JPS5933651B2 - Method for extracting copper valuables from aqueous solution using hydroxy-oxime, novel oxime, and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the separation of copper values from an acidic aqueous solution containing copper values by liquid-liquid extraction using an organic solvent and an extractant containing dissolved hydroxyoxime. and novel oximes.

Oxime extractants are described in the following literature: (A) British Patent No. 1322532; this includes the general formula [
In the formula, R represents an aliphatic group, and A represents at least the carbon atom of the ring at the 21st position (assuming the carbon atom of the ring to which the -C(-NOH)-R group is bonded is the 11st position) as a substituent. The use of hydroxy-oximes is disclosed.

(B) U.S. Patent No. 3,428,449;
The use of 2-hydroxybenzophenone oximes substituted with one or more saturated or ethylenically unsaturated aliphatic groups or one or more corresponding ether groups is disclosed.

(0 German Patent Application Publication No. 2334901; this includes the general formula (in the formula, all R's may be the same or different, but include a halogen atom, a nitro group, a cyano group, a primary amino group, a secondary
Amino group, tertiary amino group, alkyl group, alkenyl group,
represents a cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkoxy group or acyloxy group or substituted derivatives thereof, n is an integer from 1 to 4, and the aldoxime is one or more The use of salicylaldoximes having a total of at least 3 carbon atoms in the alkyl group R is disclosed.

The extraction can be carried out continuously by contacting the acidic aqueous solution with a solution of the hydroxyoxime, for example kerosene, preferably with vigorous stirring.

The organic phase is then separated from the aqueous phase and stripped with an aqueous solution containing a strong acid. The copper values are thus transferred as copper salts to the stripping aqueous solution and then recovered, for example by crystallization or as copper by electrolysis, while the organic phase containing the liberated hydroxy oximes is removed. is advantageously used again for the subsequent copper extraction. This extraction is very suitable for separating copper from iron values. In U.S. Patent No. 3,428,449,
The 2-hydroxybenzophenone oxime described in (B) above can be synthesized by the general formula It is disclosed that copper extraction efficiency is improved when used in combination with aliphatic alpha-hydroxy oxime (which may be atomic).

It has now been found that other oxime combinations can be used to achieve the improvements described above, and the degree of improvement is often even greater.

The present invention relates to an organic solvent, and a compound having the general formula (a) (wherein R represents a hydrogen atom or an aliphatic group, and A represents a bond with a -C(=NOH)-R group) dissolved in the organic solvent. having a hydroxyl group as a substituent at the carbon atom position of the ring at the 21st position, assuming that the carbon atom of the ring is the 11th position,
and an aromatic group optionally having an organic group D as a substituent], and/or one or more saturated or ethylenically unsaturated aliphatic groups. or 2-hydroxybenzophenone oxime substituted by one or more corresponding ether groups and dissolved in said organic solvent (
a) hydrocarbyl hydroxymethyl ketone oxime,
(b) 2-hydroxyaldoximes in which the carbon atom bearing the hydroxyl group also carries two hydrocarbyl groups or one hydrocarbyl group and one hydrogen atom;
and/or (C) a 2-hydroxycycloalkanone oxime whose alicyclic ring also carries one or more organic groups. The present invention relates to a method for separating copper valuables from an acidic aqueous solution of a substance.

The method according to the present invention has a remarkable synergistic effect on the extraction rate compared to the method using the oximes (a), (b), and (c) above in the absence of the oximes (a), (b), and (c). This is economically very advantageous.

There is little adverse effect on the extraction selectivity with respect to iron, so aqueous solutions that also contain iron values are very suitable starting solutions. Preferably, the acidic solution has a pH of O-3. (a), (b) calculated based on the oxime described in (a) and/or (g) above;
, (c) is not critical.

The mole percentage that can best be applied can be easily established by simple extraction experiments in which the percentage is increased starting from, for example, 0.1. The best percentage is the value when the extraction rate reaches a certain level. The percentage will almost always be 1-100. Percentages of 2-20 and especially 4-12 are preferred.

The hydrocarbyl group of the hydrocarbyl hydroxymethyl ketone oxime may be, for example, an alkyl group, aromatic group or cycloalkyl group, with or without heteroatoms or substituted or unsubstituted.

