Method for utilization of chlorine-containing waste

FIELD: chemistry, in particular utilization of chlorine-containing waste.

SUBSTANCE: claimed method includes passing of organochlorine compound vapors blended with oxygen-containing reaction gaseous mixture through catalyst layer providing oxidation of starting organochlorine compounds. Said catalyst represents geometrically structured system from microfibers with length of 5-20 mum. Catalyst has active centers which are characterized by presence of absorption band in absorbed ammonia IR-spectrum with wave number ν = 1410-1440 cm-1; contains platinum group metal as active ingredient; and glass fiber carrier. Said carrier in NMR29Si-spectrum has lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio of Q3/Q4 = 0.7-1.2; in IR-spectrum it has hydroxyl absorption band with wave number ν = 3620-1440 cm-1 and half-width of 65-75 cm-1; has specific surface, measured by BET using argon thermal absorption: SAr = 0.5-30 m2/g; surface area, measured by alkali titration: SNa = 10-250 m2/g, wherein SNa/SAr = 5-30.

EFFECT: selective oxidation of starting organochlorine compounds to safe and easily utilizing substances without toxic by-product formation.

3 cl, 4 ex

 

The invention relates to the field of chemistry, and in particular to methods of disposal of chlorinated wastes, and can be used for purification of gaseous and liquid emissions from toxic organochlorine contaminants in the first place, chlorohydrocarbons.

A known method of disposal of chlorinated compounds, including homogeneous oxidation of chlorinated organic compounds by oxygen refractory-lined furnace at a temperature of at least 600° (U.S. Patent No. 4018879, priority from 21.06.76, publ. 19.04.77, IPC 01 7/00).

The disadvantage of this method is low efficiency of transformation of initial chlorine-containing waste into non-toxic or legkodelimae compounds (HCl, H2O and CO2), as well as the formation of significant quantities of hazardous by-products of oxidation (elemental chlorine, phosgene, dioxins, nitrogen oxides).

Known methods of utilization of organochlorine wastes, based on the reactions of oxidation of chlorinated organic contaminants in the presence of a catalyst. In particular, known methods, including the use of catalysts based on oxides of zirconium, vanadium, manganese, cobalt or cerium, and at least one of platinum group metals (U.S. Patent No. 5578283, priority from 30.12.94, epubl, IPC 01 7/00), on the basis of transition metals deposited on a zeolite wear the spruce (U.S. Patent No. 3989806, priority from 10.02.75, epubl, IPC 01 7/02), on the basis of carbon-containing media (U.S. Patent No. 5344630, priority from 28.06.91, publ. 06.09.94, IPC B 01 J 8/02, 01 7/01) and on the use of alkaline salts of vanadium (U.S. Patent No. 5075273, priority from 28.11.89, publ. 24.12.91, IPC B 01 J 21/04, B 01 J 21/08, B 01 J 23/04, B 01 J 21/08).

The use of these catalysts increases the overall efficiency of the oxidation of chlorinated organic impurities, however, that does not exclude the formation of harmful by-products of oxidation. In addition, a common disadvantage of the known methods is the low stability of the above-mentioned catalysts and their rapid decontamination, practically excluding the possibility of their industrial applications.

Known method of sharing catalytic oxidation of organic and chlorinated organic impurities, comprising passing the reaction gas mixture of organochlorine impurities with oxygen sequentially through two layers of catalyst, the first of which uses a catalyst based on media with low acidity, and the second catalyst based on media with high acidity (U.S. Patent No. 5451388, priority from 21.01.94, publ. 19.09.95, IPC B 01 D 50/00, B 01 D 53/00). The use of such a combination of catalysts provides a highly efficient oxidation of both organic and chlorinated organic impurities, however), the government reduced the amount of harmful impurities (CO, the phosgene, dioxins, nitrogen oxides).

The disadvantage of this method is that its implementation is not excluded unwanted education trudnootdelyaemogo and highly toxic elemental chlorine.

