RU2142931C1 - Method of processing of organic raw material and catalyst for its embodiment - Google Patents

Abstract

FIELD: methods and catalysts for processing of organic raw materials. SUBSTANCE: organic raw material is processed in three-section reactor. Reactor includes section of boron trifluoride source, catalytic section and section of boron trifluoride absorbent. In section of boron trifluoride source, raw material flow in contact with metal tetra fluoroborate applied t porous carrier, and in section of boron trifluoride absorbent, flow of products of catalytic reaction comes in contact with boron fluoride applied to porous carrier and capable of absorption of boron trifluoride. In so doing, periodically, as metal tetrafluoroborate becomes decomposed in section of boron triflouride source and accumulation of metal tetrafluoroborate in section of boron trifluoride absorbent, inversion of functions of these sections of reactor is effected simultaneously with inversion of direction of flows of organic raw material and products of reaction. Used in process is catalyst whose active component is in form of catalytic complex applied to porous carrier and consisting of boron trifluoride and heteropoly compound in ratio of 0.1 to 0.5, preferably, from 0.5 to 2 in amount of 0.1 to 55 wt. %, preferably, from 2 to 30 wt.%. Heteropoly compound is produced from one or several oxides of elements of groups III, IV, V, VI and from one or several salts of metals with general formula (Me)_x(XO₄)_y, where Me is metal of groups III and IV; x=1-2; y=2-3;X is sulfur or phosphorus taken in molar ratio of oxides to salts equalling 0.5 to 20, preferably, from 1.5 to 10, or from compounds forming said oxides and salts in preparation of heteropoly compounds. Composition of heteropoly compound in terms of oxides is described by empirical formula Me_kX_mO_n, where Me are elements taken from group including Ga, B, Al, Ti, Zr, Sn or their mixtures; X are elements taken from group including P, S or their mixtures; k=1-80; m=1-100 with heteropoly compound acidity determined by Hammet's scale within interval pKa from minus 5.6 to minus 12.7. EFFECT: higher yield of desired product and increased efficiency of catalyst. 24 cl, 11 tbl, 44 ex

Description

 The present invention relates to the field of catalytic chemistry relating to processes for the processing of hydrocarbon and other organic raw materials from the refining and petrochemical industries. The invention allows, using a complex of acid catalysts with boron trifluoride, to carry out the processes of conversion of organic compounds to obtain high-octane components of motor fuels and valuable petrochemical feedstocks.

State of the art
For over 60 years, acid catalysts have been used in industry in catalytic processes for the conversion of hydrocarbons and other organic compounds. Over 70% of oil refining and petrochemicals are produced using acid catalysts. The most common processes are: cracking of hydrocarbons, alkylation of isoparaffins and benzene compounds, isomerization of hydrocarbons, polymerization of various organic compounds. The role of acid catalysis in the reforming and hydrocracking of petroleum feeds is noticeable.

 Two classes of acidic catalysts that are widely used at present can be distinguished: traditional Friedel-Crafts catalysts and heterogeneous acidic catalysts. The advantage of Friedel-Crafts catalysts (boron, aluminum and other metal halides, sulfuric, phosphoric and hydrofluoric acids) is versatility and extremely high activity. This class of catalysts has a wide field of application and is used or can be used in the processes of alkylation, isomerization, polymerization, etc. Classical Friedel-Crafts catalysts, the nature of their action and field of application are discussed in detail in GAOlah's books "Friedel-Crafts Chemistry", Wiley Interscience, NY, 1973; G.A. Olah, G.K.S. Prakash, J. Sommer "Superacid", Wiley Interscience, N. Y., 1986.

 At the same time, traditional Friedel-Crafts catalysts have drawbacks that make it difficult or impossible to use them in modern heterogeneous catalysis processes. Such disadvantages include the fact that these are mainly volatile compounds, partially or completely soluble in the reaction mixture, as well as a significant consumption of catalyst per unit of production; high toxicity, corrosiveness of catalysts; problems of utilization, regeneration of spent catalysts.

 The catalytic properties of Lewis acid liquid complexes are known, such as boron trifluoride, aluminum chloride, gallium chloride, zirconium chloride, etc. with oxygen-containing compounds: sulfuric, phosphoric acid, etc. The use of these complexes in the processes of conversion of organic substances, in particular in the processes of alkylation, isomerization and polymerization, is considered, for example, in the book of B. Brooks et al. "The Chemistry of Petroleum Hydrocarbons", NY, 1965. The advantage of catalytic complexes of Lewis acids and oxygen-containing compounds is the low solubility of the complexes in the feed mixture and reaction products and, consequently, the relatively high stability of the chemical composition of the catalysts compared to catalytic complexes based on acids Lewis and other compounds with weak electron-acceptor properties.

Processing of organic compounds using catalytic complexes of oxygen-containing compounds and boron trifluoride includes a number of stages: synthesis of a catalytic complex, saturation of an oxygen-containing compound with boron trifluoride; contacting the initial mixture of organic compounds with a catalytic complex; separation of the catalytic complex and reaction products; removal of boron trifluoride from reaction products; regeneration of boron trifluoride and catalytic complex. A detailed description of the synthesis processes of various catalytic complexes of Lewis acids and oxygen-containing compounds is given in GAOlah's book Friedel-Crafts Chemistry, Wiley Interscience, NY, 1973 and a number of patents (British Patents N 545,441; N 550,711; US Patents N 2,345,095; N 3,873,634; N, 5.173.467). The contacting of the feedstock and the catalyst in processes using liquid catalytic complexes is carried out, as a rule, in apparatuses with stirring, for example, in autoclaves. After contacting with the liquid catalytic complex, the reaction products and the catalyst are separated in a sump and sent for purification from boron trifluoride. A number of known methods for the isolation of boron trifluoride from a stream of hydrocarbon products. In alkylation processes, the removal and regeneration of boron trifluoride is carried out at the fractionation stage of the reaction products (US Pat. No. 4,992,616). After removal of the main amount of boron trifluoride, the recycle stream is purified from the decomposition products of boron trifluoride on various solid adsorbents, for example, aluminum oxide. To purify Lewis acids, the alkalization of reaction products with the formation of alkali metal halides, hydroxides or soluble metal compounds is most widely used (US Pat. No. 5,173,467). Accordingly, with this separation method, the catalyst cannot be reused in the process. The processes of processing organic substances are more advanced, providing for the possibility of isolating Lewis acids from reaction products, regeneration and their reuse. US Pat. No. 4,454,336 discloses a method for recovering boron trifluoride using solid organic oxygen-containing polymers, for example polyvinyl alcohol or polyvinyl acetate. When thermal decomposition of the complex of polyvinyl alcohol and boron trifluoride at 100-150 ^o C under vacuum or in an inert gas stream, gaseous boron trifluoride is obtained, which is returned to the process. US Pat. No. 5,173,467 teaches a possible process for recovering boron trifluoride using Lewis solid bases, for example calcium fluoride, but specific examples are not given to illustrate the use of this process for recovering boron trifluoride. The use of liquid complexes of Lewis acids and oxygen-containing compounds is associated with a number of technological difficulties arising from the need to use special devices to separate the catalytic complex and reaction products, purify hydrocarbon products from excess dissolved Lewis acid, and regenerate the catalyst.