Very good results have been obtained with hydrocarbyl hydroxymethyl ketone oximes having an alkyl group, in particular with alkyl hydroxymethyl ketone oximes and alkylphenyl hydroxymethyl ketone oximes,
The extraction rates achieved applying each of these two groups of oximes in the process of the invention are described in US Pat.
The values obtained with the oxime mixture used according to No. 49 are usually higher than those obtained with the oxime mixture used according to No. 49. It is preferable that the alkyl group has more than 5 carbon atoms. Excellent results were obtained with n-dodecylhydroxymethylketone oxime and p-n-decylphenylhydroxymethylketone oxime. Other examples of such oximes include p-n-dodecylphenyl hydroxymethyl ketone oxime, p-n-nonylphenyl hydroxymethyl ketone oxime, p-tert-nonylphenyl hydroxymethyl ketone oxime, p-n-nonylphenyl hydroxymethyl ketone oxime, Nonylhydroxymethylketone oxime, 2-methylnonylhydroxymethylketone oxime and pn-decylbenzylhydroxymethylketone oxime. The hydrocarbyl group present in the 2-hydroxy-aldoxime according to (b) above is, for example, an alkyl group, an alkenyl group, an aromatic group or a cycloalkyl group.

Substituents or heteroatoms such as oxygen atoms may be present on these hydrocarbyl groups. The 2-hydroxyaldoxime is preferably a 2-hydroxyalkanaloxime, especially one having 820 carbon atoms per molecule.

Particularly high extraction rates were achieved with 2-hydroxy-2-methylpentadecanaloxime, 2-hexyl-2-hydroxydecanaloxime and 2-hydroxy-2pentylnonanaloxime.

Other examples of these oximes include 2-hydroxy-
2-methyltetradecanaloxime, 2-ethyl-2
-Hydroxydodecanaloxime, 2-butyl-2-
Hydroxydecanaloxime, 2-hydroxy-2-
Pentyl decanal oxime and 2-hydroxy-2
-There is pentyl undecanal oxime. (c) above
The group or groups attached to the cycloaliphatic ring of the 2-hydroxycycloalkanone oxime described in 2-hydroxycycloalkanone oxime may be, for example, an aromatic group, an alicyclic group, an alkenyl group or, suitably, an alkyl group. Substituents or heteroatoms such as oxygen atoms may be present on these hydrocarbyl groups. 2
-Hydroxycyclododecanone oximes, especially those whose ring carries one or more alkyl groups, are preferred.

Using 2-alkyl-2-hydroxycyclododecanone oxime, especially 2-hydroxy 2-methylcyclododecanone oxime and 2-hydroxy-2,6,10-
Very high extraction rates were achieved using trimethylcyclododecanone oxime.

Other examples of these 2-hydroxycycloalkanone oximes are 2-hydroxy-4-nonylcyclohexanone oxime, 4-dodecyl-2-hydroxy-cyclohexanone oxime, 2-hydroxy-3-methylcyclododecanone oxime, 2-hydroxy-4-nonylcyclohexanone oxime, Ethyl-2-hydroxycyclododecanone oxime, 2,6,10-triethyl-2-
There are hydroxycyclododecanone oxime and 2-hydroxy-6-nonylcyclododecanone oxime. The aromatic group A in general formula (1) is a carbocyclic group, that is, it consists of a benzene ring or a combination of benzene rings.

Phenyl groups are preferred. One or more organic groups D bonded to the aromatic group A are, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkaryl group, an aralkyl group,
It may be an alkenyl group, an alkapolyenyl group, an alkoxy group, an alkylthio group, an aryloxy group, an aralkoxy group or an alkoxycarbonyl group.