Closest to the present invention is a process comprising passing vapors of chlorinated organic compounds in the composition of the oxygen-containing reaction gas mixture through the catalyst bed to ensure oxidation of the source of organochlorine compounds (U.S. Patent No. 4423024, priority from 26.05.82, publ. 27.12.83, IPC 01 21/20, 01 7/01). High selectivity for the catalytic oxidation of chlorinated organic impurities in the hydrogen chloride, water and carbon dioxide without the formation of harmful impurities in the known method is achieved by the use of catalysts based acid resistant zeolite molecular sieves.

The disadvantages of this method are not sufficiently high stability of the zeolite catalyst systems in the presence of water vapor, causing their rapid deactivation and a limited lifetime, as well as their relatively low catalytic activity.

The authors sought to develop a method of disposal of chlorinated wastes, providing high efficiency oxidation of organochlorine contaminants in HCl, H2O and CO2without education element of the ary chlorine and other harmful and trudnoozhidaemyh impurities (CO, the phosgene, dioxins etc) while ensuring high stability and high performance of the catalyst.

The problem is solved in that in the method of disposal of organochlorine compounds comprising passing vapors of chlorinated organic compounds in the composition of the oxygen-containing reaction gas mixture through the catalyst bed to ensure oxidation of the source of organochlorine compounds, using a catalyst comprising a geometrically structured system of microfibers with a diameter of 5-20 μm, having active centers, which are characterized in the IR spectra of adsorbed ammonia in the presence of absorption bands with wave numbers in the range ν=1410-1440 cm-1containing the active ingredient, which is one of the platinum group metals, and glass fiber media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (line Q3and -110±3 ppm (line Q4) when the ratio of the integral intensities of the lines of Q3/Q40,7-1,2, in the infrared spectrum absorption band of hydroxyl groups with wave number ν=3620-3650 cm-1and the width of 65-75 cm-1having a specific surface area measured by the BET method by thermal desorption of argon, SAr=0.5 to 30 m2/g, the amount of the surface of arenow using alkali titrations, SPA=10-250 m2/g at a ratio of SNa/SAr=5-30. The active component of the catalyst may be at least one platinum group metals, in particular platinum. Fiberglass catalyst carrier can be structured as either non-woven or extruded material such as wool or felt, or threads with a diameter of 0.5 to 5 mm, or woven from the threads of the material with the weave type : sateen, canvas, Agur with a cell diameter of 0.5 to 5 mm

The technical effect of the proposed method is effective for the selective oxidation of the source of organochlorine compounds to legkodeformiruemyh (hydrogen chloride) and harmless (carbon dioxide, water) substances without the formation of harmful impurities (elemental chlorine, phosgene, CO, dioxins etc). This method offers improved technical and economic characteristics, due to the high catalyst activity, stability and high resistance to deactivation, including in the presence of water vapor.

For the disposal of chlorinated organic compounds, the reaction mixture containing at least a pair of these organochlorine compounds and oxygen, is passed through a catalyst layer containing the active component and glass fiber media, and IR spectra of adsorbed ammonia on the criminal code of sannam the catalyst have a characteristic absorption band with wave numbers in the range ν =1410-1440 cm-1and as the active component uses at least one of platinum group metals, in particular platinum. The presence of these bands in the IR spectra of adsorbed ammonia is clear evidence of the presence on the surface of the specific catalyst active centers, providing high selectivity of the oxidation of organochlorine contaminants in HCl, H2O and CO2without the formation of elemental chlorine and other harmful and trudnoozhidaemyh impurities (CO, phosgene, dioxins etc), as well as high activity and stability of catalyst. The establishment of such centres can be carried out by targeted modification of the catalyst surface in a variety of ways at the stage of its preparation.

For implementing the method using a catalyst formed into flexible, permeable to flow of the reaction mixture, fiberglass structures, made in the form of a woven or extruded materials. Such structuring facilitates the placement and fixation of the catalyst in the catalytic reactor and prevents entrainment of the microfibers of the catalyst from the reaction stream.