 Heterogeneous acid catalysts, which are zeolite-based catalytic systems (sulfated oxides of transition metals, heteropoly acids of tungsten and molybdenum, ion-exchange resins, etc.), are widely used in modern acid catalysis processes. The use of zeolite catalysts in the processes of conversion of organic compounds, the nature of their action and the field of application are discussed in detail in the book by J. Rabo "The Use of Zeolites in Catalysis", Moscow, Mir, 1972, as well as in a number of patented catalytic systems and processes based on them (patents U.S. N 3,251,902; N 3,549,557; N 3,655,813; N 3,893,942; N 4,992,615; French patent N 1,598,716; German patent N1118,181; author certificate of the USSR N 1622358).

 The use of sulfated metal oxides is disclosed in Japanese Patents N 51-63386; N 57-3650; N 59-40056; N 59-6181; N 61-242461 (A); U.S. Patent Nos. 3,251,902; N, 3,655,813; N, 4,377,721; N, 4,423,267; N, 5.025.094; N, 5,182,247; N, 5,321,197; N, 5,629,257. Macrocellular organic ion-exchange resins in cationic form as alkylation catalysts are described in US Pat. Nos. 3,855,342 and 3,862,258. The indisputable advantages of this type of catalysts are the possibility of application in continuous heterogeneous processes, their regenerability, as well as the environmental friendliness of the processes. The disadvantages of modern heterogeneous acid catalysts and technological processes using them are the low stability of the catalytic effect, especially in the case of sulfated metal oxides, and, accordingly, the need for frequent regeneration; low activity of zeolite and similar systems, which determines the need for the process at elevated temperatures; the molecular weight restriction of the hydrocarbon feedstock, predetermined by the feature of the microporous structure of zeolites and their analogues, which narrows the possible field of use, as well as the high cost of these catalytic systems.

Of considerable interest are catalysts that combine the advantages of traditional catalytic complexes based on Lewis acids and heterogeneous catalysts. A number of patents disclose the use of catalytic complexes of Lewis acids and solid porous materials containing functional oxygen groups. The patents declare various carriers of catalytic systems, which are used as oxides or mixtures of metal oxides of groups III-IV modified with additives of elements of other groups I to VIII (most often oxides of rare earth elements), wide-porous zeolites, ion-exchange resins and other polymeric organic compounds. US Pat. No. 5,276,242 discloses a method for producing a catalytic complex of aluminum chloride and metal sulfates of Group IB-VIII on a porous carrier, the preparation of which includes the following basic operations: synthesis of the complex from aluminum chloride and metal sulfate under conditions protected from moisture by heating metal sulfate and aluminum chloride, taken in a molar ratio of 0.2-0.5, in an organochlorine solvent for 5-30 hours; heating the resulting complex with a porous carrier in an organochlorine solvent for 5-30 hours; solvent removal under vacuum at a temperature of 25-60 ^o C. The resulting catalytic complexes had high activity in the process of isobutane alkylation with butylenes. The process of alkylation of isobutane on the catalytic complexes of aluminum chloride and metal sulfates was carried out under static conditions at a temperature of 30-40 ^o C with a total load on the catalyst for butylene at the level of 1 g / g of catalyst. The following results were obtained: the product yield on the butylenes taken in the reaction is not given; catalyst productivity and resource are not given; selectivity for trimethylpentane hydrocarbons - 30-70% wt. US Pat. No. 5,254,793 discloses a similar process for the preparation of a catalytic complex of aluminum chloride and metal phosphates and its use in the process of isobutane alkylation with butylenes. US Pat. No. 5,245,103 discloses a similar process for the preparation of a catalytic complex of aluminum chloride and sulfated alumina and its use in the isomerization of n-paraffin hydrocarbons.

A method for processing organic substances using heterogeneous catalytic complexes containing Lewis acids (AlCl ₃ ; BF ₃ ; BCl ₃ ; SbF ₅ and others) includes the following basic operations (see, for example, US patent N 2,804,491): synthesis of a catalytic complex, contacting the raw materials at a given temperature and pressure with the catalytic complex, processing the products of the catalytic reaction with the separation of substances and disposal of waste products.

 In US Pat. No. 2,804,491, the alkylation catalyst is silica stabilized alumina gel containing boron trifluoride. Zeolites of the type ZSM-4, ZSM-18, ZSM-20, Beta zeolite (US Pat. Nos. 4,484,161; N 4,992,616; PCT / US / 92/00948) modified with boron trifluoride have been proposed for the isobutane alkylation process.

The use of the active components of Friedel-Crafts catalysts (AlCl ₃ ; BF ₃ ; BCl ₃ ; SbF ₅ ) supported on solid non-zeolite inorganic oxides and fluorides in the processes of oligomerization and polymerization of olefins, isomerization of n-paraffins is claimed in US patents N 3,109,041; N, 4,110,410; N, 4,176,342; N, 4,213,001; N, 4,395,578; N, 4,490,571; N, 4,956,518; N, 5,019,671; N, 5.245.103. US Pat. No. 5,245,103 discloses the use of complexes of aluminum chloride and sulfated aluminum oxides for the isomerization of n-paraffin hydrocarbons. The process of isomerization of n-paraffins is carried out under static conditions with stirring. The temperature of the process is 40-70 ^o C, the pressure is 1-5 atm, the loading of the isomerization feedstock is 2-5 g / g of _{catalyst mash} . The time of the process is 1-3 hours. When isomerization of n-pentane on the claimed composition the following results are achieved: the conversion of n-pentane - 20-70%, selectivity - 50-80%, the catalyst resource is unknown.

For the polymerization of butylenes, US Pat. No. 4,476,342 discloses a method for using a catalytic complex of boron trifluoride and aluminum oxide obtained by reacting boron trifluoride and aluminum oxide at a temperature of 200-350 ^o C. The resulting catalytic complex is loaded into a flow reactor with a fixed catalyst bed and it is fed a mixture of n-butenes at a rate of 1-2 g / g _{mash rolled} • h at a temperature of 110-180 ^o C. in this process the following results: conversion of butylenes - 80-85%, content of n octenes oduktah reaction - 89-91% by weight, the catalyst action resource -. not less than 1000 g / g _{mash rolled.}

 However, the expansion of the scope of such promising catalytic systems is hindered by the instability of complexes formed by the active component and the surface of the carrier. This leads to the removal of the catalytic component with the reaction products, often necessitates the regeneration or utilization of the catalyst, as well as to introduce an additional amount of the catalytic component or compounds into the feedstock that form it upon interaction with the surface of the carrier.