Alkyl groups are preferred. Alkyl groups may be straight chain or branched. The hydroxyoxime of general formula (1) preferably contains at least 7 carbon atoms in the alkyl group bonded to the aromatic group A, and in particular the number of carbon atoms should not exceed 14. desirable. More generally, the number of carbon atoms in the group(s) D may be, for example, from 1 to 20. The number of carbon atoms is the total number of carbon atoms present within the combined alkyl group. Examples of suitable alkyl groups D include ethyl, 1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-
There are methylheptyl, 1-methyloctyl, 1-methyldecyl, 1-methyltetradecyl and tertiary nonyl groups (a mixture of branched nonyl groups derived from propene trimer). Aromatic radicals A may also contain primary, secondary and tertiary amino groups and inorganic substituents such as chlorine atoms and nitro groups. The aliphatic group represented by R in general formula (1) may be, for example, an alkyl group, an alkenyl group or an alkapolyenyl group.

The aliphatic group R may be straight-chain or branched and may contain substituents such as phenyl groups and/or heteroatoms such as oxygen atoms. Straight-chain groups have generally proved to be very advantageous. The number of carbon atoms in the radical R may be, for example, 1-20. Alkyl groups are generally preferred. Examples of suitable alkyl groups include methyl, ethyl, n-pentyl, n-heptyl, n-octyl, n-nonyl, n-undecyl, n-tridecyl and n-heptadecyl. The methyl group is very suitable, since it gives the oxime the highest extraction and stripping efficiency. Benzyl groups are also very suitable. Examples of very suitable hydroxy oximes include methyl 4-butyl-2-hydroxyphenyl ketone oxime, methyl 2-hydroxy-5-tert-nonylphenyl ketone oxime, n-heptyl 2-hydroxy-5- (1-methylhexyl) phenyl ketone oxime, n-octyl 2-hydroxy-5-(1-methylheptyl) phenyl ketone oxime, n-nonyl 2-hydroxy-5-(1-methyloctyl) phenyl ketone oxime and n-nonyl 2-hydroxy-5-(1-methylhexyl) phenyl ketone oxime. Examples further include n-tridecyl 2-hydroxy-5-methylphenyl ketone oxime, methyl 2-hydroxy-5
-(1-methylhexyl)phenylketone oxime, ethyl 2-hydroxy-5-(1-methylundecyl)phenylketone oxime, n-pentyl 2-hydroxy-
5-(1-methyldecino(ha)phenylketone oxime, n-undecyl 2-hydroxy-5-(1-methylpentyl) phenyl ketone oxime, n-heptyl 2-hydroxy-5-(1-methyltetradecyl) Phenylketone oxime, n-undecyl 2-hydroxy-5-(
1-methylheptyl)phenylketone oxime and.
-heptadecyl 2-hydroxy-5-(1-methylheptyl)phenyl ketone oxime. Methyl 2
Excellent results were obtained with -hydroxy-5-tert-nonyl phenyl ketone oxime and benzyl 2-hydroxy-5-tert-nonyl phenyl ketone oxime. These two compounds may be prepared using 4-tertiary-nonylphenol obtained by alkylation of phenol with propene trimer as a precursor. Examples of hydroxyoximes represented by the general formula (1) where R is a hydrogen atom include 5-3-butyl-2-hydroxy-benzaldoxime, 5-dodecyl-2-hydroxybenzaldoxime, 3,5 -di-tert-butyl-2-hydroxybenzaldoxime, 2-hydroxy-5-octylbenzaldoxime, 2-hydroxy-3,5-di-tert-benzaldoxime, 2
-Hydroxy-5-3-nonylbenzaldoxime and 2-hydroxy-3,5-di(1-methylbutyl)
There's benzaldoxime. Very high extraction rates were obtained with this last mentioned oxime. The 2-hydroxybenzophenone oxime described in (1) above is disclosed in US Pat. No. 3,428,449.
Among these oximes, those substituted at one 5-1 position are preferred, and those having an alkyl substituent are particularly desirable. Very good results were obtained using 2-hydroxy-5-tert-nonylbenzophenone oxime.

Excellent results were obtained using the following oxime combinations; methyl 2-hydroxo-3-nonylphenyl ketone oxime and n-dodecylhydroxymethyl ketone oxime or p-n-decylphenylhydroxymethyl Ketone oxime; benzyl 2-hydroxy-5-tertiary
Nonylphenyl ketone oxime and n-dodecylhydroxymethyl ketone oxime or 2-hydroxy-2-methylpentadecanal oxime: 2-hydroxy-5-
(1-methyloctyl)benzophenone oxime and n-
dodecyl hydroxymethyl ketone oxime, 2-hydroxy-2-methylbentadecanal oxime or 2-
Hydroxy-2,6,10-trimethyl-cyclododecanone oxime; 2-hydroxy-3,5-di(1-methylbutyl)benzaldoxime and n-dodecylhydroxymethylketone oxime.

