Method of selective catalytic methane chlorination to methyl chloride

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining methyl chloride by selective catalytic chlorination of methane, involving throughput of a source reaction gas mix containing at least methane and chlorinating agent in the form of either elementary chlorine or a mix of chlorine hydride with oxygen, through at least one catalyst layer. At that, the catalyst features additionally active centres with increased acidity and deuterium/hydrogen exchange depth not less than 10% at the temperature of 350-355°C in the deuterium and hydrogen mix containing 0.6% of hydrogen, 0.6% of deuterium, 0.05% Ar and 98.75% nitrogen, at the volume deuterium-hydrogen mix feed rate of 20000 hours-1 in the thermal regulated reaction mode at the heating rate of 10 K/minute. Active catalytic component is either platinum or copper, or silver. Catalyst carrier is microfibre of diametre of 1 to 20 micron, which can be structured in either non-woven or pressed material similar to wad or felt, or fibre of diametre of 0.5-5 mm, or woven material with lattice similar sateen, canvas, or openwork, with weave diametre of 0.5-5 mm.

EFFECT: high activity and selectivity of methane chlorination to methyl chloride at lower temperatures without production of polychlorinated hydrocarbons.

6 cl, 6 ex

 

The invention relates to the field of chemical industry, namely the method of obtaining valuable intermediate - methyl chloride, which, including, is a promising raw material for the production of ethylene and other light olefins.

Light olefins (ethylene, propylene) are valuable monomers used in industry for the production of polymers and other valuable products of organic synthesis. Currently, the main source of light olefins is oil feedstock. Limited oil reserves and the growth rates limit the possibilities to increase the production of light olefins market demand which displays a strong tendency to increase. In this regard, the actual problem is the expansion of the resource base to produce light olefins, primarily used as a raw material natural gas. One of the promising ways of obtaining light olefins from methane based on the intermediate catalytic synthesis of methyl chloride in the chlorination of methane. Methyl chloride can also be used in the production of other valuable chemical products. The key factors determining the effectiveness of the method of producing methyl chloride, are the high selectivity of the chlorination of methane with minimum formation of undesirable by-product is in (especially polychlorinated hydrocarbons) and a high degree of conversion of methane and chlorine, determined by the activity of the catalyst.

Known way catalytic chlorination of methane using silicalite a catalyst 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 and vysokoglinozemistyj media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (structural type3Q) and -110±3 ppm (structural type4Q) when the ratio of the integral intensities of the lines3Q/4Q from 0.7 to 1.2, in the infra-red spectrum with absorption bands 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 (RF Patent No. 2250890, IPC SS 17/10, B01J 21/08, priority 26.12.2003, publ. 27.12.2005, BI No. 12).

The disadvantages of this method are relatively low activity of the catalyst and the consequent necessity of increasing temperature is eakle (300° C)to achieve maximum conversion of methane, and, as a consequence, the formation of undesirable by-products polychlorinated methanes (methylene chloride, chloroform, carbon tetrachloride).

The authors sought to develop a method of selective catalytic chlorination of methane, providing a high activity and selectivity for the conversion of methane to methyl chloride at low temperatures.

The problem is solved in that in the method of selective catalytic chlorination of methane, including the transmission source of the gas reaction mixture, containing at least methane and gloriouse agent, representing either elemental chlorine or a mixture of hydrogen chloride with oxygen through at least one layer of catalyst 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 and vysokoglinozemistyj media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (structural type3Q) and -110±3 ppm (structural type4Q) when the ratio of the integral intensities of the lines3Q/4Q from 0.7 to 1.2, in the infrared spectrum bands at which the surface 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, optionally in form the active catalyst centers with high acidity, characterized by depth waterboarding exchange at least 10%, at a temperature 350-355°With a mixture of deuterium and hydrogen, containing 0.6% hydrogen, 0.6% deuterium, 0.05% Ar and 98.75% of nitrogen, at a volumetric feed rate specified deuteronomion mixture 20000 h-1mode thermopropionicum reaction at a heating rate of 10 K/min active component of the catalyst is one of the metals or platinum, or copper, or silver. The catalyst carrier is in the form of microfibers with a diameter of from 1 to 20 μm, which 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 to achieve high activity and selectivity of the chlorination of methane to methyl chloride at low temperatures without the formation of polychlori the bathrooms hydrocarbons.