The known process for the alkylation of isoparaffins with 4-22 carbon atoms, olefins with 2-12 carbon atoms (US patent N 4,992,616), in which the widely used porous zeolites ZSM-3, ZSM-4, ZSM-12, ZSM-18, ZSM -20 modified with Lewis acids (AlCl ₃ ; BF ₃ ; BCl ₃ ; SbF ₅ ). To improve and stabilize the process, an additional Lewis acid of 3% wt. Is added to the initial alkylation mixture. and water or oxygen containing compounds. This process and the catalyst used for its implementation is selected as a prototype as the closest to the claimed invention. The process of alkylation of isobutane with butylenes on heterogeneous complexes of boron trifluoride and zeolites is carried out as follows: a heterogeneous complex of boron trifluoride and zeolite is prepared, for which a zeolite containing from 6 to 16% wt. water, placed in an autoclave and isobutane added. The zeolite is saturated with boron trifluoride in a gaseous state at a temperature of 0 ^o C and stirring. The resulting complex is used to alkylate a mixture containing isobutane and butene-1 in a molar ratio of 10 with the addition of excess boron trifluoride in an amount of 3% wt. The process is carried out at a temperature of 0 ^o C, a weight feed rate of butylene 1.2 g / g _{rolled mash} • h, a stirring speed of 1900 rpm. The reaction products enter the sump, where the suspension of the solid catalyst and the alkylation products are separated. From the sump, the catalyst is returned to the autoclave, and the alkylation products enter the separation system. Boron trifluoride is removed from the reaction products by distillation and returned to the autoclave. The product yield on olefins, productivity and resource of the catalyst are, respectively: 190-210% wt .; 2.0-2.1 g / g _{rolled mash} • h; 500-600 g / g of _{catalysis of the torus} .

SUMMARY OF THE INVENTION
An object of the invention is the formation of a catalytic system capable of retaining the active components of the catalyst inside the reaction zone and using catalytic complexes with boron trifluoride for highly efficient processing of organic raw materials in various acid catalysis processes.

 The problem is solved in that in the known method of processing organic raw materials (including preparing a mixture of organic raw materials with boron trifluoride, contacting the stream of the resulting mixture with a catalyst and isolating boron trifluoride from the products of the catalytic reaction), the process is carried out in a three-section reactor, consisting of a section of the source of boron trifluoride, the catalytic section and the boron trifluoride scavenger section; in the boron trifluoride source section, the feed stream is contacted with metal tetrafluoroborate deposited and the porous carrier, and in the absorber section of boron trifluoride, the catalytic reaction product stream is in contact with a metal fluoride deposited on the porous carrier capable of absorbing boron trifluoride, and periodically, as the metal tetrafluoroborate decomposes in the source section and the metal tetrafluoroborate accumulates in the absorber section, the functions of these sections are inverted reactor, which is carried out simultaneously with the inversion of the direction of flow of raw materials and reaction products.

In accordance with a particular embodiment of the method, a catalyst is used containing an active component supported on a porous carrier in the form of a catalytic complex of boron trifluoride and a heteropoly compound with a molar ratio of boron trifluoride to heteropoly compound from 0.1 to 5, preferably from 0.5 to 2, in an amount of from 0.1 to 55 % wt., preferably from 2 to 30% wt. moreover, the heteropoly compound is obtained from one or more oxides of elements of groups III to VI and from one or more metal salts with the general formula (Me) _x (XO ₄ ) _y , where Me is a metal of groups III, IV, x = 1-2, y = 2-3, X is sulfur or phosphorus, taken in the molar ratio of oxides to salts of from 0.5 to 20, preferably from 1.5 to 10, or from compounds forming the oxides and salts in the preparation of the heteropoly compound, the composition of the heteropoly compound in terms of oxides is described empirical formula Me _k X _m O _n, where Me - elements selected from the series: Ga, B, Al, Ti , Zr, Sn and or mixtures thereof; X - elements selected from the series: P, S, or mixtures thereof, k = 1-80, m = 1-100, n = 100-400 and the heteropoly acidity determined on the Hammett scale in the pKa range from - 5.6 to - 12.7.

 According to a particular embodiment of the method, the temperature of the reactants in the source section is set higher than the decomposition temperature of the metal tetrafluoroborate, and the temperature of the reactants in the boron trifluoride absorber section is set lower than the decomposition temperature of the metal tetrafluoroborate.

 In accordance with a particular embodiment of the method, the inversion of the functions of the sections of the source and absorber of boron trifluoride is carried out by changing the temperature of the reactants in these sections.

 In accordance with a particular embodiment of the method, the inversion of the functions of the source and absorber sections of the reactor is carried out with a degree of decomposition of metal tetrafluoroborate in the source section of boron trifluoride of not more than 95% wt.

 In accordance with a particular embodiment of the method, tetrafluoroborate and metal fluoride of groups I, II, III and IV are used.

 In accordance with a particular embodiment of the method, inorganic or organic or carbon materials are used as a porous carrier for tetrafluoroborate and metal fluoride.

 According to a particular embodiment of the method, metal tetrafluoroborate is applied to the porous carrier in an amount of from 0.1 to 90% by weight, preferably from 30 to 70% by weight, and metal fluoride is applied to the porous carrier in an amount of from 0.1 to 90% wt., preferably from 20 to 50% wt.

In accordance with another particular embodiment of the method, the organic alkylation feed and the alkylating agent are contacted with a catalytic complex containing a heteropoly compound with an acidity on the Hammett scale in the range of pKa from −5.6 to −11.4 at a temperature from 0 to 200 ^° C, pressure from 1 to 200 atm and contact time, providing a sufficient depth of conversion of the alkylation feedstock.

 According to another particular embodiment of the method, the organic alkylation feed contains isoparaffin hydrocarbons with 4-6 carbon atoms and olefinic hydrocarbons with 2-8 carbon atoms, in a molar ratio of 2-200.

 According to another particular embodiment of the method, the organic alkylation feed contains aromatic hydrocarbons with a carbon number of 6-12 and olefinic hydrocarbons with a carbon number of 2-20 in a molar ratio of 2-200.

In accordance with another particular embodiment of the method, the organic feed for isomerization is contacted with a catalytic complex containing a heteropoly compound with an acidity on the Hammett scale in the range of pKa from -11.4 to -12.7 at a temperature of from 20 to 300 ^o C, pressure from 1 to 200 atm and time contact, providing a sufficient depth of conversion of raw materials isomerization.

 In accordance with another private variant of the method, the organic raw material for isomerization contains paraffinic hydrocarbons with the number of carbon atoms 4-30.

 In accordance with another private variant of the method, the organic feed for isomerization contains aromatic hydrocarbons with a carbon number of 8-30.

In accordance with another particular embodiment of the method, the organic polymerization feed is contacted with a catalytic complex containing a heteropoly compound with an acidity according to the Hammett scale in the range of pKa from -5.6 to -11.4 at a temperature of from 10 to 300 ^o C, pressure from 1 to 200 atm and time contact, providing a sufficient depth of conversion of the polymerization feed.

 According to another particular embodiment of the method, the organic polymerization feed contains olefinic hydrocarbons with a carbon number of 2-20.

 According to another particular embodiment of the method, the organic polymerization feed contains oxygen-containing compounds with a carbon number of 2-20.

 In accordance with another particular embodiment of the method, the organic polymerization feed contains halogen-containing organic compounds with a carbon number of 2-20.

