The method of stabilization of chlorinated hydrocarbons

 

(57) Abstract:

The invention relates to the technology of organic synthesis, in particular to a method of stabilizing chlorinated hydrocarbons. Carry out the stabilization of the liquid chlorinated hydrocarbon fraction WITH14-C32chlorinated 24-55 wt.% by introducing a stabilizing mixture in an amount of 10 wt.% from stabilized chlorohydrocarbons. Stabilizing system contains epoxygenase resin, 2,6-di-tert-butyl-4-METHYLPHENOL, hexamethylenetetramine and chlorohydrocarbons fraction14-C32when the ratio of the components, equal wt.%: epoxygenase resin (brand ED-20 ED-16) : 2,6-di-tert-butyl-4-METHYLPHENOL(BHT) : hexamethylenetetramine : chlorohydrocarbons fraction14-C32(methenamine) (10-20):(0-3):(0-0,02):(80-90). The technical result is an increase in thermal stability of the product, preventing corrosion of the equipment, caused by hydrogen chloride. table 1.

The invention relates to the technology of organic synthesis, in particular to a method of stabilizing chlorinated hydrocarbons chlorinated 24-55 wt.%, prepared by the chlorination of waste produced by oligomerization of ethylene - -olefin fraction WITH14-C32. On Prauda multifunctional additives to polymeric materials, possessing the properties of secondary plasticizer and lubricant. However, they are characterized by low thermal stability.

Destruction of chlorinated hydrocarbons due to energy impacts: temperature and light. The predominant direction of destruction is the elimination of hydrogen chloride, which is accelerated in the presence of salts of metals of variable valency: iron, copper, and other (Korotkevich, S. H., I. Pimenov F., Gelfand E. A., Sokolov N. G., Zeidman O. A. Methods of preparation and applications of chlorinated paraffin wax in the capitalist countries // xn abroad. - 1975. No. 7. - S. 80-88).

Known method of stabilizing chlorinated, predominantly linear paraffins WITH7-C35chlorinated 10-72% by adding 0.1 to 3% (based on paraffin) aminonicotinate fats (Germany, application No. 3928319. The method of stabilization of chlorinated paraffins. Declared 26.08.89. Published 28.02.91).

The disadvantage of this method is the use of hard-to-reach stabilizer.

There is a method of stabilizing a lower aliphatic chlorohydrocarbons from decomposition by introducing a stabilizing agent containing phosphites: (RO)3R, where R3-C8and chenil12-C16when the weight ratio 4-19:1 and the concentration of the stabilizing agent is 0.1-5% by weight of chloropetalum (A. S. No. 743986 the USSR, MKI 07 With 17/42. The method of stabilization of the lower aliphatic chlorohydrocarbons /N. A. Macmania, P. A. Kirpichnikov, C. H. Kadyrov, A., Liokumovich, A. N. Ziyatdinova, P. C. Vershinin, S. I. Aghajanyan, A. S. Asanov, V. P. Vasiliev, Y. D. Morozov, M. C. Vagapov, L. C. Verizhnikov. - Publ. 30.06.80, bull. No. 24.)

The disadvantage of this method is the use of hard-to-reach stabilizer.

There is a method of stabilizing a lower aliphatic chlorohydrocarbons from decomposition by introducing a stabilizing agent containing an ester of phosphoric acid: (RO)3RO, where R is ethyl, butyl, CRISIL; together with glycerin in the following content of components in the calculation of the stabilized chloropetalum, wt.%:

Ether phosphoric acid 0,01-0,50

Glycerin 0,01-0,50

The disadvantage of this method is the use of hard-to-reach stabilizer.

Closest to the claimed invention to the technical essence and the expected effect is a method of stabilizing chlorinated paraffins of different epoxy resins (ED-20 ED-16). The effectiveness of stabilization, the.F. Krištáľ. Stabilization of chlorinated paraffin wax //INF. bull. according to chem. industry CMEA. - 1989. No. 4. - S. 48-52. - Rus.).

The disadvantage of this method is the low thermal stability.

Object of the present invention to provide an effective method for stabilizing chlorinated hydrocarbons. When carrying out the invention may be obtained from the technical result, which is expressed in the possibility of:

- produce a marketable product with high thermostability;

- to prevent corrosion of the equipment, caused by the hydrogen chloride released during the decomposition process chlorohydrocarbons fraction14-C32.

To improve thermal stability of the injected stabilizer, representing a complex system that includes the antioxidant ionol (2,6-di-tert-butyl-4-METHYLPHENOL), to bind transition metals - methenamine (hexamethylenetetramine) and acceptor of hydrogen chloride - epoxygenase resin (brand ED-20 ED-16), the next time their ratio, wt.%:

Epoxygenase resin

brand ED-20 ED-16 10-20

BHT 0-3

Methenamine 0-0,02

The chlorohydrocarbons14-C3280-90

The stabilizing system is prepared peremeshivaniem system in the amount of 10% by weight of chlorohydrocarbons fraction14-C32and stirring at a temperature of 40-50C in a stream of nitrogen for 0.5 hours. The method is confirmed by examples.