Disposal of chlorinated organic compounds by the described method provides a high selectivity of the oxidation source of organochlorine compounds to legkodeformiruemyh (chlorine is East hydrogen) and harmless (carbon dioxide, water) substances without the formation of harmful impurities (elemental chlorine, phosgene, CO, dioxins etc). The only chlorine-containing product of the reaction, hydrogen chloride can be readily recycled as a valuable industrial product - product hydrochloric acid. The catalyst has high activity, stability and high resistance to deactivation, including in the presence of water vapor. It also provides mechanical stability of the catalyst layer, allowing you to create different types of catalyst (axial, radial, and others) and to have a catalytic reactor in any geometric orientation (vertical, horizontal etc), which significantly increases efficiency and extends the application of the method.

Example 1

Produce utilization of dichloroethane, to which the pair of dichloromethane is mixed with air (volume concentration dichloroethane 3.5%) and passed through the catalyst bed. The catalyst contains glass fiber media (structured in the form of a woven material) and active component (platinum), and in the preparation of the catalyst is modified so that the IR spectra of adsorbed ammonia on the specified catalyst had a characteristic absorption band with wave numbers in the range ν=1410-1440 cm-1. P and temperature 500° C and space velocity of the reaction mixture 18 thousand hours-1achieved complete conversion of dichloroethane in hydrogen chloride, water vapor and carbon dioxide. Other oxidation products (products of incomplete oxidation, elemental chlorine, phosgene, dioxin) not detected just at the threshold of sensitivity analysis not higher than 1 ppm. Conducting the experiment under these conditions for 6 hours shows no decrease in activity and selectivity of the catalyst.

Using the same unmodified catalyst (not with these bands in the IR spectra of adsorbed ammonia), leads to the formation of significant quantities of unwanted by-products (vinyl chloride WITH). The use of other known catalysts is also associated with the formation of undesirable side products, in addition, they are strong deactivation in these conditions.

Example 2

Recycling in similar conditions are chlorobenzene and butyl chloride. At temperatures of 400°achieved full conversion of hydrogen chloride, water vapor and carbon dioxide. Education other oxidation products, as well as deactivation of the catalyst is not found.

Example 3

Spend disposal dichloroethane, chlorobenzene or butyl chloride, as in example 1, but a pair of these compounds are mixed in with the spirit, containing 3.1% of water vapor, and then passed through the layer steklotarnogo catalyst. Throughout the specified range, the introduction of water vapor does not change the activity of the catalyst and the composition of the formed reaction products.

Example 4

Same as in example 1, but using a catalyst in which the optical fiber is structured in the form of a nonwoven extruded felt. Achieved results similar to those described.

1. The method of disposal of organochlorine compounds comprising passing vapors of chlorinated organic compounds in the composition of the oxygen-containing reaction gas mixture through the catalyst bed to ensure oxidation of the source of organochlorine compounds, characterized in that the use of catalyst comprising a geometrically structured system of microfibers with a diameter of 5-20 μm, having active centers, which are characterized in the IR spectra of adsorbed ammonia in the presence of absorption bands with wave numbers in the range ν=1410-1440 cm-1containing the active ingredient, which is one of the platinum group metals, and glass fiber media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (line Q3and -110±3 ppm (line Q4) when the ratio of integrated intensities if the s Q 3/Q4from 0.7 to 1.2, in the infrared spectrum absorption band of hydroxyl groups with wave number ν=3620-3650 cm-1and the width of 65-75 cm-1having a specific surface area measured by the BET method by thermal desorption of argon, sAr=0.5 to 30 m2/g, the magnitude of the surface, measured by the method of alkaline titration, SNa=10-250 m2/g at a ratio of SNa/SAr=5-30.

2. The method according to claim 1, characterized in that the active component of the catalyst is platinum.

3. The method according to claims 1 and 2, characterized in that the optical fiber catalyst is structured in the form of either non-woven or extruded material such as wool or felt or material, woven from filaments with a diameter of 0.5-5 mm



 

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3 cl, 4 ex

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4 tbl, 30 ex

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2 cl, 1 tbl, 4 ex

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8 cl, 1 tbl, 16 ex

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