CA2107455A1

CA2107455A1 - Process for the disposal of chlorinated organic products by oxidation treatment

Info

Publication number: CA2107455A1
Application number: CA002107455A
Authority: CA
Inventors: Ivan Wlassics; Fulvio Burzio; Mario Alfieri
Original assignee: Individual
Current assignee: Solvay Specialty Polymers Italy SpA
Priority date: 1992-09-30
Filing date: 1993-09-30
Publication date: 1994-03-31
Also published as: EP0593895B1; EP0593895A1; HU9302745D0; JPH06198000A

Abstract

ABSTRACT

A process for the disposal of chlorinated organic products, wherein said products are treated with a H2O2 aqueous solution in the presence of Fe(II) ions, optionally in association with other transition metal ions selected from Cu(II), Ti(IV), Mn(II), Co(II), Ni(II), W(IV) and Mo(IV), or mixtures thereof, and in the presence of a phase transfer agent. The process leads to a substantially complete oxidation of the chlorinated organic product, with formation of non-toxic substances and good mineralization degree of chlorine atoms.

Description

2~7~

The present invention relates to a proce~ for the dis-po~al of chlorinated organic product~. More particularly, the present invention relates to a proces~ for the disposal of chlorinated organic product~ by an oxidation treatment with hydrogen peroxide (~2) ~ in th~ pre~ence of F~(II) ion~, optio~ally a~sociated with other transition metal ion~, and of a phaae tran~fer agent.
Chlorinated organic product~ are a clas~ of 9ub-sta~ce~ widely u~ed in varlou~ technological f ielda . Among them, the compound~ ha~ing alkyl, aromatic, or alkylarornatic structure, such as polychlorobiphenyl~ (PCB~), 1,1,1-trichloro-2 , 2 -bis (p-chlorophenyl) e~hane (DDT), tetrachloroethane, dlchloroberLzene~3, chlorophenol~, hexachlorocyclohexane, or ole~inic ~tructure, ~uch aa ~richloroethylene, are mor~ ~ommo~.
Generally, chlorinated organic products are toxic and highly polluting products, whose disposal after us~ involves many problems. In fact, it is necessary to utilize a disposal process, applicable also on a large scale, which is as m~ch as possible efficacious, economical and free from risks for the en~ironment. It is particularly difficult to reach this optimum objective, since the chlorinated organic products are very stable and, when treated with chemical and/or physical means, form highly polluting by-products.

~1~7~

For in9tance, polychlorobiphenyls (PC~) are highly toxic and cancerogenou3 chloroaromatic compounds, which were broadly utilized even recently, due to their dielectric properties, as oils for electrical equipment, and in particular for capacitors. Due to their high toxicity, the regulations in foxce impose the elimina~ion o~ PCBs and sub~ti~ution therefor with hydrocarbon mineral oils. This nec~s~itates removal ~
great amounts o~ PCB~, which usually are either dissolved in organic solvents (for ~xample h~xachloroben~ene), or impregnated in isolating and/or supporting materials, such as paper, paper-board, wood, etc. Further, it i5 oft~n necessary to remove the PCBs from mineral oils, which could be contaminated in consequence o~ inadequate cleaning of the electrical equipment before the replacement.

The mo~t commo~ly utilized trea~ment for the dispo~al of chlorinated organlc product~ is burning, w~ich i~ carried out in properly equipped plants in order to prevent the ~ormation o~ utmo8t toxic chloro-organic compound~, ~uch a~ parachloro-dibenzodioxine~, parachlorodibenzofuran~ ~nd the like. In any event, thi~ i~ an expen~ive proces~, not free from risk~ for thq en~ironment, apart from the fact that it in~olveY the elimination not only of the chlorinated compou~ds, but al~o of the materials polluted by them.
The Applican~ has now found a proce~s for the di~posal of chlorinated organic product~, which compri~es oxidating such 2 ~

products with ~2 in the presence of suitable catalysts and phase tran~fer agents, with forma~ion of non-toxic sub~tance~
and possibility of reco~ering the polluted material, with con-~iderable economical and environmental advantages in compari-son with the processes utilized 80 far.