Example 1.

A stabilizing system consisting of 1.48 g (10 wt.%) epoxy resin ED-20 and 13,32 g (90 wt.%) chlorohydrocarbons fraction14-C32prepare by mixing the components in a stream of nitrogen at 40-50C until dissolved. Charged to the reactor 148 g chlorohydrocarbons fraction C14-C32(the chlorine content of 45.6 wt.%, mass fraction of acids in terms of HCl 0,0003 wt.%, mass fraction of iron 0,0013 wt.%) and added 14.8 g of a stabilizing system. Stabilization is carried out at 40-50C in a stream of nitrogen for 0.5 hours. The effectiveness of the stabilizing compounds was evaluated according to THE 6-01-16-90 the amount of released HCl for 4 hours at C.

Example 2.

Analogously to example 1 stabilizing system is prepared by mixing 2,22 g (15 wt.%) epoxy resin ED-20 and 12,58 g (85%) chlorohydrocarbons fraction C14-C32.

Example 3.

Analogously to example 1 stabilizing system is prepared by mixing 2,96 g (20 wt.%) epoxy resin ED-20 and 11,84 g (80 wt.%) chlorohydrocarbons fraction C14-C32.

Example 4.

Analogously to example 1 stabilizing system serves to shift the B>-C32.

Example 5.

Analogously to example 1 stabilizing system is prepared by mixing 2,22 g (15 wt.%) epoxy resin ED-20, 0,444 g (3 wt.%) of ionol and 12,136 g (82 wt.%) chlorohydrocarbons fraction C14-C32.

Example 6.

Analogously to example 1 stabilizing system is prepared by mixing 0,00148 g (0.01 wt.%) urotropine and 14,79852 g (99.99 wt.%) chlorohydrocarbons fraction C14-C32.

Example 7.

Analogously to example 1 stabilizing system prepare a mixture of 1.48 g (10 wt.%) epoxy resin ED-20, 0,00148 g (0.01 wt.%) urotropine and 13,31852 g (89,99 wt.%) chlorohydrocarbons fraction C14-C32.

Example 8.

Analogously to example 1 stabilizing system prepare a mixture of 1.48 g (10 wt.%) epoxy resin ED-20, 0,0074 g (0.005 wt.%) urotropine and 13,31926 g (89,995 wt.%) chlorohydrocarbons fraction14-C32.

Example 9.

Analogously to example 1 stabilizing system prepare a mixture of 1.48 g (10 wt.%) epoxy resin ED-20, 0,296 g (2 wt.%) of ionol, 0,0074 g (0.005 wt.%) urotropine and 13,0166 g (87,995 wt.%) chlorohydrocarbons fraction C14-C32.

Example 10.

Analogously to example 1 stabilizing system is prepared by mixing 2,96 g (20 wt.%) epoxy resin ED-20, 0,296 g (2 wt.%) the data of examples 1-9 are summarized in table.

The proposed method of stabilization allows to obtain a stabilizing effect on the action exceed the effects of the individual components (examples 1-3 and 6). The proposed method in its intensity significantly better than the known.

The method of stabilization of a liquid chlorinated hydrocarbon fraction WITH14-C32chlorinated 24-55 wt.%, consisting in the introduction of a stabilizing mixture in an amount of 10 wt.% from stabilized chlorohydrocarbons, containing epoxygenase resin, 2,6-di-tert-butyl-4-METHYLPHENOL, hexamethylenetetramine and chlorohydrocarbons fraction C14-C32in the following ratio, wt.%:

Epoxygenase resin brand ED-20 ED-16 10-20

2,6-di-tert-butyl-4-METHYLPHENOL (BHT) 0-3

Hexamethylenetetramine (urotropine) 0-0,02

The chlorohydrocarbons fraction C14-C3280-90

 

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FIELD: chemical technology.

SUBSTANCE: invention relates to technology manufacturing halide-substituted hydrocarbons, in particular, to stabilization of halogenated paraffins that are used as plasticizers, antipyrenes and special additives for polymeric materials and rubber mixtures, and in leather industry and in manufacturing depressants and lubricants also. Method is carried out by addition of stabilizing system comprising epoxy-compound and chelate compound forming chelate with iron ions. Stabilizing system comprises additionally acceptor of hydrogen chloride as a stabilizing agent that represents aliphatic carboxylic acid ketene comprising carbon number in chain in the ranges (C10-C23) and alkaline-earth metal of the 2-d group of periodic system in the following ratio of components as measured for the parent halogenated paraffin, wt.-%: chelate compound, 0.03-0.50; acceptor of hydrogen chloride as a stabilizing agent, 0.05-0.30; epoxy-compound, 0.20-0.80. Addition of indicated components of stabilizing system to halogenated paraffin is carried out simultaneously or successively at temperature in the ranges 40-90oC. Stabilizing system can comprise additionally also antioxidant - a stabilizing agent of phenol type representing sterically hindered di- or trialkylphenol or its derivative, or their mixtures taken in the mount 0.01-0.15 wt.-%. Addition of indicated antioxidant - stabilizing agent is carried out before blowing or steaming acid mixtures at temperature in the ranges 40-90oC in common or separately with chelate compound. Halogenated paraffin represents chlorinated paraffin with mass part of chlorine in the ranges 12-75%. Invention provides enhancing quality of stabilized halogenated paraffins by indices "color index" and "mass part of acids", reducing consumption norm of epoxy-compound.

