, which is easily soluble in kerosene and without

further purification can be used as an extractant for copper.

c) Methods analogous to those described in section a) - are used to produce the following ketone oximes manufactured:

(2-hydroxy-5-sec.-heptylphenyl) -methyl-

ketone oxime
(2-hydroxy-5-sec-heptylphenyl) -n-heptyl-

ketone oxime
(2-hydroxy-5-sec-octylphenyl) -n-octyl-

ketone oxime
(2-hydroxy-5-sec-undecylphenyl) -n-pentyl-

ketone oxime
(2-hydroxy-5-sec-hexylphenyl) -n-undecyl-

ketone oxime
(2-hydrexy-5-sec-pentadecylphenyl) -n-heptyl-

rvCiGnoxirn
(2-hydroxy-5-sec-octylphenyl) -n-undecyl-

ketone oxime
(2-hydroxy-5-sec-octylphenyl) -n-heptadecyl-

ketone oxime
(2-hydroxy-5-sec-nonylphenyl) -n-nonyl-

ketone oxime and
(2-hydroxy-5-sec-heptylphenyl) -n-nonyl-

ketone oxime.

d) Preparation of (5-sec-octyl-3-chloro-2-hydroxyphenyl) -n-nonylketone oxime

490 g (2.36 mol) of 4-sec-octylphenol (commercial product) are dissolved in 1.5 liters of chloroform. 53 liters (2.37 mol) of chlorine gas are then added to the solution obtained at temperatures from -15 to -1O ^{0 C with a}

Γι throughput of 20 liters / h initiated. Then will the mixture was allowed to stand overnight, after which the chloroform was evaporated. This gives 564 g (2.34 Moles) 4-sec-octyl-2-chlorophenol (product I). The yield is 98.7%.

in 430 g (2.5 mol) of CapnnÄure are 4 hours below
Boiled reflux with 950 g (8 mol) of thionyl chloride. After the unreacted thionyl chloride has been separated off under reduced pressure, 456 g (2.5 mol) of crude n-decanoyl chloride (product II) are obtained. the

ι-, yield is 100%.

The total amount of the product I is then heated in a flask equipped with stirrer, reflux condenser and dropping funnel, three-neck flask at 80 ⁰ C, and then 450 g (2.48 mol) of the product II within

-, ο added dropwise for 90 minutes while stirring. The heating to ST C is continued until the evolution of hydrogen chloride has ceased and then for a further hour. The mixture is then poured into water and the aqueous mixture is heated to 80 ° C. for 1 hour. After cooling, the mixture is extracted with ether and the ether extract is washed with water, sodium bicarbonate solution and again with water. After drying over sodium sulfate, the ether is reduced under reduced pressure

bo disconnected. This gives 840 g (2.13 mol) of crude Capric acid ^ -sec.-octyl ^ -chlorophenyl ester. The yield is 91%.

The aforementioned ester is 49 hours at 80 ⁰ C and a further 10 hours at 105 ° C with 314 g (2 ^ 5 mol) of AlCl ₃

“5 heated the still well mixture is then in a Excess of a mixture of equal parts by volume of concentrated aqueous hydrochloric acid and water poured, and the resulting mixture is to

Complete decomposition of the complex formed on Table I 80 ⁰ C heated. The oil layer is extracted with ether and the ether extract is washed repeatedly with water and sodium bicarbonate solution and then dried over sodium sulfate. After distilling off the ether under reduced pressure, 630 g (1.6 mol) of crude (5-se ^ .- octyl-3-chloro-2-hydroxyphenyl) nonyl ketone are obtained. The yield is 75%.

The aforementioned ketone is finally converted into the oxime by leaving it in 100 percent for 72 hours Ethanol together with 140 g (2MoI) hydroxylamine hydrochloride and 390 g (4 mol) of sodium acetate is refluxed. The ethanol is then evaporated, the residue taken up in ether and the ether layer washed and dried over sodium sulfate. Receives after evaporation of the ether one 591 g (1.45 mol) of (S-sec.-octylO-chloro ^ -hydroxyphenyl) -n-nonylketone oxime. The yield is 90.5%.

attempt PH value Extracted lot Fe " (additive), wt .-% 2.2 Cu ^ff 4.7 1 0.20 12.1 7.1 2 0.55 33.6 10.4 3 0.90 63.3 15.5 4th 1.25 89.5 24.2 5 1.55 98.9 43.8 6th 1.85 100.0 7th 2.25 100.0

Example 2

rrii · '2-H vriroy v- .S- ^

B. Extraction attempts
example 1

Extraction tests are carried out in a specially constructed separating funnel that consists of one with a measuring unit, straight-walled Contains a vessel with a capacity of 0.25 liters. At the lower end of the funnel has a Stopcock for emptying. The upper opening is used to introduce the double-paddle stirrer and also serves as a feed inlet. To carry out the extraction experiments, 50 ml treated an aqueous solution containing metal components with 100 ml of the organic extraction solution, stirring at a speed of about 2000 rpm.

