JPH06198000A - Method of processing chromed organic product by oxidation - Google Patents

Abstract

PURPOSE: To dispose of chlorinated organic products by combining chlorinated organic products with other optional transitional metallic ion, and performing an oxidizing treatment through the use of hydrogen peroxide (H202) under the presence of Fe(II) ion and a phase transfer agent. CONSTITUTION: I is a method for disposing of chlorinated organic products by oxidizing the chlorinated products under the presence of the hydrogen peroxide, and appropriate catalyst and phase transfer agent, forming a non-toxic material, and treating the chlorinated organic products capable of recovering a polluted material. The chlorinated organic products are treated with an aqueous liquid (H20) under the presence of Fe(II) ion combined optionally with more than one of the phase transfer metallic ion selected from a group consisting of Cu(II), Ti(IV), Mn(II), Co(II), Ni(II), W(IV) and Mo (IV), and also under the presence of the phase transfer agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for disposing of chlorinated organic products. More particularly, the invention relates to chlorination by oxidation treatment with hydrogen peroxide (H ₂ O ₂ ) in the presence of a phase transfer agent and Fe (II) ions, which may optionally be combined with other transition metal ions. The present invention relates to a method of disposing chemical organic products.

[0002]

BACKGROUND OF THE INVENTION The chlorinated organic products are a group of substances which are widely used in various technical fields. Among these are polychlorobiphenyls (PCBs), 1,1,1, trichloro-2,2.
-Bis (p-chlorophenyl) ethane (DDT), tetrachloroethane, dichlorobenzenes, chlorophenols, alkyls such as hexachlorocyclohexane,
Compounds having an aromatic or alkylaromatic structure, or having an olefinic structure such as trichlorethylene, are more common.

Generally, they are toxic and highly pollutant,
Their disposal after use involves many problems. In fact, it can be applied on a large scale, is as economical as possible,
It is necessary to use a disposal method that is not dangerous to the environment. It is particularly difficult to achieve the above optimal goals because chlorinated organic products have high stability and form high contaminating by-products when treated by chemical and / or physical means.

For example, polychlorobiphenyls (PCB
s) is a highly toxic and carcinogenic aromatic chloro compound, which has been widely used until a while ago, thanks to its insulating property as an oil for electric devices, especially for captors. Due to its high toxicity, currently valid regulations mandate the elimination of PCSs and their replacement with hydrocarbon mineral oils. It is necessary to remove large amounts of PCBs which are usually dissolved in organic solvents (eg hexachlorobenzene) or impregnated into separating and / or supporting materials such as paper, paperboard, wood and the like.
Further, it is often necessary to remove PCBs from contaminated mineral oil prior to replacement due to improper cleaning of electrical equipment.

The most commonly used treatment for the disposal of chlorinated organic products is combustion, which results in the formation of the most toxic chlorinated organic compounds such as parachlorodibenzodioxins, parachlorodibenzofurans. To prevent, it is done in a properly equipped plant. In any case, the burning method is an expensive method, apart from the fact that it is at risk to the environment and involves the removal of not only the chlorinated compounds but also the substances contaminated therewith.

[0006]

Applicants have found that chlorinated products can be oxidized in the presence of hydrogen peroxide, a suitable catalyst and a phase transfer agent to produce non-toxic substances and pollutants can be recovered today. We have found a way to dispose of chlorinated organic products, which has considerable economic and environmental advantages compared to the methods used up to now.

Therefore, an object of the present invention is to provide chlorinated organic products with Cu (II), Ti (IV), Mn (II), Co
Fe optionally combined with one or more transition metal ions selected from (II), Ni (II), W (IV) and Mo (IV)
(II) H ₂ O _{2 in} the presence of ions and a phase transfer agent
The present invention provides a method for disposing of chlorinated organic products, which comprises treating with an aqueous liquid.

Examples of chlorinated products to which the present invention can be applied include the following. (A) those having an aromatic structure such as polychlorobiphenyls (PBCs), chlorobenzenes (eg ortho or meta-dichlorobenzene), chlorophenols (eg para, tri or pentachlorophenol),
(B) 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane (DDT), such as those of alkyl aromatic structure, (c) trichloroethylene, perchlorobutadiene, etc. Those having an olefin structure, and (d) those having an aliphatic or alicyclic structure such as tetrachloroethane, hexachlorocyclohexane, chloral hydrate, hexachloroethane, and perchloroacetone.