The objective is also achieved by creating a catalyst (including an active component containing boron trifluoride), in which the active component is a catalytic complex of boron trifluoride and a heteropoly compound supported on a porous carrier with a molar ratio of boron trifluoride to heteropoly compound from 0.1 to 5, preferably from 0.5 to 2 in an amount of from 0.1 to 55% wt., preferably from 2 to 30% wt. moreover, the heteropoly compound is obtained from one or more oxides of elements of groups III to VI and from one or more metal salts with the general formula (Me) _x (XO ₄ ) _y , where Me is a metal of groups III, IV, x = 1-2, y = 2-3, X is sulfur or phosphorus, taken in the molar ratio of oxides to salts of from 0.5 to 20, preferably from 1.5 to 10, or from compounds forming the oxides and salts in the preparation of the heteropoly compound, the composition of the heteropoly compound in terms of oxides is described empirical formula Me _k X _m O _n, where Me - elements selected from the series: Ga, B, Al, Ti , Zr, Sn and or mixtures thereof; X are elements selected from the series: P, S, or mixtures thereof, k = 1-80, m = 1-100, n = 100-400, and the heteropoly compound acidity determined by the Hammett scale in the pKa range from -5.6 to -12.7.

 According to another particular embodiment of the catalyst, the active component further comprises an excess of boron trifluoride entering the catalytic section with a stream of processed organic materials in an amount of from 5 to 50,000 ppmw, preferably from 10 to 200 ppmw.

In accordance with a particular embodiment of the catalyst, the heteropoly compound is synthesized on the surface of a porous support at a temperature of 150-550 ^° C. In accordance with a specific embodiment of the catalyst, an organic or inorganic or carbon material having an average pore radius of at least 30 A is used as the porous support the pore volume is not less than 0.55 cm ³ / g, the surface is not less than 170 m ² / g, including group VIII metal in an amount of 0.1-1.0% wt.

 In accordance with another particular embodiment of the catalyst, a catalytic complex containing a heteropoly compound with acidity according to the Hammett scale in the pKa range from -5.6 to -11.4 is used for the alkylation and polymerization processes.

 In accordance with another particular embodiment of the catalyst, a catalytic complex containing a heteropoly compound with an acidity on the Hammett scale in the pKa range from -11.4 to -12.7 is used to conduct the isomerization process.

The essence of the invention lies in the fact that the conditions are determined under which within the reactor block the processes of generation of boron trifluoride, the formation of a mixture of raw materials and boron trifluoride, the catalytic processing of organic raw materials and the complete absorption of boron trifluoride from the reaction products are carried out. To realize a boron trifluoride closed cycle, the properties of metal tetrafluoroborates with the general formula Me (BF ₄ ) _{x were used} to isolate boron trifluoride at a temperature equal to or higher than the temperature of thermal decomposition, and metal fluorides with the general formula MeF _x to absorb boron trifluoride at a temperature below the temperature of thermal decomposition in accordance with with a reversible reaction Me (BF ₄ ) _x = xBF ₃ + MeF _x . Thus, metal tetrafluoroborates can be used in catalytic processes to introduce the required amount of boron trifluoride into the reaction medium. The absorption of boron trifluoride by metal fluoride proceeds quantitatively with the formation of the corresponding metal tetrafluoroborate. As follows from table 1 (see the end of the description), the temperature of the reaction of absorption of boron trifluoride by metal fluoride is 10-50 ^o C lower than the temperature at which decomposition of tetrafluoroborate of this metal begins.

 The most advantageous is the use of metal tetrafluoroborates, which are characterized by a high capacity for boron trifluoride, ease of preparation, low temperature of reversible decomposition, low cost of starting materials. In particular, tetrafluoroborates of magnesium and aluminum fully meet these requirements.

 The laws of thermal decomposition of tetrafluoroborates have been investigated. Table 2 shows the data on magnesium tetrafluoroborate, from which it follows that by changing the temperature of the source it is possible to smoothly control the content of boron trifluoride in the feed stream of the process in the range from tens to tens of thousands ppmw. The rate of release of boron trifluoride varies slightly over time; a significant decrease in speed is observed only in the range of 90-95% wt. decomposition of tetrafluoroborate.

The process of processing organic raw materials using a catalytic composition consisting of a source of boron trifluoride, a catalytic complex and an absorber of boron trifluoride is carried out in a three-section reactor, which ensures the maintenance of an optimal temperature regime in each section. When preparing the reactor for operation, metal tetrafluoroborate deposited on a porous carrier is loaded into the source section, the catalyst itself is loaded into the catalytic section, and metal fluoride deposited on the porous carrier is loaded into the absorber section. Prior to the start of the process, the catalyst is activated with boron trifluoride obtained by thermal decomposition of metal tetrafluoroborate in the source section and transfer of boron trifluoride by a stream of raw material, an inert solvent, or an inert gas into the catalytic section. By catalyst activation is meant the formation of a catalytic complex of boron trifluoride with a heteropoly compound. During activation, the process temperature is maintained in the catalytic section, and the temperature in the absorption section is lower than the decomposition temperature of the metal tetrafluoroborate. The maximum ranges of the parameters of the catalyst activation process are as follows: the temperature in the source section is from 20 to 400 ^o C, in the catalytic section from 20 to 300 ^o C, in the absorber section from 10 to 375 ^o C; pressure from 1 to 200 atm .; the duration of the process is from 0.5 to 24 hours. The end of the process is determined by the slip of boron trifluoride into the product stream of the catalytic section, after which the reactor is transferred to the supply and processing of organic raw materials.

 When processing organic materials in the sections of the reactor, the following processes occur. In the source section, the metal tetrafluoroborate decomposes to form the required amount of boron trifluoride, which enters the feed stream and with it further into the catalytic section, in which boron trifluoride, considered here as excessive with respect to the complex, provides increased activity and selectivity catalytic complex. Further, boron trifluoride in a stream of cooled reaction products enters the absorber section and, interacting with metal fluoride, forms metal tetrafluoroborate. Upon reaching a certain degree of decomposition of metal tetrafluoroborate in the source section and a proportional degree of its accumulation in the absorber section, the functions of these sections are inverted and the direction of flow of organic substances in the reactor is inverted. In this case, the heated raw materials are sent to the absorber section, which becomes the source, and the reaction products from the catalytic section after cooling are sent to the source section, which becomes the absorber. Tests have shown that the release-absorption cycle of boron trifluoride can be repeated more than 50 times, without significant changes in the properties of tetrafluoroborate, metal fluoride and the carrier.

Another object of the invention is the development of catalytic complexes that can be used in various conversion reactions of organic raw materials, including alkylation, isomerization and polymerization processes. The studies made it possible to synthesize a number of compounds containing boron trifluoride and heteropoly compounds of a certain chemical composition and acidity, as a result of the interaction of which a catalytic complex with controlled surface acidity is formed. At the same time, process indicators improved in comparison with the prototype are achieved due to the fact that with a change in the concentration of boron trifluoride and / or the composition of the heteropoly compound, catalytic complexes with different acidity and a narrow distribution of the strength of acid centers are obtained. By heteropoly compound here is meant anionic type complex compounds containing in the internal coordination sphere anions of inorganic isopolyacids as ligands. The chemical nature of heteropoly compounds is described in detail in the book by J. Aix, “Chemistry of heteropoly compounds and heteropoly acids,” Moscow, Mir, 1971. The effect of boron trifluoride concentration in the catalytic complex is illustrated by a change in the relative concentration of strong acid sites on the sample, measured by IR spectroscopy. An increase in the temperature of complexation from 25 to 75 ^o C and, accordingly, a decrease in the content of boron trifluoride in the complex from 9.3 to 2.4% by weight, caused a decrease from 96 to 39% of the relative concentration of strong acid sites that form complexes with CO in the range of 2195-2198 cm ^-1 . Table 3 (see the end of the description) shows the starting components, synthesis conditions, compositions of the obtained heteropoly compounds and the results of measurements of their acidity by a known method, titration of heteropoly compounds in the presence of Hammett's indicators in benzene solution.

