The use of quaternary fofanah salts as catalysts photolytic decomposition of 2,3,7,8 - tetrachlorodibenzo-p-dioxin

 

(57) Abstract:

Use: as catalyst photolytic decomposition of 2,3,7,8-tetrachlorodibenzo-n-dioxin. Products: Quaternary postname salt f-crystals RR'R"R"'P+X-where R'=R"=R'=C6H5R=CH3X=J, if R'=R"=R'=N(C2H5)2R=CH3X=J, if R'=R"=R'=N(C2H5)2R=CH2C6H5X=Cl. Reagent 1: R R"R"'P Reagent 2: RX. Reaction conditions: in a medium of an organic solvent. table 1.

The invention relates to the neutralization of harmful chemicals, specifically to the field of photolytic decomposition of 2,3,7,8-tetrachlorodibenzo-n-dioxin (TCDD).

The high toxicity of TCDD combined with its chemical and thermal stability, significantly complicating the decomposition. However, some known methods of decomposition of TCDD by chemical, physical-chemical and other methods.

As analogs of the invention were examined following the methods of decomposition of TCDD.

1. Burning.

Pure TCDD during pyrolysis in the quartz tube is completely biodegradable without significant evaporation into the atmosphere when 800.1000oC (Esposito M. P. Drake, H. M. Smith J. A. Owens T. W. Dioxins. Volume 1. 's the attachment (106rad/h) decomposes for 30 h at 97% (ibid.).

3. Catalytic oxidation.

At room temperature TCDD and its analogues, in suspension RUO Li4in CCl4decomposes in less than 1H. (New Scientist, 1981, 90, 1253, 421).

As a prototype method was chosen photolytic decomposition in the presence of Quaternary ammonium salts (H) (Botre C. Meloni A. Alhaigue F. Environ. Sci. Technol. 1978, 12, 3, 335-336) /4/.Research carried out in this work showed the relative instability of polychlorinated dibenzo-n-dioxins to UV radiation. Photo-destruction of chlorinated dibenzo-n-dioxin is carried out by sequential reactions dekhlorirovanie TCDD or the products of its decomposition. It is shown that in aqueous solutions containing H, occurs as solvation TCDD and its subsequent accelerated fotorazlozheniya. For example, the destruction of 8 µg/ml TCDD in 0.02 M solution of 1-hexadecylpyridinium when UV irradiation is terminated for 4h to 90% whereas in the solution of methanol after 8 h of irradiation is 25% TCDD.

Although TCDD in aqueous solutions H decomposes more fully than in methanol, however, are still quite large concentrations. High toxicity and stability of the TCDD elimination of industrial waste.

Known Quaternary postname salt containing hydrocarbon radicals, and dialkylamino /Portela Etc. Vulcano R. Chemistry of organic compounds of phosphorus. M: Chemistry, 1972, S. 219,232/. Obtaining mentioned salts described in literature /A. C. the USSR N670575, class C 07 F 9/54, publ. 1979; A. S. USSR N1271862, class C 07 F 9/54, publ. 1986; U.S. patent N2730547, class C 07 F 9/54, publ. 1956/. /1, 2, 3/

It is known the use of Quaternary fofanah salts as accelerators of vulcanization of forecasters in the manufacture of rubber products /Novitskaya S. P. and other Forecaster. M: Nauka, 1988.-S./. Quaternary postname salts are also used for unsaturated compounds from halogenoalkanes /Demlow E. Demlow H. interfacial catalysis. M. Mir, 1989-485 with./.

However, the use of Quaternary fofanah salts as catalysts photolytic (UV-irradiation) decomposition TCDD unknown.

The task of the invention is the use of Quaternary fofanah salts as catalysts for the photolytic decomposition of 2,3,7,8-tetrachlorodibenzo-n-dioxin with the aim of increasing degree of decomposition and expand the Arsenal of surface-active substances with catalytic activity in the process photolytic (UV-oblici:

RR'R"R"'P+X-,

where R'=R"=R'=C6H5R=CH3X=J;

when R'=R"=R'=N(C2H5)2R=CH3X=J;

when R'=R"=R'=N(C2H5)2R=CH2C6H5X=Cl.