A convenient volume ratio of extractant to acidic aqueous solution is 1:3-3:
It turned out to be 1.

However, ratios outside this range can also be used. Generally,
Extraction proceeds smoothly at 15-35°C. However, higher or lower temperatures such as 0°C-15°C and 35°C-75°C may also be used. Preferably, the mutual miscibility of the aqueous acid solution and the organic solvent should not exceed 5% by volume and in particular should be lower than 1% by volume.

Suitable solvents are, for example, halogenated solvents such as chloroform, 1,2-dichloroethane, 1,2-dichloropropane and di(2-chloroethyl)ether, and especially hydrocarbons such as kerosene, toluene and xylenes. 2-alkyl-2-hydroxycyclododecanone oxime in which 10 carbon atoms of the ring are unsubstituted, such as 2-hydroxy-2-menalcyclododecanone oxime, in which 3 alkyl groups are identical and 8 of the ring atoms 2,6,10-trialkyl- in which carbon atoms are not substituted
2-Hydroxycyclododecanone oxime, such as 2-hydroxy-2,6,10-trimethylcyclododecanone oxime, and 4-alkyl-2-hydroxycyclohexanone oxime, such as 2-hydroxy-4-n-
4-alkyl- in which the alkyl group has more than 3 carbon atoms, such as pentylcyclohexanone oxime
2-Hydroxycyclohexanone oxime is a new compound.

These novel compounds are produced by reacting the corresponding ethylenically unsaturated precursors with nitrosyl sulfate and then forming the 2-
Hydroxyimino hydrogen sulfate (2-HydrOx
yiminOhydrOgensulfate) with water.

Thus, 2 in which 10 carbon atoms of the ring are not substituted
-Alkyl-2-hydroxycyclododecanone oximes are produced by reacting the corresponding 2-alkylcyclododecenes with nitrosyl sulfuric acid and then forming the 1-alkyl-2-
Formed by reacting hydroxyiminocyclododecyl hydrogen sulfate with water.

For example, 2-hydroxy-2-methylcyclododecanone oxime is produced by reacting 2-methylcyclododecene with nitrosyl sulfate and then reacting the formed 1-methyl-2-hydroxyiminocyclododecyl hydrogen sulfate with water. It is formed by 2,6,10-trialkyl-2-hydroxycyclododecanone oximes in which the three alkyl groups are identical and 8 carbon atoms of the ring are unsubstituted are the corresponding 2,6,10-trialkyl- Reacting 1-cyclododecene with nitrosyl sulfate and then forming 1,5,9-trialkyl-2-
Formed by reacting hydroxyimino hydrogen sulfate with water.

For example, 2-hydroxy-2,6,10-trimethylcyclododecanone oxime is produced by reacting 2,6,10-trimethyl-1-cyclododecene with nitrosyl sulfate and then forming the 1,5,9 - Trimethyl-2-hydroxyimino hydrogen sulfate is formed by reacting with water. 4-Alkyl-2-hydroxycyclohexanone oximes, especially those in which the alkyl group has more than 3 carbon atoms, are formed by reacting the corresponding 4-alkyl-1-cyclohexene with nitrosyl sulfuric acid, and then It is formed by reacting 5-alkyl-2-hydroxyiminocyclohexyl hydrogen sulfinate with water.

For example, 2-hydroxy-4-n-pentylcyclohexanone oxime is produced by reacting 4-n-pentyl-1-cyclohexane with sulfuric acid and then converting the formed 5-n-pentyl-2-hydroxyiminocyclohexyl hydrogen sulfate into water. It is formed by reacting with The invention will be further illustrated by the following example.

The extraction described in the example was carried out in a separatory funnel consisting of a graduated continuous-walled vessel with a capacity of 0.25 t, equipped with a double paddle stirrer and with a bottom part for drainage. was equipped with a stopcock.The two starting liquids were conducted through the upper opening.