 From the data of table 3 it follows that the acidity of heteropoly compounds can be changed over a wide range by selection of the chemical composition and temperature of synthesis. The interaction of boron trifluoride with heteropoly compounds increases the strength of acid centers by 3–4 units of the Hammett scale and, accordingly, forms catalytic complexes with an acidity of –9 to –16 pKa units.

суммарный объем пор - не менее 0.55 см³/г, поверхность - не менее 170 м²/г. Перечисленные закономерности образования каталитических комплексов являются необходимыми и достаточными условиями синтеза селективных катализаторов с высоким ресурсом и производительностью, применимых в разнообразных процессах кислотного катализа.The data of acidity measurements by the IR method allow us to compare the change in strength and the distribution of acidity during the formation of the catalytic complex with boron trifluoride. The initial heteropoly compound of the above complex, as shown by IR spectroscopy of adsorbed molecules, contains mainly acidic centers of medium strength. In the catalytic complex, the relative concentration of strong centers on the surface of the heteropoly compound increased from 5 to 96%. A decrease in the fraction of medium strength acid sites on the catalyst surface, which are responsible for the intensity of decontamination processes, is the main condition for the synthesis of catalytic complexes with a high resource. An additional increase in the activity of the catalytic complex is achieved by using the known method of dispersing the active component on a carrier with the following characteristics: average carrier pore radius is not less than

the total pore volume is not less than 0.55 cm ³ / g, the surface is not less than 170 m ² / g. The listed regularities of the formation of catalytic complexes are necessary and sufficient conditions for the synthesis of selective catalysts with a high resource and productivity, applicable in a variety of acid catalysis processes.

 Some common features of the preparation, modes of use and regeneration of the catalysts, contributing to the manifestation of the advantages of the claimed invention are set forth in the following paragraph.

Various porous materials can be used to prepare the catalytic complex: inorganic (oxides of elements of groups III-IV and their mixtures), carbon, organic polymers that are used in known catalytic systems. The highest rates of activity, selectivity and resource of the catalyst composition are achieved under process conditions in which the components of the initial mixture in the reaction volume are in the liquid phase, and also due to the known method of introducing 0.1-1.0% wt. Group VIII metal — palladium, platinum, nickel, etc., and the introduction of a small amount of hydrogen into the reaction mixture. The porous support is regenerated in a known manner by extracting the deactivating components from the surface of the catalyst with a solvent. As the latter, both single-component and complex solvents are used that belong to different classes of organic substances, for example aromatic hydrocarbons - benzene, toluene, xylenes, etc .; oxygen-containing organic compounds - diethyl ether, dioxane, methyl ethyl ketone, etc .; halogen-containing organic compounds - carbon tetrachloride, dichloromethane, dichloroethane, etc. Extraction regeneration is carried out at a temperature of 50-200 ^o C and pressure, providing in combination the conditions for finding the solvent in the liquid phase. This condition is necessary for the destruction and extraction of relatively heavy products from active centers and the restoration of the activity, selectivity and resource of the regenerated catalyst to the initial level. Extraction at a temperature higher than the temperature of the catalytic process is preceded by the decomposition of part of the catalytic complex when the catalytic section is heated to the extraction temperature. The boron trifluoride released in this process in a stream of cooled solvent is discharged into the absorber section. The mild conditions of extraction regeneration prevent the destruction of the porous structure of the catalyst, the change in the chemical composition of the active centers, which significantly increases the period of effective operation of the catalyst. When introduced into a porous carrier, 0.01-1.0% wt. metal of group VIII, the regeneration is carried out at a temperature of 70-100 ^o C, preferably in a liquid solvent with the addition of hydrogen. The addition of hydrogen provides hydrogenation of unsaturated compounds, the interaction of which with the catalyst surface is most pronounced. The conditions of operation and regeneration of the catalyst described above contribute to an increase in the activity, selectivity and stability of the catalyst composition.

In the following paragraph, a General description of the preparation of the catalytic composition for the processing of organic raw materials in accordance with the claimed invention. To synthesize a source of boron trifluoride, the porous support is impregnated with an aqueous solution of metal tetrafluoroborate of groups I-IV, dried at 20-100 ^° C. under a vacuum of 2-3 mmHg. within 12-24 hours to a moisture content of 0.1-0.3% wt. To synthesize a boron trifluoride scavenger, the porous support is impregnated with an aqueous solution of a metal salt of groups I-IV and dried at 30-250 ^° C., then treated with an aqueous solution of ammonium fluoride. The resulting material, consisting of metal fluoride of groups I-IV, deposited on a porous support, is washed with distilled water to a pH of 7-8 and dried at a temperature of 200-250 ^o C for 12-24 hours to a moisture content of 0.1-0.2% wt. To synthesize the basis for the catalytic complex, the porous support is treated with a Group VIII metal salt solution, and then dried at 100-300 ^o C. The resulting material is treated with aqueous solutions of substances belonging to the above classes. A material containing the starting components for synthesis on a porous support is separated from the impregnation solution and the heteropoly compound is formed by drying at 120 ^° C, then by heat treatment at 150-550 ^° C for 2-12 hours.

 Examples of the practical implementation of the method and catalyst are given below.

=0.59 мл/г, насыпная плотность - 0.60 г/мл пропитывают раствором тетрафторобората магния, сушат на воздухе, затем под вакуумом. Получают источник трифторида бора, содержащий 61.2% мас. тетрафторобората магния или 41.9%мас. трифторида бора, связанного в форме тетрафторобората магния.Example 1
A. Preparation of a source of boron trifluoride. A carbon carrier having the following characteristics: surface - 280 m ² / g, total pore volume in water -

= 0.59 ml / g, bulk density 0.60 g / ml is impregnated with a solution of magnesium tetrafluoroborate, dried in air, then under vacuum. Get a source of boron trifluoride containing 61.2% wt. magnesium tetrafluoroborate or 41.9% wt. boron trifluoride bound in the form of magnesium tetrafluoroborate.

 B. Preparation of a boron trifluoride scavenger. The carbon carrier used in Part A of Example 1 is impregnated with a solution of magnesium salt, then treated with a solution of ammonium fluoride to form magnesium fluoride, which is deposited on the surface of the carbon carrier. After washing and drying, an absorber of boron trifluoride containing 19.4% wt. magnesium fluoride and having a capacity for absorption of boron trifluoride 61.6% wt.

B. Preparation of the catalyst. To prepare the catalyst, the carbon carrier indicated in Part A of Example 1 containing 0.15% wt. applied palladium, contribute to a solution containing phosphoric acid and aluminum sulfate. After washing and drying, the material is heat treated at a temperature of 200 ^o C. Get the catalyst of the following composition (calculated on oxides)% wt .: Al ₂ O ₃ - 1.1; P ₂ O ₅ - 3.6; SO ₃ - 0.57; the rest is Pd - 0.14, a carbon carrier. The empirical formula of the synthesized heteropoly compound obtained on the basis of the indicated oxide composition is Al ₂₁ P ₄₈ S ₇ O ₁₇₁ .