Selective extraction of Cu ^{2 f} with (2-hydroxy-5-sec-octylphenyl) -n-octylketone oxime

The aqueous starting material used is a solution which contains 3.18 g Cu ^{2 +} and 2.79 g Fe '* per liter in the form of the sulphates in question and an additional 20 g H ₂ SO ₄ . The pH of the solution is 0. The solution is then treated with a 0.5 M solution of the hydroxyoxime in kerosene, the volume ratio of the organic phase to the aqueous phase being 2: 1. Neutralization is then carried out with vigorous stirring at room temperature by adding 25 weight percent aqueous ammonia at a rate of 0.1 ml / min. The addition of ammonia is interrupted at various intervals.

After a further two minutes of stirring, the phases separate from each other, and it is the pH of the aqueous phase determined The organic phase is then regenerated by back wash with 2 η H ₂ SO _4, and it is the present in the aqueous phase obtained copper and amount of iron determined.

From Table I are the amounts of copper extracted at different pH values and the proportions of the same pH value extracted at the same time. Iron visible. The pH values are defined as the respective pH of the aqueous solution in equilibrium with the corresponding organic phase.

phenyl) ethyl ketone oxime

In each experiment 50 ml of a copper sulphate solution (0.05 m Cu), which has a pH value of 0.7, with 100 ml of a 0.5 M solution of (2-hydroxy-5-sec-dodecylphenyl) ethyl ketone oxime stirred in kerosene. While stirring, the pH is increased by adding 25 percent strength by weight aqueous ammonia set a throughput of 0.1 ml / min. Stirring is then continued for 2 minutes. If then has separated the organic from the aqueous layer, the pH of the aqueous layer is measured. The copper content in the organic layer, which is backwashed with 100 ml of 2 η Sulfuric acid was determined. Table II shows the results.

Table II pll-Wcrt Amount of copper extracted attempt (additive). Weight percent 0.32 12.9 1 0.60 41.2 2 1.04 73.8 3 1.32 97.3 4th 2.14 100.0 5

From the values listed in Table II it can be seen that those used according to the invention Hydroxyoxime is highly effective at least down to a pH value of 1.04 and even a little below that Represent copper extractants. This pH range is the same for copper extraction as it is for ore leaching accruing fluids of interest.

Example 3

Selective extraction of Cu ²⁺ with (5-sec-octyl-3-chloro-2-hydroxyphenyl) -n-nonylketone oxime

The aqueous starting material used is a solution which contains 3.18 g Cu ²⁺ and 2.79 g Fe ³⁺ per liter in the form of the sulfates in question and an additional 20 g HiJO _4. The pH of the solution is 0. The solution becomes treated with a 0.5 M solution of the hydroxyoxime in kerosene, the volume ratio of the organic to the aqueous phase being 1: 1

J3

with vigorous stirring at room temperature, neutralization by adding certain proportions made of 25 weight percent aqueous ammonia with a throughput of 0.1 ml / min.

After stirring for a further two minutes, the phases separate from one another and the pH of the aqueous phase is determined. The organic phase is then regenerated by backwashing with 2η H2SO4. The amount of copper and iron are then determined by atomic absorption measurements of the aqueous phase obtained.

The extracted at different pH values, copper values are the same as the units of ^be: the same pH values simultaneously extracted from table 111 F.isens visible. The pH values are given as the respective pH value of the aqueous solution in the state of equilibrium with the corresponding organic

Table III

attempt

PH value

Extracted amount (additive). (iew .-%

Cu

I. 0.06 59.1 2 0.21 90.9 3 0.56 95.9 ι 0.77 96.8

le ''

4.9 5.4 6.1

7.3

Example 4

Extraction of Cu * with (5-sec-Octy! -3-ch! Or-2-hydroxyphenyl) -n-nonylketone oxime

An aqueous solution which contains 3.18 g of Cu ¹ - in the form of the sulfate and 20 g of H ₂ SO * per liter is extracted with a 0.5 M kerosene solution of the hydroxyoxime. The method described in Example 3 is used analogously . The results are shown in Table IV.

