The method shown in fig chloroaromatics connections


(57) Abstract:

Usage: golozhabernyi aromatic compounds, the dehydrochlorination of chlorobenzene and chlorophenols, palladium catalyst. The invention: the hydrochlorination mono - or dichloropropane benzene or phenol are in the vapor phase fluidized bed of catalyst containing 0.5 wt.% palladium on aluminum oxide, in the presence of hydrogen diluted with an inert gas, at 80 to 150C, molar ratio chloroaromatic compounds and hydrogen is 1 : 10. The content of hydrogen in the inert gas of 10 vol.%, the volumetric rate of feed of the mixture of the reactants in an inert gas 2000-25000 h-1exit 94 - 99%. 3 table.

The invention relates to catalytic methods reductive dechlorination of highly dangerous organic substances and can be used for detoxification of chlorinated aromatic compounds, in order to obtain the target products. Thus obtained benzene and phenol are a valuable target products. Chlorine is removed in the form of hydrogen chloride and is used to produce hydrochloric acid.

Widespread use of polychlorinated organic compounds (PHOS) in chemical industrial the person is associated with high toxicity PHOS, their carcinogenic and mutagenic activity, as well as cumulative accumulation in the food chain. In this regard, the urgent development of the detoxification processes of the most dangerous substances of this class.

To destroy PHOS used and developed different methods, resulting in dechlorination of these substances or their complete destruction. The first group of methods dechlorination include: hydrolysis of PHOS alkaline solution poliatilenglikola dechlorination of PHOS metal oxides at a temperature of 200-800aboutC; dechlorination over molten aluminum or metallic sodium. These methods have a rather low efficiency.

The second group includes more technological methods of catalytic and thermal oxidation in a furnace at a temperature of 600-1300aboutWith plasma-chemical decomposition and UV-ozone oxidation. However, detailed studies in recent years have shown that the oxidation processes as byproducts phosgene and especially dangerous chlorinated dibenzodioxin, which dramatically increase the environmental risk technologies oxidative dechlorination.

Analysis of various options for detoxification chlorite is novillero dechlorination due to the fact, that the resulting products are always less dangerous than the original compounds.

Known methods reductive dechlorination of chlorobenzene at 80aboutWith the damages of the catalysts Pd/Al2O3Rh/Al2O3Pd-Rh/Al2O3obtained by ion exchange or by impregnation of the support with solutions of PdCl2or RhCl2. The major transformation products are benzene and cyclohexane. The disadvantage of this method is low (less than 20%) the degree of transformation of chlorobenzene. In addition, dechlorination of other aromatic compounds has not been studied.

The aim of the invention is to develop a method of complete dechlorination of dichlorbenzene, chlorophenols and dichlorphenol with the formation of the high selectivity of benzene and phenol. This goal is achieved by passing steam-hydrogen mixture through the catalyst bed Rd/Al2ABOUT3at a temperature of 80-180aboutAnd space velocities of the reaction mixture 2000-25000 h-1.

All of the examples were used, the catalyst obtained by impregnation-Al2O3an aqueous solution of palladium chloride containing 0.5 wt. metal relative to the mass media, with subsequent recovery of 10% of the temperature 120-150aboutC. Before the experiments, the sample of catalyst was recovered hydrogen for 2 hours at a temperature of 300aboutC and flow rate of hydrogen 8000-10000 h-1. Upon recovery, the temperature was dropped to the reaction temperature and the catalyst was fed a mixture of a given composition.

The experiments were conducted in flow-through catalytic installation in the reactor with a fluidized bed of catalyst. To prevent condensation of the initial reagents and reaction products, all communication lines and valves dispensers were heated in a heating Cabinet at a temperature of 140aboutC. analysis of the reaction mixtures was carried out by gas chromatography using detectors of ionization in flames and heat.