EFFECT: improved stabilizing method.

8 cl, 1 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of stabilising organochlorine solvents selected from perchloroethylene, trichloroethylene, dichloroethylene and chloroform, in which the stabiliser is used in amount of 0.01-1.0% of the weight of the stabilised organochlorine solvent. The stabiliser used is epoxidated soya bean oil, or a stabilising system consisting of 95.55-98.90 wt % epoxidated soya bean oil, 0.10-0.40 wt % urotropin, 1.00-4.00 wt % ethanol and 0.00-0.10 wt % epichlorohydrin, or a stabilising system consisting of 50.0-96.0 wt % epoxidated soya bean oil and 4.0-50.0 wt % ethanol.

EFFECT: highly efficient stabilisation of organochlorine solvents, availability and low cost of stabiliser components and relatively low environmental hazard.

10 tbl

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SUBSTANCE: target product represents 1,2-epoxydodecane and combined with it 1,2-dodecanediol, in a weight ratio of 3:1. The catalytic oxidation of 1-dodecen with sodium hypochlorite is carried out with the application of the catalyst KBr for 10 h in the presence of a solvent - acetonitrile, with a volume ratio 1-dodecene:acetonitrile, equal to 1:8÷15.

EFFECT: increased rate of carrying out the reaction and an increase of the target product output.

3 dwg, 2 tbl, 5 ex

FIELD: chemistry.

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EFFECT: use of the present method enables to obtain an end product in a single reaction step, which ensures acceptable process performance.

21 cl, 4 tbl, 7 ex, 2 dwg

FIELD: chemical technology.

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EFFECT: improved stabilizing method.

8 cl, 1 tbl, 16 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to manufacturing chloro-containing hydrocarbons, in particular, tert.-butyl chloride used for preparing addition agents and as activator for dehydrogenation catalysts. Method for preparing involves interaction gaseous isobutylene and hydrogen chloride in the presence of catalyst in the amount 0.02-0.3 wt.-% of parent reagents mass. Water is used as a catalyst. Process is carried out at volume rate of feeding reagents from 1400 h-1 to 1500 h-1, at temperature from 0oC to -5oC and in the mole ratio isobutylene : hydrogen chloride = (1.01-1.015):1 in the bubbling reactor. Method provides elevating yield of tert.-butyl chloride up to 99.2-99.5 wt.-%.

EFFECT: improved preparing method, enhanced yield.

2 cl, 1 tbl, 4 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention is dealing with production of chlorohydrocarbons exhibiting plasticizing properties in polymer compositions in production of synthetic building materials, varnishes and paints, artificial films and leathers, in rubber industry, and as fire-retardant additives in polymers. Process comprises chlorination of waste obtained in production of C14-C32 fraction by ethylene-α-olefin oligomerization. Chlorination is accomplished in two steps: addition chlorination at 35-55°C followed by substitution chlorination at 40-105°C. Chlorohydrocarbons thus obtained can, in particular, be used as secondary plasticizer in polyvinylchloride compositions.

EFFECT: reduced expenses due to using production waste.

4 tbl, 30 ex

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.

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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

FIELD: organic chemistry, chemical technology, petroleum-chemical synthesis.

SUBSTANCE: invention relates to a method for preparing liquid chloroparaffins. Liquid chloroparaffins are prepared by the hydrochlorination reaction of olefin with hydrogen chloride in the presence of a catalyst wherein α-olefins of (C18-C28)-fraction are used as olefins and water is used as a catalyst taken in the amount 0.02-0.03 wt.-%. The hydrochlorination reaction is carried out at temperature 20-25°C and the volume feeding rate of hydrogen chloride 21-24 h-1 followed by chlorination of the prepared reaction mass with chlorine in the presence of zeolite CaX taken in the amount 2-3 wt.-% at temperature 80-90° and the volume feeding rate of chlorine 19-22 h-1. Using this process promotes to increasing conversion of HCl and chloroolefin, enhances the yield of products, simplifying and reducing cost of the process.

EFFECT: improved preparing method.

2 cl, 7 tbl, 7 ex

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