For implementing the method, the reaction mixture containing at least methane and gloriouse agent is elemental chlorine or a mixture of hydrogen chloride with oxygen, is passed through a bed of catalyst 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 and vysokoglinozemistyj media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (structural type3Q) and -110±3 ppm (structural type4Q) when the ratio of the integral intensities of the lines3Q/4Q from 0.7 to 1.2, in the infra-red spectrum with absorption bands 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, which is additionally formed active centers with high acidity, which is characterized by the depth waterboarding exchange not less than 10%, carried out under the following conditions: temperature 350-355°C, the mixture dei is a series and hydrogen - 0.6% hydrogen, 0.6% deuterium, 0.05% Ar and 98.75% nitrogen, the volumetric rate of feed of the mixture 20000 h-1mode thermopropionicum reaction at a heating rate of 10 K/min Specified depth waterboarding exchange under these conditions is unambiguous evidence of the presence of the specific catalyst supercolony active centers, providing high activity (including at low temperatures) and selectivity of the catalyst in the reaction of chlorination of methane methyl chloride. The establishment of such centres can be carried out by targeted modification of the catalyst of various known methods at the stage of its preparation, in particular by sulfation (X.Song, A.Sayati, Catal. Rev., - Sci. Eng., 38(3), p.329-412, 1996). The active component of the catalyst may be any one of the platinum group metals or copper, or silver.

For implementing the method using a catalyst prepared using a carrier in the form of microfibers with a diameter of from 1 to 20 μm. The carrier can be formed into flexible, permeable to flow of the reaction mixture, fiberglass structures, made in the form of yarns, 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 with the reaction the output stream.

The chlorination of methane by the described method provides a high yield of methyl chloride at low temperatures, and thus practically no formation of polychlorinated hydrocarbons. Used in the way that the catalyst has high selectivity, activity, stability and high durability without the need for procedures regeneration and reactivation.

Example 1.

The process of chlorination of methane is carried out at atmospheric pressure, temperature 240°C, space velocity of the mixture 500-800 h-1, volumetric ratio of methane and chlorine in the original mixture of 2:1. Using a catalyst containing platinum on glass fiber media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (structural type3Q) and -110±3 ppm (structural type4Q) when the ratio of the integral intensities of the lines3Q/4Q from 0.7 to 1.2, in the infra-red spectrum with absorption bands 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, and in the process p. the production of the catalyst is subjected to gas-phase sulfation mixture of SO 2(5-15%) and air at a temperature of 200-500°followed by calcining for the formation of acidic active sites, characterized by depth waterboarding exchange at least 10%, at a temperature 350-355°With a mixture of deuterium and hydrogen, containing 0.6% hydrogen, 0.6% deuterium, 0.05% Ar and 98.75% of nitrogen, at a volumetric feed rate specified deuteronomion mixture 20000 h-1mode thermopropionicum reaction at a heating rate of 10 K/min

The catalytic activity increases sharply so that by conversion of the chlorine - achieved 100% conversion of methane, which is close to stoichiometric, the selectivity of the formation of methyl chloride reaches 96%, with the only byproduct of chlorination is methylene chloride. Chloroform and carbon tetrachloride in the reaction products are not available.

In the method adopted for the prototype, which uses a catalyst, in which the depth waterboarding exchange under these conditions is less than 2%, in similar conditions is equal to the level of methane conversion was observed at temperatures below 300°C, and the selectivity for methyl chloride is reduced to 85%among products along with methylene chloride appear polychlorinated hydrocarbons (chloroform).

Example 2.

The process of chlorination of methane is carried out at atmospheric pressure, a temperature of 10° C, space velocity of the mixture 300-500 h-1, volumetric ratio of methane and chlorine in the original mixture of 4:1. Using a catalyst containing platinum on glass fiber media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (structural type3Q) and -110±3 ppm (structural type4Q) when the ratio of the integral intensities of the lines3Q/4Q from 0.7 to 1.2, in the infra-red spectrum with absorption bands 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, and in the process of preparing the catalyst is subjected to gas-phase sulfation mixture of SO2(5-15%) and air at a temperature of 200-500°followed by calcining for the formation of acidic active sites, characterized by depth waterboarding exchange at least 10%, at a temperature 350-355°With a mixture of deuterium and hydrogen, containing 0.6% hydrogen, 0.6% deuterium, 0.05% Ar and 98.75% of nitrogen, at a volumetric feed rate specified deuteronomion mixture 20000 h-1mode thermopropionicum the reaction is AI at a heating rate of 10 K/min

Under these conditions, the catalyst exhibits high catalytic activity so that the conversion of chlorine - achieved 100% of the stoichiometric conversion of methane and almost 100% selectivity to methyl chloride. In the method adopted for the prototype, in these conditions, the conversion of methane at the same selectivity of formation of methyl chloride does not exceed 10%, so that among the reaction products observed unreacted chlorine.