Accordingly, in one of its a~pects, the present invention provides a proces~ for the disposal o~ chlorinated organic products, which comprises treating the product~ with a H20~
aquaous solution, in the pre~encQ of Fe(II) ion~, optionally in association with one or mor~ transition ~etal ions s~lected from Cu(II), Ti(IV, Mn(II), Co(II), Ni(II3, ~(IV) and Mo~IV), and in the presence of a pha~e tran~er ag~nt.
Non-limiting examples of the chlorinated pr~duots to which the process of the present invention can be applied include thos~ compounds having:

(a) an aromatic structure, such a~ polyc~lorobiphe~yl~
(PC3s), chlorobe~zene~ t~or i~stance, ortho- and me~ha-dichlorobenzene), chlorophenols (for instance para-, tri-and penta-chlorophenol), etc.;
(b) an alkylaromatic ~tructure, ~uch as 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT), and other~;
(c) an olefinic structure, such a~ trichloroethylene, perchlorobutadiene, etc.;
(d) an aliphatic or cycloaliphatic atructure, such a~
tetrachloroethane, hexachlorocyclohexane, hydrated chlor-2 1 ~

al, hexachloroethane, perchloroacetone, e~c.
The reaction involved in the procesl of the present invention i9 an oxidation reaction in heteroyeneous phase, as the chlori~ated orgarlic product~3 ar~ inloluble irl the aqueou~
pha~e cont~lning the ~02/F~+ ox~dizing 0y~em. It is important therefore to include a pha e transfer agent, i.e. o a produce whiCh act~ a~ a "}:~ridge " b~twe~n ~h~ molecule~ of thechlorinated organic product and the oxldlzing ~y~tem. For an exhau~ive di~CU~ioA of such product~ ~e~ C. ~tark~, C. ~iot-ta, RPha~a ~ra~er ca~aly~t~, Acad~ic Pre~ 7a).
Among th~ product~ known i~ th~ art a~ phas~ tran~f er agent~, the one~ whlch are ad~a~tageou~ly utilizable in the proce~ of the prese~t i~v~io~ are th@ ~mmo~lum, pho~phonium or arsonium salt~ of ge~eral ~ormula~/
~ 1 ~"
R~ R4 ~, ,, R9 wherei~:
elected fro~ No P and A~;
Rl, R2, R3 and ~, like or different fro~ one another, are selec~ed from hydrogen, C~-C35, preferably Cl-C12, alkyl groups, C6-C,O aryl group~, ~-C~, preferably ~-CI2, arylalkyl or alkylaryl group~, on condition ~hat at least one out of Rl, ~, R3 and ~ i~ different ~rom hydrogen;
X~ i~ ~elected from OH-~ Cl-, ~r~, I- and B~-.

Another class of pha~e transfer agen~ useful in the process of the pre~ent invention i~ repre~ented by th~
pyridinium salts of formula:
R -+N ~ X~
wherein R i~ a Cl-C~ alkyl group, while X~ i~ the same a~
defined above.
A further cla~ of products useful a~ pha~e tran~fer agents in ~he proce~ of the pre3en~ invention i~ the one of ephedri~e salt3 ha~ing the formula:

tC~- C~I - C~I - N ( Rg) 3~ + X--OH C~3 wherein:
R3, like or different ~rom each other, are C,-C6 alkyl group~;
X- i9 the ~ame a~ defined above. ~uch product~ are de~cribed by Gani V., Tapinte C., Viout P. in ~Tetrahedron Let~ers", p.
4435, 19~3, and by Bun o~ C., Robi~o~ L., Stam M. i~
nTs~rahedro~ ~etter~q, p. 121, 1971.
I~ iB al~o po~ible to utilize mixtureæ of different pha~ tran~fer agent~, ~o a~ to combine i~ the be t way the charac~eris~ iC8 of each type of transfer agent, in order ~o obtain a good mineralization of the chlorine a~om~ a~ well as a complet2 elimina~ion of the chlorinated orga~ic product~.
Examples of pha e tran~fer agent~ useful ln the pro-ces~ of the pre~ent in~ren~ion are:
~C4E~9)4N+ X~; tC~ )3N~C3H~ X-- ; (C~ 7)3N+C~