Temperature of 25 ⁰ C brought. This solution contained 0.2 mol of ketone oxime per liter of diluent (a low aromatic kerosene fraction) as the organic phase. The temperature of the double-walled vessel was kept ^{at 25 0} CiO ^ ^{0 C with a thermostat.} A six-blade turbine stirrer, which was started after the organic phase had been introduced, was arranged in the vessel. The agitator worked at 2000 rpm. 100 ml of copper sulfate solution were then quickly introduced into the double-walled glass vessel as an aqueous phase at a temperature of 25 ° C. This aqueous phase was prepared from a solution of 3.95 g of O1SO4 · 5H> O and 16.1,; NajSOj · IOH2O in 500 ml of water and was adjusted to a pH of 1.93 with concentrated IKSOj The solution contained exactly 2 g of Cu per liter.
The organic and aqueous phases were

The dispersion obtained were taken after 30, 60, 90, 120 and 600 seconds, homogeneous samples. While Upon stirring, Cu was taken up into the organic phase containing the ketone oxime. It was possible, homogeneous samples can be taken because the vessel was provided with a sample drain cock without dead space. The samples immediately formed a layer. A standard set of the resulting upper ones Layer (organic phase) was made using an automatic diluter with an exactly known Amount of 0.5 percent ENT mixed. The mixture was then shaken for 10 minutes so that a complete washing out of the copper in the ENT solution took place.

The degree of dilution was chosen so that the Final concentration of Kup'xr in the HNOi solution was within the range in which the copper content was determined directly by atomic absorption spectrometry could be. That value of the sample at which there is no change in the Cu absorption in the organic phase can be determined and for the established that the state of equilibrium has been reached had been. was rated 100. All other values are expressed as percentages been.

Table IV

Try pH amount of extracted

Cu "^ (additive),

Weight percent

1 C. 72.8 2 0.05 82.8 3 0.12 90.9 4th 0.20 97.0 5 0.35 100.0

The following ketone oximes according to the invention were found

2-Hydroxy-5-tert.-non \ I-acetophenonox'm *)

2-hydroxy-5-tert.-octylaceto.phenonox.im

2-Hydroxy-5-octyl phenyln-heptyikeioxime

(Oxime B)

Melting point 83.5-85 C (oxime c)

Melting point 70 ° C (Oxirn D)

*) With a 66 percent content of pure oxime maximum copper acceptance test.

The results listed in Table IV show that extraction of the copper down to the very effective a pH of 0 is achieved. Of course, you can also work with a higher acidity.

Example 5

In a double-walled glass vessel with a capacity of 250 ml, 100 ml of normal solution of the ketone oxime to be examined were added to a compared to 2-hydroxy-5-nonylbenzophenone oxime (Oxime A), which is commercially available under the name LIX ö5 N® is available as a solution of 's mol per liter of kerosene fraction. All three oximes B, C and D were made as a solution of 0.2 Moles of oxime tested in the aforementioned low aromatic kerosene fraction. Oxime A was made with the the same diluent diluted in a solution of 0.2 mol.

15th A (comparison) organic 21 25 % 095 16 % Oxime D % % Oxime 84.0 92.8 g / L 79.3 Tabel Absorbed Cu in the 68.4 g / L 93.6 99.0 1.55 93.1 time in Oxime 84.7 1.66 Layer in g / l 96.8 100 1.82 98.2 Seconds g / L 89.8 1.85 B. 100 1.92 100 1.34 91.8 1.92 and% of equilibrium concentration 1.96 30th 1.66 1.98 Oxime C 60 1.76 g / L 90 1.80 1.82 120 1.94 1.96

600 1.96 100 1.98 100 1.96 100

From the above kinetic experiments it appears that the commercially available 2-hydroxy-5-nony benzophenone oxime compared to the compounds according to the invention needed a longer time to full the Cu constantly extracting.

Claims (1)

Patent claims: 1. Process for separating the metal components from an aqueous medium by liquid / Liquid extraction using a hydroxyoxime type extractant using the aqueous medium treated with an organic phase, which an organic, with water not Miscible solvent and a hydroxyoxime as extractant contains, at least a part the metal components are transferred into the organic phase and optionally from the organic phase Phase after their separation from the aqueous phase, one or more metal components and / or metal (s) insulated, characterized in that that you have a hydroxyoxime of the general formula