The following is loaded into a flowing isothermal three-section reactor: in the source section (1), 2.5 g of magnesium tetrafluoroborate obtained in accordance with paragraph A; to the catalytic section (2) - 4.05 g (6.23 ml) of the catalyst obtained in paragraph B; in the absorber section (3), 1.7 g of magnesium fluoride obtained in step B. The reactor is purged with nitrogen at 25-30 ^° C, the temperature in the source section is raised to 85 ^° C and the catalyst is activated by passing isobutane through the reactor at a rate of 32 g / g of _{catalyst mash} • h for 20 hours. In the catalytic section and the absorber section maintain a temperature of 50 and 35 ^o C, respectively, the pressure in the reactor is 20-22 atm. As a result of activation, the content of boron trifluoride in the catalytic complex is 6.5% wt. Upon completion of the activation temperature of the source section is reduced to 50 ^o C, the reactor pressure - 15-16 atm, and the feed of a mixture of isobutane and butylene at a speed of 20.8 g / mL • hr _{rolled mash.} The molar ratio (internal) of isobutane to butylenes in the mixture is 30, the dissolved hydrogen content is 180 ppmw, the boron trifluoride content is 15 ppmw. The composition of the reaction products is determined by gas chromatography using a high pressure microdoser. For analysis, a Fiezen DB-1 capillary column of 60 m length and an inner diameter of 0.25 mm was used. Based on the data of chromatographic analysis, the following parameters are calculated: catalyst productivity (R) (R = G _alkylate / V _cat , where G _alkylate is the amount of alkylate, g / h; V _cat is the volume of catalyst, ml; R is the catalyst productivity, g _alkylate / ml _cat-ra • h); the degree of conversion of α butylene: α = 100 • (C ₀ -C _x ) / C ₀ , where C ₀ is the concentration of butylene at the inlet of the reactor, mol%; C _x is the concentration of butylenes at the outlet of the reactor,% mol .; α degree of butylene conversion,%); yield alkylate ω for olefins: (ω = 100 × R / (G _mixtures × C _ON), wherein R - Catalyst productivity g _alkylate / mL _cut-pa • h; G _mix - Consumption of raw mix, g / mL _cut-pa • h; C _OB is the concentration of butylenes in the raw material mixture,% wt; ω is the yield, alkylate for olefins, g / g _butylene ); octane content (S _C8 ) in the alkylate: (S _C8 = G _octanes / G _alkylate , where G _octanes is the number of octanes in the alkylate, g / h; G _alkylate is the amount of alkylate, g / h; S _C8 is the octane content in the alkylate, % wt.); the content of trimethylpentanes (TMP) in the alkylate (S _TMP ): (S _TMP = 100 • G _TMP / G _alkylate , where G _TMP is the amount of trimethylpentanes in the alkylate, g / h; G _alkylate is the amount of alkylate, g / h; S _TMP - the content of trimethylpentanes in the alkylate,% wt.); resource (P) action of the catalyst: (P = R • T, where R - Catalyst productivity g _alkylate / mL _cut-pa • h; T - process duration, h; P - catalyst resource g _alkylate / mL _cut-pa) .

Every 1000 hours the sections of the source and the absorber are switched over the flows of raw materials and reaction products: the temperature, respectively, is increased to 50 ^° C in the section of the source and reduced to 35 ^° C in the section of the absorber of boron trifluoride. The conditions and indicators of the alkylation process of Example 1 are shown in Table 4. The results obtained show the possibility of stably maintaining the rate of release and absorption of boron trifluoride, the functioning of the source and sink of boron trifluoride over a long period of time.

Examples 2-6
The alkylation process is carried out as in example 1, except that along with the temperature, the feed rate of the initial mixture and the pressure in the reactor are varied.

 The conditions and results of the experiments are presented in table 5. Examples 2-6 show the possibility of carrying out the alkylation process at various combinations of the temperature of the source of boron trifluoride and the catalytic complex.

Examples 7-11
The alkylation process is carried out as in example 1, except that in the process the molar ratio (internal) of isobutane to butylene and the concentration of hydrogen in the feed are varied. The conditions and results of the process are presented in table 6. The results of the experiments show the beneficial effect of hydrogen supply and an increase in the molar ratio of isobutane to butylenes on the selectivity of the process.

Examples 12-14
The alkylation process is carried out as in example 1, except that in the process the content of boron trifluoride in the initial alkylation mixture is varied in the absence of hydrogen in the raw material mixture. The conditions and results of the process are presented in table 7. From examples 12-14 it follows that the range of concentrations of boron trifluoride in the initial alkylation mixture, providing a selective process, is in the range of 10-80 ppmw.

Example 15
The alkylation process is carried out as in example 1, except that for the process using alkylation feedstock containing isobutane and propylene in a molar ratio (internal) 31. As a result of the process, receive: the degree of conversion of propylene,% -100.00; Catalyst productivity g _alkylate / ml _cat • _h-ra - 1.43; the yield of alkylate, g / g _propylene - 2.31; octane content in alkylate,% wt. - 53.62; the content of trimethylpentanes in the alkylate,% wt. - 46.21
Example 16
The alkylation process is carried out as in example 1, except that for the process using alkylation feedstock containing isobutane and amylenes in a molar ratio (internal) 31. The result is: the degree of conversion of amylene,% - 100.00; Catalyst productivity g _alkylate / ml _cat • _h-ra - 1.16; the yield of alkylate, g / g of _amylene - 1.89; octane content in alkylate,% wt. - 48.35; the content of trimethylpentanes in the alkylate,% wt. - 40.93.

Example 17-21
The alkylation process is carried out as in Example 1, except that tetrafluoroborate and magnesium fluoride synthesized on a number of carriers are used as a source and an absorber of boron trifluoride. The results of the alkylation of isobutane with butylenes are shown in Table 8. The examples show a wide range of carriers suitable for preparing a source and scavenger of boron trifluoride.

Example 22-26
The alkylation process is carried out as in example 1, with the exception that tetrafluoroborates and fluorides of a number of metals of groups I-IV synthesized on a number of carriers are used as a source and an absorber of boron trifluoride. The results of the alkylation of isobutane with butylenes are shown in table 9.

Example 27-32
The alkylation process is carried out as in example 1, except that a catalytic complex obtained by reacting various heteropoly compounds and boron trifluoride dispersed on a carrier is used to carry out the process. The results of the alkylation of isobutane with butylenes are shown in Table 10. Examples 27-32 show that a large group of substances belonging to the classes listed in the disclosure of the invention can be used to form the catalytic complex.