2~7 1~

~C~I}I37)lN ~CH3~2 X~; (C~H9)3P+C~6H33 X~ )3N~CH3 X-;
(C~H~)3AJ3+CH3 X-; (C~H~CH2)N+ (CH3)~ X ; C~l33-+l~ X~; e~cc~
Particularly prefarred embodiments of the phass transfer agents are the tQtraalkylammonium salts, in which the alkylff, like or ~i~ferent from one another, have ~ to 35 car-bon ato~E~, preferably 1 to 12 carbon a~om~.
U~ually, the chlorinateca orgaIl~c produc~ to b~ remo~ad are pre~ent in amount~3 raLnging ~ro~n 100 ~o 5, OOû ppm, while the phakle transfer agent ia utilized in conce~tration~, relative t~ ttle aqueous phase, ranging from 20 to 500 ppm pre~erably from 100 ~o 300 ppm.
In additiorl to the phase transfer agents, the prs~cess of the presen~ invention cQmpriQe~3 ~he u~ o Pe ( II ) iOI~ a~ cata -lyst~, optionally a~3~0clated with one or rnor~ tra~sition metal ion~3 ~elec~ed from Cu(II), T~ (IV), ~n(II), Co(II), Ni (II), W(IV) and Mo(IV). Among ~che~, Cu(II) ioIl~ are pre~erred. Me~al ion~ are added in amount~ uflually rasging rom 50 to 1, 000 ppm for the Fe (II) ion~ and ~rom 0 to 400 ppm for the other tran-eition metal iorl~ indicated above. In a preferred e~dbodiment, mixture~ of Fe(II) ion~3 ar~.d Cu(II), Ti(IV~, P~tII), Co(II), Ni (~I), W~IV), or ~o (IV~ ion~3 are utilized in equimolar amounts, each o:E th~m in concentration~3 ranging from 50 to 400 ppm, preferably ~rom 150 to 250 ppm.
The above men~ioned metal ion3 are added in the form of 80~ e ~alts. In particular, a~ to Fe (II) ions, it i3 pO~38-~1074~

ible to use for in3tance: ferrous sulphate, ferrous chloride,~errou~ nitrate, a~runonium ferrous ~ulphate, etc. E~eptahydrate ~errous sulphate FeSO~ 7H20 i9 preferred ~rom the operative and economic viewpoint. Among the Cu(II) ~alts, for in~tance pentahydrate cupric sulphate CuS04- 5H2O can be used.
A~ regards hydrogen peroxide, it i~ utilized in the form of an aqueous solution, in such amount~ that the molar ratio of added H22 to initially presen~ chlorina~ed product gen-erally ranges from 0.2 to 100, preferably from 0.2 to 30. The concentration of the hydrogen peroxide aqueous ~olution i8 not a discriminating parameter. To simpli~y the operative modalities, hydroge~ peroxide solution~ at 30-50~ by volume are generally u~ed. The hydrogen peroxide ~olution i~ prefer-ably added gradually and continuou ly to the reaction mixture in order to more ea~ily control the reac~ion conditions, in particular temperature and pH. The addition rate usually ranges from 0.2 to 3 ml/min, but it can b* varied over a wider range, depending on the ~pecific reaction condition~.
The reaction temperature can vary over a wide range, gen-erally from 40 to 200C, preferably from 70 to 120C. The p~
generally ranges from 2 to 7, approximately, preferably from 3 to 4, approximately, and it i9 maintained in such range~ dur-ing the reaction by adding small amounts of a aqueous solution of an acid (for example H2SO4) or of a base (for example NaOH).