Example 3.

The process of chlorination of methane is carried out at atmospheric pressure, a temperature of 260°C, space velocity of the mixture 500-800 h-1, volumetric ratio of methane and chlorine in the original mixture of 3:1. Using a catalyst containing platinum on glass fiber media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (structural type3Q) and -110±3 ppm (structural type4Q) when the ratio of the integral intensities of the lines3Q/4Q from 0.7 to 1.2, in the infra-red spectrum with absorption bands 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/S Ar=5-30, and in the process of preparing the catalyst is subjected to gas-phase sulfation mixture of SO2(5-15%) and air at a temperature of 200-500°followed by calcining at amounts to 400-650°for the formation of acidic active sites, characterized by depth waterboarding exchange at least 10%, at a temperature 350-355°With a mixture of deuterium and hydrogen, containing 0.6% hydrogen, 0.6% deuterium, 0.05% Ar and 98.75% of nitrogen, at a volumetric feed rate specified deuteronomion mixture 20000 h-1mode thermopropionicum reaction at a heating rate of 10 K/min

The catalyst shows high activity, so that when complete conversion of the chlorine is achieved almost stoichiometric methane reforming. Thus the selectivity of the formation of methyl chloride is 97% and the only byproduct of the reaction is methylene chloride. Chloroform and carbon tetrachloride in the reaction products are not available.

In the method adopted for the prototype, which uses a catalyst, in which the depth waterboarding exchange is less than 2%, in similar conditions is not achieved complete conversion of the chlorine, and the selectivity for methyl chloride is 96%.

Example 4.

The process of chlorination of methane is carried out with a mixture of HCl and air at atmospheric pressure, a temperature of 350°C, space velocity of the mixture 500800 h -1, volumetric ratio of methane, HCl and air in the mixture 2:1:3. Using a catalyst containing platinum on glass fiber media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (structural type3Q) and -110±3 ppm (structural type4Q) when the ratio of the integral intensities of the lines of Q3/Q4from 0.7 to 1.2, in the infra-red spectrum with absorption bands 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, and in the process of preparing the catalyst is subjected to gas-phase sulfation mixture of SO2(5-15%) and air at a temperature of 200-500°followed by calcining at amounts to 400-650°for the formation of acidic active sites, characterized by depth waterboarding exchange at least 10%, at a temperature 350-355°With a mixture of deuterium and hydrogen, containing 0.6% hydrogen, 0.6% deuterium, 0.05% Ar and 98.75% of nitrogen, at a volumetric feed rate specified deuteronomion mixture 20000 h-1mode thermopropionicum reaction at a speed of narewa K/min

The catalyst shows high activity so that the conversion of methane reaches 54%, hydrogen chloride is close to 100%, and the selectivity for methyl chloride is 92%. In the products in addition to methyl chloride and 0.5% methylene chloride detected 0.3% of CO and CO2. In the method adopted for the prototype, the conversion of methane does not exceed 20%, and the selectivity for methyl chloride is reduced to 80%.

Example 5.

Same as in example 3. Use a catalyst containing copper on 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 infra-red spectrum with absorption bands 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, and in the process of preparing the catalyst is subjected to gas-phase sulfation mixture of SO2(5-15%) and air at a temperature of 200-500°followed by calcining for the formation of acidic active sites, characterizing the I depth waterboarding exchange at least 10%, at a temperature 350-355° With a mixture of deuterium and hydrogen, containing 0.6% hydrogen, 0.6% deuterium, 0.05% Ar and 98.75% of nitrogen, at a volumetric feed rate specified deuteronomion mixture 20000 h-1mode thermopropionicum reaction at a heating rate of 10 K/min

Under these conditions, the catalytic activity increases sharply so that when complete conversion of the chlorine is achieved techamerica methane conversion and selectivity of the formation of methyl chloride is 96%, with the only byproduct of chlorination is methylene chloride. Chloroform and carbon tetrachloride in the reaction products are not available.