The reaction involved in the process of the present invention is an oxidation reaction in a heterogeneous phase because the chlorinated organic product is insoluble in the aqueous phase containing the H ₂ O ₂ / Fe ²⁺ oxidation system.
Therefore, it must be carried out in the presence of a phase transfer agent, a substance that acts as a "bridge" between the chlorinated organic product and the molecules of the oxidizing system. For details of such substances, see C. of Academic Press (1978). Stokes, and C.I. Riota's "Phase transfer catalys"
ts) ”is referred to.

Among the products known in the art as phase transfer catalysts, those which can be advantageously used in the present invention include those represented by the general formula:

[0011]

[Chemical 2] (In the formula, Q is selected from N, P and As, and R ₁ , R ₂ and R are selected.
₃ and R ₄ are the same or different and each is a hydrogen atom, a C _{1 to} C ₃₅ alkyl group, a C _{6 to} C ₁₀ aryl group, a C _{1 to} C ₁₀ aralkyl or alkylaryl group, provided that at least one of R _{1 to} R ₄ is present. One is different from hydrogen atom, X ^- is OH ^-, Cl ^-, B
r ⁻ , I ⁻ and BH ₄ ^— ) ammonium,
A phosphonium or arsonium salt.

Another group of phase transfer agents which can be utilized in the method of the present invention is the formula:

[0013]

[Chemical 3] (R is a C ₁ -C ₂₀ alkyl group and X ⁻ has the same meaning as defined above).

Still another group of phase transfer agents which can be used in the method of the present invention are:

[0015]

[Chemical 4] (Wherein R ₅ is the same or different, and is a C _1-6 alkyl group, X
^- it is defined above and ephedrine salt of the same meaning).
Such products are available from Gany V. (Gani V., Tapinte
C., Viout P.), “Tetrahedron Letters (Tetrah
edron letters) "p. 4435 (1983), Banton C. et al. (Bunton C., Robinon L., Stam M.)," Tetrahedron Letters ", p. 121 (1971).

It is also possible to utilize a mixture of different phase transfer agents to best combine the properties of each phase transfer agent type in order to achieve sufficient mineralization of the chloro atoms and complete removal of the chlorinated organic products. It is possible.

[0017] Examples of phase transfer agents that can be used in the methods of the present _{invention, (C 4 H 9) 4} N + X -, (C 10 H 21) 3 N + C 3 H 7
^{_{X -, (C 18 H 37}} ) 3 N + CH 3 X -, (C 18 H 37) 2 N
^{_{+ (CH 3) 2 X -}} , (C 4 H 9) 3 P + C 16 H 33 X -, (C 7
^{_{H 15) 3 N + CH 3}} X -, (C 6 H 5) 3 As + CH 3 X -,
_{(C 6 H 5 CH 2)} N + (CH 3) 3 X -,

[0018]

[Chemical 5] and so on. A particularly preferred embodiment in the present invention is a tetraalkylammonium salt (wherein the alkyl groups are the same or different and have 1 to 35 carbon atoms, preferably 1 to 12 carbon atoms).

Usually, the chlorinated organic product to be removed is present in an amount in the range 100 to 5000 ppm, while the phase transfer agent is in the aqueous phase 20 to 500 ppm,
It is preferably 100 to 300 ppm. In addition to the phase transfer agent, the method of the present invention uses Cu (II), Ti (IV), Mn
(II), Co (II), Ni (II), W (IV) and Mo
It comprises the use of Fe (II) ions as a catalyst which may optionally be combined with one or more transition metals selected from (IV). Among them, Cu (II) ion is preferable. Fe (II) ions are usually 50 to 1000 as metal ions.
ppm, the other transition metal ions indicated above are added in amounts ranging from 0 to 400 ppm. In a preferred embodiment, Fe (I
I) ions and Cu (II), Ti (IV), Mn (II), C
Mixtures of o (II), Ni (II), W (IV) or Mo (IV) ions are used in equimolar amounts, each from 50 to 40
The concentration is 0 ppm, preferably 150 to 250 ppm.

The metal ions mentioned above are added in the form of soluble salts. In particular, regarding Fe (II) ions, for example, iron sulfate, iron chloride, iron nitrate, ammonium iron sulfate, etc. can be used. Ferrous heptahydrate sulfate FeSO ₄ · 7H ₂ O
Is preferable from the viewpoint of effectiveness and economy. Among the Cu (II) salts, for example, cupric sulfate pentahydrate CuSO ₄ .5H ₂ O
Is used.