Example 1. The results of experimental studies. In a quartz cuvette with a capacity of 10 ml was poured equal amounts of TCDD in hexane with a concentration of 110-2mg/ml and 0.02 M aqueous solutions of Quaternary ammonium and fofanah salts. The cell solutions were placed in a fume hood at a distance of 40 plus or minus 5 cm from working ORC-21 (irradiator mercury-quartz lamp power 400 watts). Sampling of organic and water layers is 0.5, 1.5 and 2.5 h after the start of irradiation. Samples were dried, dissolved in hexane and analyzed on the content of TCDD using chromatograph Color-560" detector constant recombination velocity (RPS).

The chromatography conditions: glass column: length 1.2 m, 3 mm, stationary liquid phase is 5% OV-101 on inerton-super (0.1 to 0.125 mm), the temperature of the evaporator 300oC, detector 300oC, thermostat 270oC, the speed of the carrier gas (nitrogen O. C. H.)-32 plus (minus)1 ml/min, volume of injected sample 1 μl.

Analysis of the results, presents the process photolytic decomposition of TCDD. The effectiveness of fotorazlozheniya TCDD increases about 2 times or more.

Thus proven method fotorazlozheniya TCDD using Quaternary fofanah salts has obvious advantages in comparison with previously known.

Example 2. Methods for the synthesis of Quaternary fofanah salts

2.1. Method for producing Tris(diethylamido)-phosphite

PCl3+6HN(C2H5)2_

The IR spectrum of the substance in the vaseline confirmed the structure and purity of the compounds (cm-1:1210 (C.)ac(NC2); 1020 (c.)ac(P-N-C); 970 (C.) (NC-C); 690 (C.) (PN3).

2.3.Method for producing Tris(diethylamido)-benzylphosphonate

P[N[C2H5)2]3+CLCH2C6H5__ M. D.): 13,19 (CH3,NCH2CH3); 40,64 (CH2,NCH2CH3);

104,17.132,41 (C6H5); 30,40 (CH2)

Jp-c=78,0 Hz.

The IR spectrum of the substance in the vaseline confirmed the structure and purity of the compounds (cm-1):3065 (SL.), 3050 (SL.) n (=CH)arene.; 1603 (SL.) 1505 (SL.) n (C= C)arene.; 1205 (C.) ac(NC2; 1015 (C.)ac(P-N-C); 960 (c.) n (NC-C).

2.4. The method of obtaining triphenyl-methylphosphonite

In trekhgolovy reactor with a capacity of 2 l moved the Reaction mixture is left at room temperature for 24 hours Then the benzene was evaporated without vacuum (with heating). To the residue was added to 1600 ml of ether. When grinding the mixture falls yellow precipitate. The precipitate was filtered and dried in vacuum. To remove color impurities) to the precipitate add 700 ml of absolute ethanol. At low heat dissolve the entire product. Then in vacuum remove most of the alcohol (approximately) 600-650 ml is Obtained yellowish syrupy mass. It added to 2000 ml of ether and triturated. It releases a colorless precipitate. The weight of sediment 376 g (62% of theoretical). From the remnants of solvents substance dried in vacuo with heating to 50oC.

Features triphenyl-methylphosphonite:

Brutto-formula C19H18PJ;

Melting point 183.185oC;

Elemental analysis,

C calc.56,44; found 56,98-56,83;

H calc.to 4.46; found 4,87 4,70;

P-calc.to 7.67; found 7,52 7-7,36.

NMR13C (CHCl3d, M. D.):7,46(CH3), 117,82.135,23 (C6H5)

Jp-c=47,6 Hz.

The IR spectrum of the substance in the vaseline confirmed the structure and purity of the compounds (cm-1:3050 (SL.) n (=CH)arene.; 1590 (SL.), 1490 (SL.) n (C=C)arene.;1440 (c.) n (P-Ph); 750 (C.), 690 (C.) d (=CH)arene.; out-of-plane.

Application is, X J, with R'= R"= R'= N(C2H5)2R CH3,X J, with R'= R"= R'= N(C2H5)2R CH2C6H5X Cl as catalysts photolytic decomposition of 2,3,7,8-tetrachlorodibenzo-p-dioxin.

 

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