In the method adopted for the prototype, which uses a catalyst, in which the depth waterboarding exchange under these conditions is less than 2%, in similar conditions equal level conversion of methane and chlorine is observed at temperatures above 300°C, and the selectivity for methyl chloride is less than 90%, and the main by-products are polychlorinated hydrocarbons (particularly methylene chloride, chloroform).

Example 6.

Same as in example 5. Use a catalyst containing silver on 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 attachment of the integral intensities of the lines of Q 3/Q4from 0.7 to 1.2, in the infra-red spectrum with absorption bands 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, and in the process of preparing the catalyst is subjected to gas-phase sulfation mixture of SO2(5-15%) and air at a temperature of 200-500°followed by calcining for the formation of acidic active sites, characterized by depth waterboarding exchange at least 10%, at a temperature 350-355°With a mixture of deuterium and hydrogen, containing 0.6% hydrogen, 0.6% deuterium, 0.05% Ar and 98.75% of nitrogen, at a volumetric feed rate specified deuteronomion mixture 20000 h-1mode thermopropionicum reaction at a heating rate of 10 K/min

The catalyst shows high activity so that the complete conversion of the chlorine is achieved stoichiometric methane conversion and selectivity of the formation of methyl chloride is 95%, with the only byproduct of chlorination is methylene chloride. Chloroform and carbon tetrachloride in the reaction products are not available.

In the method adopted for the prototype, g is e used catalyst, where the depth waterboarding exchange under these conditions is less than 2%, in similar conditions is equal to the level of methane conversion was observed at temperatures above 300°C, and the selectivity for methyl chloride is less than 90%, and the main by-products are polychlorinated hydrocarbons (particularly methylene chloride, chloroform).

1. The method of selective catalytic chlorination of methane methyl chloride comprising passing the source gas of the reaction mixture containing at least methane and gloriouse agent, representing either elemental chlorine or a mixture of hydrogen chloride with oxygen through at least one layer of catalyst 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 and vysokoglinozemistyj media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -300±3 ppm (structural type3Q) and -110±3 ppm (structural type4Q) when the ratio of the integral intensities of the lines3Q/4Q from 0.7 to 1.2, in the infra-red spectrum with absorption bands of hydroxyl groups with wave number ν=3620-3650 cm-1and polushirinoy-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, characterized in that it further catalyst to form active centers with high acidity, characterized by depth waterboarding exchange at least 10%, at a temperature 350-355°With a mixture of deuterium and hydrogen, with 0.6% hydrogen, 0.6% deuterium 0,05% Ar and 98.75% of nitrogen, at a space velocity specified deuteronomion mixture 20000 h-1mode thermopropionicum reaction at a heating rate of 10 K/min

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

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

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

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

6. The method according to any one of claims 1 to 5, characterized in that the catalyst carrier is in the form of microfibers with a diameter of from 1 to 20 μm, structured in the form of either non-woven or extruded material such as wool or felt, or thread dia is a centre 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



 

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EFFECT: increased specific output of the process and lifetime of catalyst.

1 dwg, 3 tbl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to processes for the oxidative halogenation reaction of hydrocarbons, in particular, for synthesis of haloidmethanes, their following processing to value chemical compounds. Method involves contacting methane, halogenated methane or their mixture with halogen source and oxygen source in the presence of catalyst to yield halogenated C1-hydrocarbon having more amount of halogen substitutes as compared with the parent hydrocarbon, Process is carried out at temperature above 200°C but less 600°C and under pressure 97 kPa or above but less 1.034 kPa and at the volume rate of raw feeding above 0.1 h-1 but less 100 h-1. Catalyst comprises rare earth metal halide or oxyhalide no containing iron and copper. The atomic ratio of rare-earth element to iron or copper exceeds 10:1 under condition that if catalyst comprises cerium in the amount less 10 atomic percent of the total amount of rare-earth components then catalyst comprises also one additional rare-earth element. Reacting hydrocarbon is chosen from the group consisting of methane, chloromethane, bromomethane, iodomethane, dichloromethane, dibromomethane, diiodomethane, chlorobromomethane and their mixtures. The molar ratio of hydrocarbon to halogen is above 1;1 but less 20:1 and that to oxygen is above 2:1 but less 20:1. The reaction mixture comprises additionally a diluting agent as nitrogen, helium, argon, carbon monoxide or dioxide or their mixtures. Formed methyl chloride or methyl bromide can be fed to the hydrolysis step to yield methyl alcohol or used in process of catalytic condensation to form light olefins and/or gasolines. It is possible contacting methyl halide with the condensation catalyst to form ethylene and the following preparing vinyl halide monomer, for example, vinyl chloride or acetic acid under carbonylation conditions. Invention provides enhancing output of the process at the expense of using the effective modified catalyst based on rare-earth elements.