2~ ~7~

The process of the present lnvention lead~ to a quantitative conver~ion o~ the chlorinated organic product into non-toxic products, accompanied with a good mineralization level of the chlorine atoms, i.e. conversion of the organic chlorine into chlorine ions.
In the case that th2 chlorinated product to be disposed is dissolved in an organic solvent or in a mineral oil of hydro-carbon type, the reaction mixture i~ heated to the prefixed reaction temperature and then it i9 intensely atirred in order to bring the two phases into intima~e co~tact, ~hereby obtain-ing a wa~er/oil macroemul~ion ~the predominaut pha3e being the organic phase).
The pre~ent invention i~ illu~trated more in detail by the following Ex~mples, which are given ~erely to illu~-trate and not to limit the scope o~ the invention.
In each Example, the progress of the reaction wa followed by withdrawing, after programmed additions o~ hydrogen peroxide, small amounts of the reaction mixture and by determining the following parameters thereof:
(a) Concentration of the chlorinated o~ 'c ~roduct.
It i9 determined by gas chromatographic analy~is (2-meter packed column with fixed phase Tenax~; carrying ga~:
nitrogen temperature program: isotherm at 100C for 2 minutes; gradient at 10C/min. up to 180C; isothenm at laOC for 25 minutes). Each injection (0.6 ~ carried 2~7~

out with a sample diluted with CH~Cl~ in a 1:1 ratio, to which CH30H is added a~ an in~ernal standard.
A~ regards PC~s, all the calculati4ns have been referred to the three main PC~s isomer~, for which the following compo~i~ion has been determined:
Cl2~7Cl3 : 21.21 C,2H,Cls : O . 95~
Cl2~6 : 77.83%
On ~he basis of ~uch compo~i~ion, an average molecular weight of 280.5 haY been detenmined, the average number of chlorine atom~ being equal to 3.74.
(b) Chl~rine ipn conce~ratioa~
The chlorine ions are recovered by mea~ of extraction with H20 acidi~ied with 0.1~ of HN03 and are analyzed through voltimetric titration in an acid medium with AgNO3 .
(c) CO~ (~hemisal Oxy~ ~ Demand).
It is determined by oxidation with pota2siu~ bichromate in acid medium and titration with ferrous ~ulphate, according to the method described by N.W.Hanson in "Offi-cial, Standardized and Recommended Methods o~ Analy~
(page 333, The Society for Analytical Chemistry, 1973).
ExAMpLE~ 1-3 455 ml of a mineral oil contaminated with PCBs (3~31 ppm) were introduced into a reaction flask equipped wi~h condensex, dropping funnels, pH-meter and magnetic stirrer. There~fter, an aqueous solution was added consistiny of 45 ml of H2O, in which ~here were dis~olved: FeSO~7H2O and CuS04 5H2O in ~uch amounts a~ to obtain a concentration of 200 ppm for both the Fe2~ ions and the Cu2~ ions; tetrabutylammonium hydroxlde (IT~A) in amount~ equal to:
- 150 ppm (Example 1);
- 300 ppm (Example 2);
- O ppm (Example 3, comparative).
The re~ulting mixture wa~ heated in an oil bath to 95C
and the p~ was adjusted by mean~ of 3mall addition3 of a 10%
NaOH aqueous solution or of a 15~ ~S04 aqueou3 solutions until a value of about 3.0 wa~ obtained. The mixture wa3 inten~ely stirred in order to form a water-in-oiil macroemul~ion. Then, a ~2 aqueou~ solution (45% by volume) was gradually added at a rate of about 0.6 ml/min. After programmed addition~ of hydro-gen peroxide (as indicated in Table I), reaction mixture 3amples (5 ml each) were drawn for the analysis. For each ~ample, the residual PC~s concentration ([PCB~) and the chlorine ion concentration ([Cl-]) were determined according to-the above described modalities. The results are reported in Table I, where also the mineralization per cent (~[Cl-]) is indicated, expressed as ratio between the actually obtained Cl- ion concentration and the maximum obtainable Cl- ion con-centration.