For hydrogen peroxide, the molar ratio of H ₂ O ₂ added to the initially present chlorinated product is generally less than 0.1.
It is used in the form of an aqueous solution so as to be 2 to 100, preferably 0.2 to 30. The concentration of the hydrogen peroxide aqueous solution is not a distinguishable parameter and 30-50% by volume hydrogen peroxide solution is usually used to simplify the operating mode. The hydrogen peroxide solution is preferably added slowly and continuously to the reaction mixture at a particular temperature and pH to more easily control the reaction conditions. The rate of addition is usually in the range 0.2 to 3 ml / min, but can be varied over a wide range depending on the particular reaction conditions.

The reaction temperature can be varied over a wide range and is usually from 40 ° C to 200 ° C, preferably 7 ° C.
It is 0 to 120 ° C. This pH is usually in the range of about 2 to 7, preferably about 3 to 4,
Acid (eg H ₂ SO ₄ ) or base (eg Na) during the reaction
It is maintained by adding a small amount of an aqueous solution of (OH).

The process of the invention leads to the quantitative conversion of chlorinated organic products into non-toxic substances, with a sufficient level of mineralization (mineralization) of the chlorine atom, in other words the conversion of organic chlorine to chlorine ions. Accompany. If the chlorinated product to be disposed of is dissolved in an organic solvent or a hydrocarbon type mineral oil, the reaction mixture is heated to a predetermined reaction temperature and then the two phases are in good contact. Vigorously stir to obtain a water / oil fine emulsion (the predominant phase is the organic phase).

[0024]

The present invention will be illustrated in more detail in the following examples, which are merely illustrative and do not limit the scope of the present invention. In each example, this reaction trend was determined by recovering a small amount of the reaction mixture after hydrogen peroxide was added as scheduled and determining the following parameters.

A) Concentration of chlorinated organic products determined by gas chromatographic analysis (stationary phase Tem
2 meter packed column with ax ^(R) , transfer gas is nitrogen, temperature program is isothermal for 2 minutes at 100 ° C, then 18
The temperature was raised to 0 ° C with a gradient of 10 ° C / minute, and then 25 ° C at 180 ° C.
Is isothermal for minutes). Each injection (0.6 μl)
Performed with a sample diluted 1: 1 with CH ₂ Cl _{2 to} which CH ₃ OH was added as an internal standard.

For PCBs, all calculations are 3
It relates to one of the main PCB isomers and the following composition has been determined. _{C 12 H 7 Cl 3: 21.21} % C 12 H 5 Cl 5: 0.95% C 12 H 6 Cl 4: 77.83% on the foundation of such a composition, average molecular weight 280.5 and chloride The average number of atoms, 3.74, is determined.

B) Chloride Ion Concentration Chloride is H ₂ acidified with 0.1% of HNO _3.
It is recovered by extraction with of O, analyzed by potentiometric titration (Voltimetric titration) in an acid medium containing AgNO _3.

C) COD (Chemical Oxygen Demand) Using the oxidation with potassium dichromate in acid medium and titration with ferrous sulfate, the "official, standardized recommended analytical method (Of
ficial, Standardized and Recommended Methods of An
analysis) ”by NW Hanson (The Society of Analytical Chemistry, page 383, 1973).

Examples 1-3 455 μl of mineral oil contaminated with PCBs (3431 ppm)
Was introduced into a reaction flask equipped with a condenser, dropping funnel, pH-meter and magnetic stirrer. Then 4
5 ml of water and an amount of FeSO ₄ .7H ₂ O in which both Fe ²⁺ ions and Cu ²⁺ ions have a concentration of 200 ppm
And CuSO ₄ .5H ₂ O and 150 ppm (Example 1), 30
An aqueous solution of tetrabutylammonium hydroxide (ITBA) in an amount equal to 0 ppm (Example 2) and 0 ppm (Example 3, Comparative Example) was added.

The resulting mixture was heated to 95 ° C. in an oil bath and the pH was either 10% aqueous NaOH or 15% H ₂
It was adjusted to a value of about 3.0 by adding a small amount of SO ₄ aqueous solution. This mixture was stirred vigorously to form a water-in-oil emulsion. Then an aqueous solution of H ₂ O ₂ (4
5% by volume) was gradually added at a rate of about 0.6 ml / min. After the scheduled addition of hydrogen peroxide (as shown in Table 1), reaction mixture samples (5 ml each) were withdrawn for analysis. Remaining PCB for each sample
Concentrations ([PCBs]) and chloride ion concentrations ([C
l ^-]) were determined by the aforementioned method. While results are shown in Table 1, wherein mineralization percentage (% [Cl ^-])
Is expressed as the ratio of the actually obtained Cl ^- ion concentration to the maximum obtainable Cl ^- ion concentration.