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33 cl, 1 tbl, 1 ex

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

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EFFECT: method of increased yield.

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16 cl, 6 tbl, 1 dwg, 20 ex

The invention relates to the production of chlorine-methanes, primarily chloroform
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13 cl, 15 tbl, 11 ex

FIELD: chemical industry; methods of production of the chloroform.

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5 cl, 4 ex, 1 tbl

FIELD: chemical industry; apparatuses for production of the chlorinated allyl.

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EFFECT: the invention provides, that the presented design of the reactor allows to increase the selectivity of the process of production of the chlorinated allyl.

1 ex, 1 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to processes for the oxidative halogenation reaction of hydrocarbons, in particular, for synthesis of haloidmethanes, their following processing to value chemical compounds. Method involves contacting methane, halogenated methane or their mixture with halogen source and oxygen source in the presence of catalyst to yield halogenated C1-hydrocarbon having more amount of halogen substitutes as compared with the parent hydrocarbon, Process is carried out at temperature above 200°C but less 600°C and under pressure 97 kPa or above but less 1.034 kPa and at the volume rate of raw feeding above 0.1 h-1 but less 100 h-1. Catalyst comprises rare earth metal halide or oxyhalide no containing iron and copper. The atomic ratio of rare-earth element to iron or copper exceeds 10:1 under condition that if catalyst comprises cerium in the amount less 10 atomic percent of the total amount of rare-earth components then catalyst comprises also one additional rare-earth element. Reacting hydrocarbon is chosen from the group consisting of methane, chloromethane, bromomethane, iodomethane, dichloromethane, dibromomethane, diiodomethane, chlorobromomethane and their mixtures. The molar ratio of hydrocarbon to halogen is above 1;1 but less 20:1 and that to oxygen is above 2:1 but less 20:1. The reaction mixture comprises additionally a diluting agent as nitrogen, helium, argon, carbon monoxide or dioxide or their mixtures. Formed methyl chloride or methyl bromide can be fed to the hydrolysis step to yield methyl alcohol or used in process of catalytic condensation to form light olefins and/or gasolines. It is possible contacting methyl halide with the condensation catalyst to form ethylene and the following preparing vinyl halide monomer, for example, vinyl chloride or acetic acid under carbonylation conditions. Invention provides enhancing output of the process at the expense of using the effective modified catalyst based on rare-earth elements.

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33 cl, 1 tbl, 1 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

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

The invention relates to the production of freon and/or OCTAFLUOROPROPANE, which is used as a mixed refrigerant gas dielectrics, reagents dry etching of semiconductor materials, laser working media

The invention relates to the cleaning of TETRAFLUOROMETHANE, which is used as a gas for etching or cleaning gas in the production of semiconductor devices

The invention relates to the processing of the products of oxidative pyrolysis gas metadatareader

The invention relates to the field of organic chemistry, in particular to a method for monochloramine derivatives of adamantane and diamantane, which are used in the production of thermo - and hemostatic polymers that serve as the raw material for the synthesis of medicines and are used in the synthesis of other derivatives adamantanone (amines, alcohols, acids)

FIELD: chemistry.

SUBSTANCE: invention relates to the catalyst for synthesising the 2- and 4-picolines, method for its producing and the method for producing the 2- and 4-picolines. The catalyst which can be used in synthesis of 2- and 4-picolines containing the heteropolyacid from the group containing the silicon tungsten acid, phosphorus tungsten acid and the vanadium tungsten acid applied upon the silica gel substrate with the particles size of 6-14 mesh, is described. The method for producing the catalyst is also described, which includes the dissolution of heteropolyacid in distilled water, stirring the obtained mixture with the needed amount of the silica gel to obtain the suspension; mixing the suspension till even impregnation, air drying the suspension at 200-250°C up to 1.5 hour; following heating the suspension at 300 to 400°C within 0.5 to 1.5 hours and cooling the obtained product till the room temperature in the exiccator to obtain the needed catalyst. The method for producing the of 2- and 4-picolines is described which includes the interaction of acetaldehyde and ammonium hydrate at heating in presence of the said catalyst.

EFFECT: stable highly selective and active catalyst is available.

14 cl, 3 ex

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