The starting aqueous solution contains copper sulphate and ferric sulphate at concentrations of 63 and 36 mm01/t, respectively, and has a pH of 1.9.
Contains free sulfuric acid in an amount of 0. The organic solvent was a kerosene fraction having a boiling range of 210°C-240°C at atmospheric pressure. A mixture of starting aqueous solution 100 WLI and starting organic extractant 100a was stirred in the funnel at a temperature of 25° C. at a rate of 2000 re/min. Samples of the stirred mixture were taken at various times. The two phases of the sample were separated - the equilibrium percent of copper extracted was determined. The above (Ak(b), (c) used in Example 1-
The oximes belonging to ) and (d) were of the compound names shown in Table 1 and numbered as shown in the table.

Example 1 (4) Experiment 1 not according to the invention The kerosene fraction contained 0.2 mole of methyl 2-
It contained only hydroxy-5-3-nonylphenyl ketone oxime.

The oxime was prepared by oximation of 2-hydroxy-5-3-nonylphenyl methyl ketone with hydroxylamine. The ketone was obtained from commercially available 4-tert-nonylphenol/Sl).
It was formed by Friis rearrangement of 1-tert-nonylphenyl acetate. The 4-tertiary-nonylphenol was obtained by alkylation of the phenol with a condensate of branched propene trimers. The table shows the percentage of copper extracted at various times after the start of the experiment, below experiment 1'.

In the following description, the symbol "%m" represents "mol%". 03) The experimental kerosene according to the invention contained 0.2 mol per liter of methyl 2-hydroxy-5-tert-nonylphenyl ketone oxime and a second oxime numbered as indicated in the second row of the table. Inclusive.

The third line of the table shows the concentration of the second oxime present therein, calculated on the basis of the methyl 2-hydroxy-5-3-nonylphenyl ketone oxime.

The table also shows the percentage of copper extracted in experiment number 2-1.
7 shown below. These results demonstrate a significant synergistic effect on extraction rate compared to Experiment 1. C) Experiments not according to the invention The kerosene used in experiment number 18 contains 0.2 mol of 2-hydroxy-5-tert-nonylbenzophenone oxime per liter and It contained 11% of 5,8-diethyl-6-dodecanone oxime.

The results are shown in the first column from the right of the table. oxime l and 2
The extraction rates achieved with oximes 3, 4, 7, and 8 are higher than those obtained with the known oxime mixture used in experiment 18, and the extraction rates achieved with oximes 3, 4, 7, and 8 are higher than those obtained with the known oxime mixture used in experiment 18. The extraction rate was almost equal to that in Experiment 18. Column - Experiments not according to the invention Kerosene contains only 0.2 moles per liter of benzyl 2-hydroxy-5-tertiary-nonylphenyl ketone oxime and the percentage of copper extracted is as per experiment number 1 in the table.
It was as shown in

}) Experimental kerosene according to the invention contains 0.2 mol per liter of benzyl 2-hydroxy-5-tert-nonylphenyl ketone oxime; Calculated based on 10%m
oxime, the number of which is shown in the second row of the table.

The percentage of copper extracted is shown in the table under experiment number 2-5. The results of Experiments 2-5, compared to the results of Experiment 1, show that a significant synergistic effect on the extraction rate can be obtained.

However, Experiment 5 is a comparative experiment, and its results are clearly somewhat inferior to the results of Experiments 2-4 according to the present invention. The extraction rates achieved using oximes 1 and 3 are:
higher than the extraction yield obtained with the known mixture of two oximes in experiment 18 of Example 1, and oxime 8
The extraction rate achieved using this method is approximately equal to the extraction rate obtained in Experiment 18. Example 1 Experiments not according to the invention Kerosene contained only 0.2 moles of 2-hydroxy-5-(1-methyloctyl)benzophenone oxime per liter.

In the table, the percentage of copper extracted is shown under run number 1. (8) Experimental kerosene according to the invention contains 0.2 mol per liter of 2-hydroxy-5-(1-methyloctyl)benzophenone oxime and contains 2-hydroxy-5-(1-methyloctyl)benzophenone oxime. Contains 10% m of a second oxime calculated on the basis of the phenone oxime, the number of which is given in the second row of the table.