During the reaction, the pH was adjusted to NaOH or H ₂ S.
O ₄ adding a small amount of solution by (0.1-0.3ml) 3.
It was maintained near 0, while this temperature was kept constant at 94 ° C. The reaction using 150 ppm of ITBA (Example 1) and the reaction not using ITBA (Example 3) were continued for 60 minutes,
Meanwhile, the reaction using 300 ppm of ITBA (Example 2) was continued for 95 minutes.

From a comparison between the data obtained, it can be inferred that, first of all, the oxidation of PCBs does not occur without the aid of a phase transfer agent. The addition of a phase transfer agent results in almost complete elimination of PCBs with a sufficient mineralization rate, especially in the case of reactions with low concentrations of ITBA (Example 1).

Examples 4-6 Another phase transfer agent, tetrabutylammonium bromide (TB), was used following the same procedure described in Examples 1-3.
The effect of AB) was investigated by comparing the following reactions. -150 ppm of TBAB was used (Example 4), -472 ppm of TBAB was used (Example 5) and -TBAB was not used (Example 6, Comparative Example).

The data obtained are shown in Table 2. Example 1
-3, this reaction does not occur without a phase transfer agent, and the best results in mineralization of PCBs, ie oxidation of PCBs, are obtained with low concentrations of transfer agent (Example 4). It is possible to observe.

Examples 7-9 Another phase transfer agent, tetrabutylammonium iodide (TB), was used following the same procedure described in Examples 1-3.
The effect of AI) was investigated by comparing the following reactions. -166 ppm of TBAI was used (Example 7), -460 ppm of TBAI was used (Example 8) or -TBAI was not used (Example 9, Comparative Example) The data obtained are shown in Table 3. .

Examples 10-11 Following the same scheme described in Examples 1-3, the effect of the phase transfer agent mixture (ITBA + TBAB) was investigated by comparing the following reactions. -100 ppm of ITBA + 100 ppm of TBAB were used (Example 10) -No phase transfer agent was used (Example 11, Comparative example) The data obtained are shown in Table 4.

From the comparison of the results obtained in Example 10 with Examples 1, 4 and 7, the combination of the two phase transfer agents of Example 10 was found to be substantial with mineralization of the PCBs in sufficient proportion. It is clear that this is the best combination that can quantitatively perform the quantitative oxidation of PCBs.

In the same reactor used in the [0038] Example 12 above embodiment, satisfy the 500ml of H ₂ O, in this, for both Fe ^{2 +} and Cu ²⁺ ions 2
FeSO ₄ · 7H _{2 in} an amount equivalent to obtain a concentration of 00 ppm
O and CuSO ₄ .5H ₂ O and tetrabutylammonium hydroxide (ITBA) in an amount of 150 ppm were dissolved.

Next, 20 g of the PCBs-containing paper, previously cut into small pieces, was introduced into the reactor. P in this paper
The concentration of CBs is 1060 ppm. This concentration was determined by continuously extracting a paper sample (1 g) with 20 ml of CH ₂ Cl ₂ at room temperature for 14 hours and then analyzing by gas chromatography using PCBs containing solvent as internal standard with methanol. did.

While maintaining the solution under vigorous stirring, 4
A 5% aqueous hydrogen peroxide solution was added to give a total H ₂ O ₂ concentration of 127.5.
Slowly added until g / l. In conclusion of this reaction, the chloride ion concentration was determined in the aqueous phase by potentiometric titration in an acid medium with AgNO ₃ . Residual PCBs concentrations in both the aqueous phase and paper pulp were determined by gas chromatography after extraction with CH ₂ Cl ₂ as described above. The data obtained are shown in Table 5.

Example 13 (hexachlorocyclohexane
The 0.5g of the oxide) hexachlorocyclohexane (ECE),
25 with dropping funnel, pH meter and magnetic stirrer
It was introduced into a 0 ml round bottom reaction flask. After this, 10
0 ml of water and a corresponding amount of FeSO ₄ to obtain a concentration of 200 ppm for both Fe ²⁺ and Cu ²⁺ ions
An aqueous solution of 7H ₂ O and CuSO ₄ .5H ₂ O and tetrabutylammonium hydroxide (ITBA) in an amount of 500 ppm was added.