Example 33
The following is loaded into a flowing isothermal three-section reactor: 2.5 g of magnesium tetrafluoroborate obtained in Example 1A in the source section; to the catalytic section - 4.05 g (6.23 ml) of the catalyst obtained in example 1B; in the section of the absorber -1.7 g of magnesium fluoride obtained in example 1B. The reactor was purged with nitrogen at a temperature of 25-30 ^o C, the temperature was raised in the source section 85 ^o C and the activation of the catalyst is carried out by passing through the reactor at a rate of benzene 15.1 g / ml _{rolled mash} • h for 20 h. The catalyst sections and absorber sections maintain a temperature of 50 and 35 ^o C, respectively, the pressure in the reactor is 10-12 atm. As a result of activation, the content of boron trifluoride in the catalytic complex is 6.5% wt. Upon completion of activation to lower the temperature source section 50 ^o C, the reactor pressure was - to 5-6 atmospheres and the feed of a mixture of benzene and ethylene at a rate of 15.1 g / mL • hr _{rolled mash.} The molar ratio of benzene to ethylene in the mixture is 3, the content of dissolved hydrogen is 180 ppmw, the content of boron trifluoride is 15 ppmw. The composition of the reaction products is determined as described in Example 1. Based on the data of chromatographic analysis, the following are calculated: catalyst productivity (R): (R = G _ab / V _cat , where G _ab is the amount of alkylbenzenes, g / h; V _cat is the volume catalyst, ml; R - catalyst performance _{alkilb enzolov} g / mL _cut-pa • h); the degree of conversion (α) of ethylene: (α = 100 × (C ₀ -C _x ) / C ₀ , where C ₀ is the concentration of ethylene at the inlet to the reactor,% mol; C _x is the concentration of ethylene at the outlet of the reactor,% mol; α is the degree of ethylene conversion,%); selectivity (S _eb ) for ethylbenzene: (S _eb 100 • (G _eb / MW _eb ) / (G _b / MW _b ), where G _eb is the rate of formation of ethylbenzene, g / h; G _b is the rate of consumption of benzene, g / h; MW _eb , MW _b - molecular weight of ethylbenzene, benzene; S _eb - selectivity for ethylbenzene,% wt.).

The process is conducted for 1000 hours, as a result, the following results are obtained: the degree of ethylene conversion,% mol. -100.00; catalyst productivity, _{alkyl benzenes} g / ml _cat • _h-ra - 5.79; ethylbenzene selectivity,% wt. - 93.19; catalyst resource to ethylbenzene is not less than g / mL _cut-ra - 5790.

 Example 34

The alkylation of benzene is carried out as in example 33, except that for the process using raw materials containing benzene and propylene in a molar ratio of 5. The result is: the degree of conversion of propylene,% mol. - 100.00; productivity of the catalyst, _cumene g / ml _cat • _h-ra - 5.21; cumene selectivity,% wt. - 97.38.

Example 35
The following is loaded into a flowing isothermal three-section reactor: into the source section - 2.0 g of magnesium tetrafluoroborate obtained in Example 1A; in the catalytic section - 6.53 g (10.88 ml) of the catalyst obtained in example 30; in the section of the absorber - 1.36 g of magnesium fluoride obtained in example 1B. The reactor was purged with nitrogen at a temperature of 25-30 ^o C, the temperature was raised in the source section 85 ^o C and the activation of the catalyst is carried out by passing through the reactor with n-butane at a speed of 7.5 g / ml _{rolled mash} • h for 20 h. The catalyst sections and sections of the absorber maintain a temperature of 50 and 35 ^o C, respectively, the pressure in the reactor is 15-16 atm. As a result of activation, the content of boron trifluoride in the catalytic complex is 4.9% wt. Upon completion of activation, reduce the temperature in the source section to 50 ^o C and begin to supply n-butane at a speed of 1.14 g / ml _{catalyzed mash} • h. The dissolved hydrogen in the mixture is 180 ppmw, boron trifluoride is 45 ppmw. The composition of the reaction products is determined as described in Example 1. Based on the data of chromatographic analysis, the following are calculated: productivity (R) of the catalyst: (R = G _product / V _cat , where G _product is the number of products, g / h; V _cat is the volume catalyst, ml; R - catalyst productivity, g _products / ml _cat. • h); degree of conversion (α) of n-butane: (α = 100 × (C ₀ -C _x ) / C ₀ , where C ₀ is the concentration of n-butane at the inlet to the reactor, mol%; C _x is the concentration of n-butane at the outlet from the reactor, mol%; α is the degree of conversion of n-butane,%); selectivity (S _iC4 ) for isobutane: (S _iC4 = 100 • G _iC4 / G _nC4 , where G _iC4 - isobutane formation rate, g / h; G _nC4 - consumption rate of n-butane, g / h; S _iC4 - selectivity for isobutane,% wt.); composition of isomerization products,% wt. After 500 hours of conducting the process, the sections of the source and absorber are switched, as described in Example 1. The process is continued for 1500 hours. The results are shown in Table 11. The experimental results show the possibility of multiple use of the isolation - absorption of boron trifluoride cycle for the isomerization process.

Example 36
The isomerization process is carried out as in example 35, except that n-pentane is used to carry out the process. The results of isomerization are summarized in table 11.

Example 37
The isomerization process is carried out as in example 35, except that n-hexane is used to carry out the process. The results of isomerization are summarized in table 11.

Example 38
The isomerization process is carried out as in example 35, except that para-xylene is used to carry out the process. The result is a mixture of xylenes of the following composition (% wt.): - para-xylene - 36.38; - meta-xylene - 49.61; - ortho-xylene -12.79; - unidentified hydrocarbons - 1.22; - conversion of para-xylene -63.62; - catalyst resource - not determined.

Example 39
The following is loaded into a flowing isothermal three-section reactor: 2.5 g of magnesium tetrafluoroborate obtained in Example 1A in the source section; to the catalytic section - 4.05 g (6.23 ml) of the catalyst obtained in example 1B; in the section of the absorber - 1.7 g of magnesium fluoride obtained in example 1B. The reactor was purged with helium at a temperature of 25-30 ^o C, the temperature was raised in the source section 85 ^o C and catalyst activation is carried out by passing helium through the reactor at a speed of 2.8 l / g _{mash rolled} • h for 10 h. The catalyst sections and absorber sections maintain a temperature of 85 and 35 ^o C, respectively, the pressure in the reactor is 20 atm. As a result of activation, the content of boron trifluoride in the catalytic complex is 3.7% wt. Upon completion of activation in a helium stream, the temperature in the source section is reduced to 50 ^° C., the helium supply is stopped, and the butylene fraction containing 99.83% wt. butene-1 and butene-2 with a speed of 2.9 g / ml _{rolled mash} • h. In the catalytic section and the section of the absorber maintain a temperature of 85 and 35 ^o C, respectively, the pressure in the reactor is 20 atm. The boron trifluoride content in the mixture is 45 ppmw. The composition of the reaction products is determined as described in example 1. Based on the data of chromatographic analysis, the following are calculated: catalyst productivity (R): (R = G _p-b / V _cat , where G _p-b is the amount of polymer-gasoline, g / h; V _cat-ra - catalyst volume, ml; R - catalyst productivity, g _{polymer- gasoline} / ml _cat-ra • h); the degree of conversion (α) of butylnols: (α = 100 × (C ₀ -C _x ) / C ₀ , where C ₀ is the concentration of butylenes at the inlet of the reactor, mol%; C _x is the concentration of butylenes at the outlet of the reactor, mol%; α is the degree of butylene conversion,%); polymer gasoline yield (ω) for olefins: (ω = 100 × R / (G × C _{Olef OB),} wherein R - catalyst productivity, _{polymer gasoline} g / mL _cut-pa • h; C _ON - the concentration of butenes in the raw mixtures wt%; g _Olef - raw meal consumption, g / mL _cut-pa • h; ω - yield polymer gasoline, g / g of _butenes); octene content (S _C8 ) in polymer gasoline: (S _C8 = 100 • G _C8 / G _p-gasoline , where G _{C8 is the} number of octenes in polymer gasoline, g; G _p-gasoline is the amount of polymer gasoline, g; S _C8 — octene content in polymer gasoline,% wt.).