The table shows the percentage of copper extracted under experiment numbers 2-4. According to the results of experiments 2, 3 and 4, experiment 1
It was shown that a significant synergistic effect on the extraction rate was obtained compared to the results of . The extraction rate was also higher than that obtained using the known oxime mixture of Example 1, Run 18. EXAMPLE Experimental kerosene not according to the invention contained only 0.2 moles of 2-hydroxy-3,5-di(1-methylbutyl)benzaldoxime per liter.

The percentage of copper extracted in the table is shown below experiment number 1.
(B) Experimental kerosene according to the invention contains 0.2 mol per liter of 2-hydroxy-3,5-di(1-methylbutyl)benzaldoxime and 2-hydroxy-3,5-di(1- 10 based on methylbutyl)benzaldoxom
%m of second oxime, the number of the second oxime is as shown in Table V
It is shown in the second bamboo.

The percent of copper extracted into the cloth V was 2-4.
Shown below. The results of Mistakes 2, 3 and 4 showed that a significant synergistic effect on extraction rate was obtained compared to the results of Experiment 1. The extraction rates achieved with oxime 1fi- are higher than those obtained with the known oxime mixture of experiment 18 of Example 1 and with oximes 3 and 8.
The extraction rate achieved with Example 18 was approximately equal to that in Example 18.

Example V 2-methylcyclododecene 0 in 150 ml n-heptane
．． A solution containing 5 mol of 75% sulfuric acid was added at a temperature of 0°C.
It was added dropwise to a solution of 0.4 mol of nitrosyl sulfuric acid dissolved in 140y of a mixture of W and 25% W of water.

After this addition, the reaction mixture was stirred vigorously until the reaction was complete. The phases were separated, the organic phase was removed and the aqueous layer was washed three times with equal volumes of n-heptane. The washed aqueous solution was diluted to 500 ml with water, and then 28% W ammonia aqueous solution was added until the pH reached 7.5.
The resulting solution was extracted with an equal volume of diethyl ether, the resulting extracted phase was dried over anhydrous sodium sulfate, and the dried phase was boiled down at a pressure of 15 nHg to obtain the converted 2-methylcyclodide. 90 based on decen
2-hydroxy-2-methylcyclododecanone oxime was obtained with a yield of . The structure was confirmed by proton magnetic resonance and mass spectrometry. Examples: 2,6,10- prepared by trimerization of isoprene and then partial hydrogenation of the 1,5,9-trimethyl-1,5,9-cyclododecatriene formed. trimethyl-1-cyclododecene,
The experiment described in the example was repeated using instead of 2-methylcyclododecene.

The yield of 2-hydroxy-2,6,10-trimethylcyclododecanone oxime was 91%, calculated based on the converted olefin. The structure was confirmed by proton magnetic resonance and mass spectral analysis. Example V
B 4-pentyl-1- instead of 2-menalcyclododecene
The experiment described in the example was repeated using cyclohexene.

Claims (1)