2~7'1~

During the reactiOn, the pH was maintained around 3.0 by means of 9mall addi~ionS (0.1-0.3 ml) o~ the NaOH or H2SO~ sol-utions, while the temperature was maintained constant at 94C.
The reaction with 150 ppm of ITBA (Exc~mple 1) and the one without ITBA (Example 3) lasted 60 minute~, while the reaction with 300 ppm of IT~A (Example 2~ la~ted 95 minute~.
From ~ comparison between the obtained data, it is noteworthy, first of all, that, without the aid of the phase transfer agent, no PCBs oxidation occurs. With the addition of the phase transfer agent~ an almost complete PC~s elimination i~ obtained, with a satisfactory mineralization degree, in particular in the case of the reactlon with a low ITBA concen-tration (Example 1).
EX~MPLES 4-~
Following the same modalities de~cribed for Examples 1-3, the effectivenes5 of another pha~e tran3fer age~t, tetrabutyl-ammonium bromid~ (TBA~), was checked by comparing the follow-ing reac~ion~:
- with 150 ppm of TBA~ (Example 4);
- with 472 ppm of T~AB (Example 5);
- . without T~A~ (Example 6, comparative).
The data obtain~d are reported in Table II. As for Examples 1-3, it is possible to observe that without the phase trans~er agent the reaction does not occur and that ~he be~t result~, in terms of PC~8 oxidation a~ well a~ of PCBs 2~7'1~5 mi~eralization, are obtained with low concentrations o~ trans ~er agent ( E.YamP1e 4 ) .

Following the sante modalities described for Examples 1-3, the effectiveness of another phase transfer agent, tetrabu~ylammonium iodide (TBAI), was checked by comparing the following reac~ions:
- with 166 ppm of TBAI (Example 7~i - with 460 ppm of TBAI (Example a);
- without TB~ (Example 9, compara~ive).
The data obtained are reported in Table III.

EXA~PL~S lQ-ll Following the same modalities described for Examples 1-3, the effective~e~s of a phase tran~fer age~t mixture (ITB~ +
TBA~) was checked by comparing the following reactions:
- with 100 ppm of ITBA ~ 100 ppm of ~AB (Example 10);
- wi~hout pha~e tran~fer age~ts (Example 11, comparative).
The data obtained are reported in Table IV.
From a comparison of the result~ of Example 10 with the ones obtained in Examples 1, 4 and 7, it i9 evident that the coupling of the two phaqe transfer agents of Example 10 permits the desirable combination of a subs~antially quantitative PCBs oxidatio~ with a good PCBs mineralization degree.

EXAMP~ 12 The same reactor utilized for the preceding Examples was ~7~

filled with 500 ml of H~O, irl which the following products were dissol~ed: FeSO, 7H~O and CuS04 5H~O in such amounts as to ohtain a 200 ppm concentration for both Fe3~ and Cu2~ ions;
tetrabutylammonium hydroxide (IT~A) in an amount equal to 150 ppm.
20 g of PCBs-contamined paper, which had been previously cut into small pieces, were then introduced into the reactor.
The PC~s concentration in the paper was equal to 106~ ppm. It was determined on a paper sample (1 g) by means of continuous extrac~ion at room temperature for 14 hours with 20 ml or CH~Cl2. The PCBs-containing solvent was then analyzed via gas chromatography usi~g methanol as internal standard.
Maintaining the solution under inten3e ~tirring, a 45~
hydrogen peroxide aqueous ~olution was gradually addad until a total ~2 concentration equal to 127.5 g/l was obtained. On conclu ion of the reaction, the chloride ion concentration was determined in the aqueous phase through voltimetric titration in an acid medium with AgNO3. The residual PCBs concentration both in the aqueous pha~e and in the paper pulp wa~ determined via ga3 chromatography after extraction with CH2Cl2, as described hereinabove. The data obtained are reported in Table V.
EX~MPLE 13 loxidation of hexachlorocyclohexane~
0.5 g of hexachlorocyclohexane ~ECE) were introduced into a 250 ml round-bottomed reaction fla~k equipped with dropping 2 1 ~ 7 1 ~ ~