In table. 1-3 shows the results of reductive dechlorination of dichlorbenzene and chlorinated phenols after reaching stationary activity and selectivity of catalysts. The time to reach the stationary activity of the catalysts depends on the nature of the source reagent, the reaction temperature and is 6-10 p.m. the Degree of conversion of the initial reagents, selectivity education and outputs products dehydrochlorination of dichlorbenzene are given in table. 1 is the join are not only chlorobenzene, but dichlorbenzene, mono-and dichlorphenol; high degree of conversion of chlorinated benzenes and phenols 90-100% with simultaneous high yield of benzene (up to 94%) and phenol (up to 83%); to increase the yield of the target products were used catalyst of 0.5% Pd/Al2O3obtained by impregnation of the support with an aqueous solution of palladium chloride, instead of ammonium chloride of palladium and not by an ion exchange method.

P R I m e R 1. To the recovered catalyst was fed a mixture of the following composition: 1,0% para-dichlorobenzene. 10% hydrogen in an inert gas at a temperature of 80aboutC.

P R I m m e R 2. The composition of the mixture as in example 1, except that the reaction temperature 100aboutC.

P R I m e R 3. To the recovered catalyst was fed a mixture containing 1.0% of meta-dichlorobenzene, 10% hydrogen in an inert gas at a temperature of 80aboutC.

P R I m e R 4. The composition of the mixture as in example 3 except that the reaction temperature 100aboutC.

P R I m e R 5. To the recovered catalyst was fed a mixture containing 1.0% of ortho-dichlorobenzene, 10% hydrogen in an inert gas at a temperature of 80aboutC.

P R I m e R 6. The composition of the mixture as in example 5, only the reaction temperature 100aboutC.

P R I m e R 7. the ri temperature 80aboutC.

P R I m e R 8. The composition of the mixture as in example 7, the temperature of the reaction 100aboutC.

P R I m e R 9. To the recovered catalyst was fed a mixture containing 1.0% of ortho-chlorophenol, 10% hydrogen in an inert gas at a temperature of 100aboutC.

P R I m e R 10. The composition of the mixture as in example 9, only the reaction temperature 150aboutC.

P R I m e R 11. To the recovered catalyst was fed a mixture containing 1,0% 2,3-dichlorophenol, 10% hydrogen in an inert gas at a temperature of 130aboutC.

P R I m e R 12. The composition of the mixture as in example 11, only the reaction temperature 180aboutC.

P R I m e p 13. To the recovered catalyst was fed a mixture containing 1,0% 2,4-dichlorphenol, 10% hydrogen in an inert gas at a temperature of 130aboutC.

P R I m e R 14. The composition of the mixture as in example 13, only the reaction temperature 180aboutC.

P R I m e R 15. Temperature as in example 14, only the composition of the mixture 1,0% 2,4-dichlorphenol, 15% hydrogen in an inert gas.

P R I m e R 16. Temperature as in example 14, only the composition of the mixture 1,0% 2,4-dichlorphenol, 5%hydrogen in an inert gas.

This shows that the proposed method allows dechlorination is s benzene and phenol. The benzene is 82-94% phenol 34-83% when the total output deklarirovannykh products 80-100% Increase in flow rate leads to a decrease in the degree of conversion of the initial reactant and the yield of the target products, the growth of output of products of incomplete dechlorination of chlorobenzene and ortho-chlorophenol. The increase in the concentration of hydrogen in the mixture leads to an increase in product yield deeper hydrogenation of phenol cyclohexanone (example 15). The reduction of hydrogen content in the mixture increases the selectivity and product yield incomplete dechlorination of ortho-chlorophenol (example 16). The optimal molar ratio chloroaromatic compounds and hydrogen is 1:10.

The METHOD shown in Fig CHLOROAROMATICS COMPOUNDS in the vapor phase fluidized bed of catalyst containing 0.5 wt. palladium on aluminum oxide, in the presence of hydrogen diluted with an inert gas, characterized in that, to increase the yield of the reaction products, as chloroaromatics connections use mono - or dichloropropane benzene or phenol, and the process is conducted at 80 180oWith a molar ratio of chloroaromatics connection; hydrogen 1 10, the content of hydrogen in inert gas about 10. with about the


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