[Scope of Claims] 1. An organic solvent, and (
b) General formula A-C(=NOH)-R(I) [In the formula, R represents a hydrogen atom or an aliphatic group, and A represents -C
(=NOH) - The carbon atom of the ring to which the R group is bonded is 1-
Indicates an aromatic group having a hydroxyl group as a substituent at the ring carbon atom position at the 2-position and optionally having an organic group D as a substituent. oxime, and/or (b)
2-hydroxybenzophenone oxime substituted by one or more saturated or ethylenically unsaturated aliphatic groups or one or more corresponding ether groups, and (a) dissolved in said organic solvent. hydrocarbyl hydroxymethyl ketone oximes, (b) 2-hydroxyaldoximes in which the carbon atom bearing the hydroxyl group also carries two hydrocarbyl groups or one hydrocarbyl group and one hydrogen atom, and/or (c
) Copper is removed from an acidic aqueous solution of copper values by liquid-liquid extraction using an extractant containing a 2-hydroxycycloalkanone oxime whose alicyclic ring also contains one or more organic groups. How to separate valuables. 2. In the method described in claim 1, (a
), (b) and/or (c),
A method used in an amount of 1 to 100 mol% calculated based on the oxime described in (a) and/or (b). 3. In the method described in claim 2, (a
), (b) and/or (c),
A method used in an amount of 4-12 mol% calculated based on the oxime described in (a) and/or (b). 4. The method according to any one of claims 1 to 3, wherein the hydrocarbyl hydroxymethyl ketone oxime shown in (a) has an alkyl group. 5. The method of claim 4, wherein the alkyl group has more than 5 carbon atoms. 6. The method according to claim 4 or 5, wherein the hydrocarbyl hydroxymethyl ketone oxime used is an alkyl hydroxymethyl ketone oxime. 7 In the method according to claim 6, the alkyl hydroxymethyl ketone oxime used is n-
The method of being a dodecyl hydroxymethyl ketone oxime. 8. The method according to claim 4 or 5, wherein the hydrocarbyl hydroxymethyl ketone oxime used is an alkyl phenyl hydroxymethyl ketone oxime. 9. The method according to claim 8, wherein the alkylphenyl hydroxymethyl ketone oxime used is p-n-decylphenyl hydroxymethyl ketone oxime. 10. The method according to any one of claims 1 to 3, wherein the 2-hydroxyaldoxime described in (b) is a 2-hydroxyalkanal oxime. 11 In the method according to claim 10,
8-2 2-hydroxyalkanal oxime per molecule
Method with 0 carbon atoms. 12. In the method according to claim 11,
The 2-hydroxy-alkanal oxime used is 2
-Hydroxy-2-methylpentadecanal oxime. 13. In the method according to claim 11,
The 2-hydroxyalkanal oxime used is 2-
A method in which hexyl-2-hydroxydecanal oxime. 14. The method according to claim 11, wherein the 2-hydroxyalkanal oxime used is 2-hydroxy-2-pentyl nonanal oxime. 15. In the method according to any one of claims 1 to 3, one or more organic groups bonded to the alicyclic ring of the 2-hydroxycycloalkanone oxime described in (c) are alkali How to be basic. 16 In the method according to claim 15,
A process in which the 2-hydroxycycloalkanone oxime used is 2-hydroxycyclododecanone oxime. 17 In the method according to claim 16,
A process in which the 2-hydroxycyclododecanone oxime used is 2-alkyl-2-hydroxy-cyclododecanone oxime. 18 In the method according to claim 17,
A process in which the 2-hydroxy-2-alkylcyclododecanone oxime used is 2-hydroxy-2-methylcyclododecanone oxime. 19 In the method according to claim 17,
A process in which the 2-alkyl-2-hydroxycyclododecanone oxime used is 2-hydroxy-2,6,10-trimethylcyclododecanone oxime. 20. The method according to any one of claims 1 to 19, in which A in general formula (I) has one or more alkyl groups as organic group D. 21 In the method according to claim 20,
In the alkyl group D bonded to the aromatic group A, the hydroxy-oxime represented by the general formula (I) has at least 7
Methods involving carbon atoms. 22. The method according to any one of claims 1 to 21, wherein R in general formula (I) represents an alkyl group. 23 In the method according to claim 22,
A method in which R represents a methyl group. 24 In the method according to claim 23,
A method in which the compound represented by general formula (I) is methyl 2-hydroxy-5-tert-nonylphenyl ketone oxime. 25. The method according to any one of claims 1 to 21, wherein R in general formula (I) represents a benzyl group. 26 In the method according to claim 25,
A method in which the compound represented by general formula (I) is benzyl 2-hydroxy-5-tert-nonylphenyl ketone oxime. 27 In the method according to any one of claims 1 to 21, the compound represented by general formula (I) is
-Hydroxy-3,5-di(1-methylbutyl)benzaldoxime. 28. The method of any of claims 1-19, wherein the 2-hydroxybenzophenone oxime has an alkyl substituent at one 5-position. 29 In the method according to claim 28,
The 2-hydroxybenzophenone oxime used is 2
-Hydroxy-5-tert-nonylbenzophenone oxime. 30. A method according to any of the preceding claims 1-29, wherein the aqueous solution has a pH of 0-3 and contains iron values.