funnel~, pH-meter and magnetic stirrer. Thereafter, an aqueous solution was ~ddeà corlsistlng of 100 ml o~ H20, in which:
FeSO~-7H20 and CuS04- 5H20 in such amounts to obtain a concentra-cion equal to 200 ppm for both Fe2+ and CuZ+ ions;
tetrabutylammonium hydroxide (ITBA~ in amounts equal to 500 ppm, had been dis~olved.
The re3ulting mixture was heated in an oil bath to 95C;
the pH was adjusted at a value o~ about 3.4-3.5 by means of 9mall additions of a 15~ H2SO4 aqueous solution or of a 10%
NaOH aqueou~ solu~ion. The mix~ure wa~ in~en~ely stirred in order to dissolve all ECE. Then, a H202 aqueous qolution (56%
by volume) wa~ gradually added at a rate of about O.4 ml/min.
A~ter programmed addi~ions Of ~2 (as indicated in Table VI), reaction mixture ~amples (5 ml each) were drawn for analy3i~.

In Table VI, the added amounts of H202 are reported a~ nu~ber of stoichiometric equivalents. By stoichiometric equivalent is meant the theoretical amount o~ H202 (100%) necessary for the complete oxidation of the organic ~ub~tances to CO2 and H20.
For each 3ample, the residual ECE concentration ([ECE]), the COD and the chlorine ion concentration ([Cl-]) were deter-mined according to the above described modalities. The result~
are reported in Table VI, where al~o the mineralization per cent (~[Cl-]) i9 indicated, expresged as ratio between the actually obtained Cl- ion concen~ration and the maximum obtainable Cl ion concen~ration.

2~07ll55 During the reaction, the pH was maintained around 3.4 by means of small additions (0.1-0.2 ml) of the NaOH or H2SO~ sol-utions, while the ~emperature was maintalned constant at 97C.
EXAMPLE 14 (oxidatlon of metha-chl~Qr~Qa~gç~
1 g (O.766 ml) of metha-dichlorobenzene (MDB) was intro-duced into a sOo ml round-bot~omed reaction fla~k equipped with dropping funnels, pH-meter and magnetic stirrer. There-after, an aqueou~ 301ution wa~ added consisting of 200 ml of H20, in which: FeSO4 7H20 and CuS04 5~0 in ~uch amounts to obtain a concentration equal to 200 ppm for both Fe2* and Cu2~
ions; tetrabutylammonium hydroxide (ITBA) in amounts equal to 500 ppm, had been dissolved.
The resulting mixtur~ wa~ heated in an oil bath to 95 c and the pH was adjusted at a value of about 3.5 by means of small additions of a 15% H~S04 aqueous 301ution or of a 10% NaOH
aqueou~ solution. The mixture was inten~ely ~tirred in order to dissolve all MDB. Then, a H2O2 aqueous solution (60~ by vol-ume) was gradually added at a rate of about 0.44 ml/min. After programmed additions of H2O2 (as indicated in Table VI), reac-tion mixture samples (20 ml each) were drawn for analysis. For each sample, the residual MD~ concentration ([MD~]) and the chlorine ion concentration ([Cl-]) were determined according to the above described modalities. The re~ults are reported in Table VI, where al~o the mineralization per cent (~[Cl-]) is indicated, e~pres~ed as ratio between the actually obtained ~a7 ~5a Cl ion concentration and the maximum obtainable Cl- ion con-c~ntration.
During the reaction, the pH was maintained around 3.5 by means of small additlons (0.1-0.2 ml) of the NaOH or H2S04 sol-utions, while the ~emperature was maintained constant at 97C.
EXAMPLES 15-17 (oxidatiQn of chlorophen~s~
6.25 g of para-chlorophenol (PCF) (Example 15), or 0.25 g of trichlorophenol (TCF) (Example 16), or 0.25 g of pentachlorophenol (PECF) (Example 17), were introduced into a 500 ml round-bottomed reac~ion flask equipped with dropping funnels, p~-meter and magnetic stirrer. Thereafter, an aqueou~
~olution was added con3i~ting of 250 ml of H20, i~ which:
FeSO4-7H20 a~d CUS04- 5~0 in ~uch amounts to obt~in a concentra~
tion equal to 200 ppm for both Fe2+ and Cu2+ ions;
tetrabutylammonium hydroxide (ITBA) in amounts equal to 500 ppm, had been di~301ved.
Th~ resulting mixture wa heated in an oil bath to 95 C and the pH was adjusted at a value of about 3.0 by mean~ of small additions of a 15% H2S04 aqueous 301ution or of a 10% NaOH
aqueous solution. The mixture was intensely ~tirred in order to dis~olve all PCF, TCF, or PECF. Then, a H2O2 aqueous 301-ution (50~ by volume) was gradually added at a rate of about O.2 ml/min. After programmed additions of H2O2 (as indicated in Table VII), reaction mixture samples (5 ml each) ~ere drawn for analysis. For each sample, the residual PCF, TCF, or PECF