Heating the resulting mixture to 95 ° C. in an oil bath,
pH was adjusted to a value of about 3.4-3.5 by a small amount addition of 15% H ₂ SO ₄ aqueous solution or aqueous 10% NaOH.
This mixture was stirred vigorously to dissolve all ECE. Then, an aqueous solution of H ₂ O ₂ (56% by volume) was added to about 0.4 ml / m 2.
Slowly added in proportion. After H ₂ O ₂ was added as scheduled (as shown in Table 6), reaction mixture samples (5 ml each) were withdrawn for analysis. In Table 6, H
The addition amount of ₂ O ₂ is shown as the stoichiometric equivalent number, and the stoichiometric equivalent is the H ₂ O ₂ (required for completely decomposing this organic substance into CO ₂ and H ₂ O). 100%) of the theoretical amount.

Residual ECE for each sample
Concentration ([ECE]), COD and chloride ion concentration ^- the ([Cl]), was determined according to the above method. The results are reported in Table 6, where the mineralization percentage (%
[Cl ⁻ ]) is shown as the ratio of the actually obtained Cl ⁻ ion concentration to the maximum obtainable Cl ⁻ ion concentration. During the reaction, the pH was maintained around 3.4 by the addition of a small amount of NaOH or H ₂ SO ₄ solution (0.1-0.2 ml), while the temperature was kept constant at 97 ° C.

Example 14 (Acid of meta-chlorobenzene
1 g (0.766 ) of meta-dichlorobenzene (MDB)
ml) was introduced into a 500 ml round bottom reaction flask equipped with a dropping funnel, pH-meter and magnetic stirrer. This is followed by a corresponding amount of FeSO ₄ to obtain a concentration of 200 ppm for both Fe ²⁺ and Cu ²⁺ ions.
An aqueous solution of 200 ml of H ₂ O in which 500 ppm of 7H ₂ O and CuSO ₄ .5H ₂ O and tetrabutylammonium hydroxide (ITBA) were dissolved was added.

The mixture obtained is heated to 95 ° C. in an oil bath,
The pH was adjusted to a value of about 3.5 by the small addition of 15% aqueous H ₂ SO ₄ or 10% aqueous NaOH. The mixture was vigorously stirred to dissolve all MDB. Then H
₂ O ₂ aqueous solution (60% by volume) was added slowly at a rate of about 0.44 ml / min. After the scheduled addition of H ₂ O ₂ (as shown in Table 6), reaction mixture samples (each 20 m
l) was withdrawn for analysis. For each sample, the residual MDB concentration ([MDB]) and chlorine ion concentration ([Cl ^-]) were determined according to the manner described above. The results are reported in Table 6, where the mineralization percentage (%
[Cl ⁻ ]) is shown as the ratio of the actually obtained Cl ⁻ ion concentration to the maximum obtainable Cl ⁻ ion concentration. During this reaction, the pH was maintained around 3.5 by the small addition of NaOH and H ₂ SO ₄ solution (0.1-0.2 ml), while the temperature was kept constant at 97 ° C.

[0046]Examples 15-17 (of chlorophenols
Oxidation) 6. Para-chlorophenol (PCF) (Example 15)
25 g or trichlorophenol (TCF) (Example 1
6) 0.25g or pentachlorophenol (PEC
F) (Example 17), 0.25 g, dropping funnel, pH
-500 ml round bottom reaction flask with meter and magnetic stirrer
Introduced in Sco. After this, Fe²⁺And Cu ²⁺Both of Aeon
Amount equivalent to obtain a concentration of 200 ppm
FeSO_Four・ 7H₂O and CuSO_Four・ 5H₂O and 500
ppm tetrabutylammonium hydroxide (ITB
An aqueous solution consisting of 250 ml of water in which A) was dissolved was added.

