Method for production of vinylchloride

FIELD: chemical industry, in particular method for production of value monomer such as vinylchloride.

SUBSTANCE: claimed method includes passing of reaction mixture containing dichloroethane vapor trough catalytic layer providing dehydrochlorination of dichloroethane to vinylchloride. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.

EFFECT: method with high conversion ratio and selectivity.

3 cl, 2 ex

 

The invention relates to the field of chemical industry, and in particular to methods of obtaining valuable monomer is vinyl chloride from ethylene dichloride by reaction of dehydrocorydaline

C2H4Hl2With2H3CL+HCl

Known methods for producing vinyl chloride by thermal dehydrochlorination vapor dichloroethane at temperatures of about 450-600° (U.S. Patent No. 3896182, priority from 27.09.73, publ. 22.07.75, IPC 21/02 C 07 C; U.S. Patent No. 4960963, priority from 12.01.90, publ. 02.10.90, IPC C 07 L 17/34; RF Patent № 2179965, priority from 04.08.00, publ. 27.02.02, IPC C 07 C 21/06).

The main disadvantages of these methods is the relatively high temperature process, low productivity and low conversion dichloroethane, the formation of significant quantities of unwanted by-products (in particular acetylene, polihlorgidratov, tar and soot).

Known methods for producing vinyl chloride, based on the reaction of dehydrocorydaline dichloroethane in the presence of catalysts. In particular, known methods, including the use of catalysts based on expanded clay (Ed. mon. The USSR №1558889, priority from 18.07.88, publ. 23.04.90, IPC C 07 C 21/06), modified zeolites (U.S. Patent No. 4384159, priority from 12.03.82, publ. 17.05.83, IPC C 07 C 1/00; Application EP No. 0565789, publ. 20.10.93, IPC C 07 C 17/34), chlorides is Asia and copper, printed on silica gel (Ed. mon. The USSR № 1564975, priority from 15.09.88, publ. 1995, IPC C 07 C 21/06), porous carbon graphite material (RF Patent No. 2053991, priority from 31.01.94, publ. 10.02.96, IPC C 07 C 21/06)and noble metals (platinum, palladium) on alumina carrier (Patent RF № 2070551, priority from 01.11.93, publ. 20.12.96, IPC C 07 C 21/06, 17/25).

The use of these catalysts increases the overall conversion and selectivity dehydrochlorinating dichloroethane, however that does not exclude the formation of harmful by-products. In addition, a common disadvantage of all these known methods is the low reliability and lack of efficiency due to the low stability of the above-mentioned catalysts and their very rapid deactivation, significantly restrict their industrial applications.

Closest to the present invention is a process comprising passing the reaction mixture containing a pair of dichloroethane through a layer of catalyst, providing the dehydrochlorination of dichloroethane to vinyl chloride, which is used a catalyst containing platinum or palladium deposited on a carbon carrier (Patent WO 0029359A1, priority from 16.11.98, publ. 25.05.00, IPC C 07 C 17/25; C 07 C 21/06). To improve the stability of the catalyst is also recommended adding to the initial mixture of water the ode.

The disadvantages of this method is its low reliability and lack of efficiency, due to insufficiently high stability of the catalyst in the absence of hydrogen, rapid decontamination and limited service life.

The authors sought to develop a method of producing vinyl chloride from ethylene dichloride, providing high conversion and selectivity in the conversion of ethylene dichloride to vinyl chloride while ensuring high stability and high performance of the catalyst.

The problem is solved in that in the method of producing vinyl chloride comprising passing the reaction mixture containing a pair of dichloroethane through a layer of catalyst, providing the dehydrochlorination of dichloroethane to vinyl chloride, 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 magnitude of the surface, measured by the method of alkaline titration, SNa=10-250 m2/g at a ratio of SNa/SAG=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 material, woven from filaments with a diameter of 0.5-5 mm

The technical effect of the proposed method is effective for the selective conversion of dichloroethane to vinyl chloride with minimal formation of harmful impurities (acetylene, tar, soot and other). When this catalyst has high activity, stability and high resistance to deactivation, including in the presence of water vapor, which results in high reliability and efficiency of the method.

To obtain a vinyl chloride the reaction mixture containing a pair of dichloromethane, passed through a layer of cat who lyst containing the active ingredient and fiberglass media, and IR spectra of adsorbed ammonia on the specified catalyst have a characteristic absorption band with wave numbers in the range ν =1410-1440 cm-1. As an active ingredient can be used at least one of platinum group metals, particularly 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 a high activity and selectivity of the catalyst in the reaction of dehydrocorydaline dichloroethane to vinyl chloride, 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.

Obtaining vinyl chloride by the procedure described in both the accounts for the high selectivity of the conversion of dichloroethane to vinyl chloride. The catalyst has high activity, stability and high durability without the need for procedures regeneration and reactivation, as well as without the need of introducing into the reaction mixture regenerating reagents (hydrogen). 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 the receipt of vinyl chloride from ethylene dichloride, for which the pair of dichloroethane is passed through the catalyst bed. The catalyst contains glass fiber media (structured in the form of material, woven from filaments with a diameter of 1 mm) 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. At a temperature of 500° and space velocity of the reaction mixture 10 thousand hour-1achieved selectivity of the conversion of dichloroethane to vinyl chloride at 98% conversion of dichlorid is at about 80%. The only byproduct is acetylene, other substances are not detected just at the threshold of sensitivity analysis not higher than 1 ppm. Coking and resinification catalyst is not observed. Conducting the experiment under these conditions for 60 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 a significant decrease in the selectivity of the reaction. 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

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 a similar result.

1. The method of producing vinyl chloride comprising passing the reaction mixture containing a pair of dichloroethane through a layer of catalyst, providing the dehydrochlorination of dichloroethane to vinyl chloride, 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 in And the 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/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 to 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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FIELD: chemical industry, in particular method for production of value products from lower alkanes.

SUBSTANCE: claimed method includes passing of gaseous reaction mixture containing at least one lower alkane and elementary chlorine through catalytic layer. Used catalyst represents geometrically structured system comprising microfiber with diameter of 5-20 mum. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.

EFFECT: method of increased yield.

3 cl, 4 ex

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EFFECT: reduced expenses on starting materials.

2 cl, 3 ex

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FIELD: chemical industry, in particular method for production of value products from lower alkanes.

SUBSTANCE: claimed method includes passing of gaseous reaction mixture containing at least one lower alkane and elementary chlorine through catalytic layer. Used catalyst represents geometrically structured system comprising microfiber with diameter of 5-20 mum. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.

EFFECT: method of increased yield.

3 cl, 4 ex

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