21 ~ 7 1 5 t~

concentratiOn ([PCF], [TCF], [PECF]), the COD and the chlorine ion concentration ([Cl-]) were deter~ined according to the above described modalities. The results are reported in Table VII, where also the mineralization per cent (~[Cl-]) is indi-cated, expressed as ratio between the actually obtained Cl-ion concentration and the maximum obtainable Cl- ion concen-tration.
During the reaction, the pH wa~ maintained around 3.0 by means of small additions (0.1-0.2 ml) o~ the NaOH or H2S04 ~ol-utions, while the temperature wa~ maintain~d con~tant at 97C.

2~07'~
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Claims

WE CLAIM:

1. A process for the disposal of chlorinated organic prod -ucts, which comprises treating said products with a H2O2 aqueous solution, in the presence of Fe(II) ions, optionally in association with one or more transition metal ions selected from Cu(II), Ti(IV), Mn(II), Co(II), Ni(II), W(IV) and Mo(IV), and in the presence of a phase transfer agent.

2. The process of claim 1, wherein the chlorinated organic products have aromatic, alkyl-aromatic, olefinic, aliphatic or cyloaliphatic structure.

3. The process of claim 2, wherein the chlorinated organic products are selected from: polychlorobiphenyls (PCBs), chlorobenzenes, chlorophenols, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT), trichloroethylene, perchloro-butadiene, tetrachloroethane, hexachlorocyclohexane, hydrated chloral, hexachloroethane, perchloroacetone.

4. The process of any of the preceding claims, wherein the phase transfer agent is selected from ammonium, phosphonium or arsonium salts of general formula:

, wherein:
Q is selected from N, P and As;

R1, R2, R3 and R4, like or different from one another, are selected from: hydrogen, C1-C35 alkyl groups, C6-C10 aryl groups, C1-C10 arylalkyl or alkylaryl groups, provided that at least one of R1, R2, R3 and R4 is different from hydrogen;
X- is selected from OH-, Cl-, Br-, I- and BH4-.

5. The process of claim 4, wherein the phase transfer agent is selected from tetraalkylammonium salts, in which the alkyls, like or different from each other, have 1 to 35 carbon atoms.

6. The process of any of the preceding claims, wherein the phase transfer agent is utilized in a concentration, referred to the aqueous phase, ranging from 20 to 500 ppm.

7. The process of claim 6, wherein the chain transfer agent is utilized in a concentration, referred to the aqueous phase, ranging from 100 to 300 ppm.

8. The process of any of the preceding claims, wherein the Fe(II) ions are utilized in a concentration, referred to the aqueous phase, ranging from 50 to 1,000 ppm.

9. The process of any of the preceding claims, wherein the Cu(II), Ti(IV), Mn(II), Co(II), Ni(II), W(IV) or Mo(IV) ions are utilized in a concentration, referred to the aqueous phase, ranging from 0 to 400 ppm.

10. The process of any of the preceding claims, wherein Fe(II) ions and one or more transition metal ions selected from Cu(II), Ti(IV), Mn(II), Co(II), Ni(II), W(IV) and Mo(IV) are utilized in equimolar amounts, each in a concentration ranging from 50 to 400 ppm.

11. The process of any of the preceding claims, wherein the H2O2 aqueous solution is utilized in such amounts that the molar ratio of added H2O2 to initially present chlorinated organic product ranges from 0.2 to 400.

12. The process of claim 11, wherein the molar ratio of added H2O2 to initially present chlorinated organic product ranges from 0.2 to 30.