The mixture obtained is heated to 95 ° C. in an oil bath,
The pH was adjusted to a value of about 3.0 by adding a small amount of 15% H ₂ SO ₄ aqueous solution or 10% NaOH aqueous solution. The mixture was stirred vigorously to dissolve all PCF, TCF or PECF. Then, an H ₂ O ₂ aqueous solution (50% by volume) was added to about 0.
It was added slowly at a rate of 2 ml / min. After the scheduled addition of H ₂ O ₂ (as shown in Table 7), reaction mixture samples (5 ml each) were drawn for analysis. For each sample, the residual PCF, TCF, or PECF concentration ([PCF], [TCF] , [PECF]), COD and chloride ion concentration ^- was determined ([Cl]) according to the above described method. The results are reported in Table 7, where the mineralization percentage (% [Cl ⁻ ]) is the actual Cl ⁻ obtained.
It is shown as the ratio of the ion concentration to the maximum obtainable Cl ^- ion concentration. During this reaction, the pH is NaOH or H ₂
The temperature was kept constant at 97 ° C. while being kept around 3.0 by a small addition of SO ₄ solution (0.1-0.2 ml).

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

[0052]

[Table 5]

[0053]

[Table 6]

[0054]

[Table 7]

[0055]

INDUSTRIAL APPLICABILITY According to the present invention, a chlorinated product can be oxidized in the presence of hydrogen peroxide, a suitable catalyst and a phase transfer agent to produce a non-toxic substance, and a pollutant can be recovered. It is possible to provide a method of disposing of chlorinated organic products, which has considerable economic and environmental advantages as compared with the above method.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Fulbio Burcio Milan, Italy 20145 Via F. Ferucchio 6 (72) Inventor Mario Alfili Milan, Italy 20131 Via Casoretto 8

Claims (12)

[Claims] 1. A chlorinated organic product containing Cu (II), Ti
(IV), Mn (II), Co (II), Ni (II), W (I
V) and Mo (IV) comprising treating with H ₂ O ₂ aqueous liquid in the presence of Fe (II) ions in any combination and in the presence of a phase transfer agent. Disposal methods for chlorinated organic products. 2. The process of claim 1 wherein the chlorinated organic product is of aromatic, alkyl-aromatic, olefinic, aliphatic or alicyclic construction. 3. The chlorinated organic product is polychlorobiphenyls (PCBs), chlorobenzenes, chlorophenols, 1,1,1-trichloro-2,2-bis (p-).
The process of claim 2 selected from chlorophenyl) ethane (DDT), trichloroethylene, perchlorobutadiene, tetrachloroethane, hexachlorocyclohexane, chloral hydrate, hexachloroethane and perchloroacetone. 4. The phase transfer agent is represented by the general formula: (In the formula, Q is selected from N, P and As, and R ₁ , R ₂ and R are selected.
₃ and R ₄ are the same or different and each is a hydrogen atom, a C _{1 to} C ₃₅ alkyl group, a C _{6 to} C ₁₀ aryl group, a C _{1 to} C ₁₀ aralkyl or alkylaryl group, provided that at least one of R _{1 to} R ₄ is present. One is different from hydrogen atom, X ^- is OH ^-, Cl ^-, B
r ⁻ , I ⁻ and BH ₄ ^— ) ammonium,
4. A method according to any one of claims 1 to 3 which is a phosphonium or arsonium salt. 5. The method of claim 4 wherein the phase transfer agent is selected from tetraalkylammonium salts, where the alkyl groups are the same or different and have 1 to 35 carbon atoms. 6. The phase transfer agent is 20 to 5 relative to the aqueous phase.
6. The method according to claim 1, wherein the method is used at a concentration in the range of 00 ppm. 7. The phase transfer agent is used in an amount of 100 to 100 relative to the aqueous phase.
The method of claim 6 used at a concentration in the range of 300 ppm. 8. Fe (II) ions are added to the aqueous phase in an amount of 50.
Use at a concentration in the range of up to 1000 ppm.
Any one of the methods. 9. Cu (II), Ti (IV), Mn (II),
The method according to any one of claims 1 to 8, wherein Co (II), Ni (II), W (IV) or Mo (IV) ions are used in the aqueous phase at a concentration in the range of 0 to 400 ppm. 10. Fe (II) ions and Cu (II), Ti
(IV), Mn (II), Co (II), Ni (II), W (I
10. The method according to claim 1, wherein V) and one or more transition metal ions selected from Mo (IV) are used in equimolar amounts at a concentration in the range of 50 to 400 ppm, respectively. 11. A H ₂ O ₂ aqueous liquid having a molar ratio of added H ₂ O _{2 to} the initially present chlorinated organic product of 0.2 to 10.
11. A method according to any one of claims 1 to 10 used in an amount such that it is in the range 0. 12. The method of claim 11 wherein the molar ratio of added H ₂ O _{2 to} the initially present chlorinated organic product ranges from 0.2 to 30.