The process is conducted for 500 hours, then the direction of the reactor flows are switched as described in Example 1. As a result of the reaction, the following indicators: the catalyst productivity, _{polymer gasoline} g / ml _cat • _h-ra - 2.6; the degree of conversion of butylenes,% wt. - 91.38; polymer-gasoline yield on olefins, g / g _butylene - 0.89; the content of octenes in polymer gasoline,% wt. - 92.65.

Example 40
The polymerization process is carried out as in example 39, except that 530 g of polymerization feed consisting of 10% wt. vinyl chloride dissolved in n-hexane with a flow rate of 29 g / g _cat-ra • h. After distillation of n-hexane from the polymer solution, 50.51 g of polyvinyl chloride with a molecular weight of 1900 is obtained. The yield of polyvinyl chloride to the monomer taken in the reaction is 95% wt.

Example 41
The polymerization process is carried out as in example 39, except that 250 g of a polymerization feed consisting of 12% wt. ethylene oxide dissolved in n-hexane with a flow rate of 41 g / g _cat-ra • h. After distillation of n-hexane from the polymer solution, 29.4 g of polyethylene glycol with a molecular weight of 1900 is obtained. The yield of polyethylene glycol per monomer taken into the reaction is 98% wt.

Example 42
To carry out extraction regeneration, a carbon tetrachloride is fed at a rate of 1.95 g / ml of _cat. • hr for 10 hours into the reactor containing the catalyst deactivated during the isomerization of Example 35. The temperature in all sections is 35 ^o C. An indicator of the end of the regeneration is the absence of hydrocarbon products in carbon tetrachloride at the outlet of the reactor. Upon completion of the regeneration process, the reactor is freed from carbon tetrachloride and the n-butane isomerization process is continued according to the conditions of Example 35. The regenerated catalyst after 100 hours of the isomerization process has the following characteristics: n-butane conversion ratio,% - 86.17; catalyst productivity, g _products / ml of _cat • h - 0.97; the selectivity of isomerization,% wt. - 94.75; composition of isomerization products,% wt .: C ₂ - C ₃ - 0.08; n-butane - 81.65; n-butane - 13.83; i-pentane - 2.73; n-pentane - 1.25; i-hexanes 0.31; n-hexane-0.08; C ₇ -C ₉ - 0.07.

Example 43
In the reactor containing the catalyst deactivated during the alkylation process of Example 1, isobutane is fed at a rate of 1.95 g / ml _cat. • h, containing 180 ppmw of hydrogen. The temperature in the sections of the source and absorber is reduced to 35 ^o C, in the catalytic section it is raised to 85 ^o C. The process of partial decomposition of the catalytic complex and then regeneration is carried out for 10 hours. The end of the regeneration is indicated by the absence of hydrocarbon products in isobutane at the outlet of the reactor. Upon completion of the regeneration and activation of the catalyst, isobutane is continued to be alkylated with butylenes according to the conditions of Example 1. The regenerated catalyst after 500 hours of conducting the alkylation process has the following characteristics: degree of butylene conversion,% - 100.00; the yield of alkylate, g / g _butylene - 1.99; Catalyst productivity g _alkylate / ml _cat • _h-ra - 1.26; octane content in alkylate,% wt. - 95.11; trimethylpentane content in alkylate. % wt. - 84.42.

Example 44
This example illustrates the possibility of applying the proposed method for carrying out the alkylation process on the catalyst of the prototype. A boron trifluoride source obtained in Example 1A with a load of 160 g is connected to a feed line of a feed mixture of alkylating a feedstock into a 150 ml flow autoclave equipped with a magnetic stirrer; boron trifluoride scavenger obtained in Example 1B in an amount of 90.8 g is installed on the exit line of reaction products. 2.0 g Beta zeolite containing 15.2% wt. is placed in an autoclave. water. The autoclave is filled with 70 ml of isobutane, stirring is started at a speed of 1900 rpm and the reaction medium is cooled to 0 ^° C. In the source section, the temperature is raised to 85 ^° C and isobutane containing 30,000 ppmw boron trifluoride is introduced into the autoclave at a speed of 27 g / g _cat. • h before the breakthrough of boron trifluoride at the outlet of the autoclave. The content of boron trifluoride in the prepared catalytic complex is 53% wt. Upon completion of the activation process, an initial alkylation mixture containing isobutane and butylenes in a molar ratio of 10 and 30,000 ppmw boron trifluoride is fed to the autoclave at a speed of 27 g / h (2.5 g / h for butylenes). The temperature in the source section is 85 ^o C, in the autoclave and the absorber of boron trifluoride 0 ^o C. As a result of the process, the following is obtained: the degree of butylene conversion,% - 100.00; Catalyst productivity g _alkylate / ml _cat • _h-ra - 2.51; the yield of alkylate, g / g _butylene - 2.01; octane content in alkylate,% wt. - 91.28; the content of trimethylpentanes in the alkylate,% wt. - 77.32
Thus, the examples of specific implementation of the method and application of the proposed catalyst allow the following conclusions:
1. The possibility of using the proposed method and a catalytic complex with controlled acidity for the alkylation, isomerization and polymerization of organic raw materials with high yield of the target product, catalyst resource and productivity was shown;
2. The possibility of producing a high-octane component of gasoline by alkylating isobutane with butylenes on a solid catalyst with a high resource, productivity, and C ₈ selectivity of 95% wt. (see example 1);
3. The method can be applied to various types of known reactor devices, as well as to known acid catalyst systems using Lewis acids;
4. The proposed invention allows you to create environmentally friendly processes in which there are no aggressive environments, harmful substances and waste.

Claims (24)

 1. A method of processing organic raw materials, including preparing a mixture of organic raw materials with boron trifluoride, contacting the stream of the resulting mixture with a catalyst and isolating boron trifluoride from the products of a catalytic reaction, characterized in that the process is carried out in a three-section reactor, consisting of a section of a source of boron trifluoride, a catalytic section and boron trifluoride scavenger sections, in the boron trifluoride source section, the feed stream is contacted with metal tetrafluoroborate deposited on a porous support, and in sec of the boron trifluoride scavenger, the catalytic reaction product stream is in contact with a metal fluoride deposited on a porous carrier capable of absorbing boron trifluoride, and periodically, as the metal tetrafluoroborate decomposes in the boron trifluoride source section and the metal tetrafluoroborate accumulates in the boron trifluoride scavenger section, the functions of these sections are inverted reactor, which is carried out simultaneously with the inversion of the direction of flow of organic raw materials and reaction products. 2. The method according to claim 1, characterized in that a catalyst is used, the active component of which is a catalytic complex of boron trifluoride and a heteropoly compound supported on a porous carrier with a molar ratio of boron trifluoride to a heteropoly compound of 0.1-5, preferably 0.5-2 , in an amount of 0.1 to 55 wt.%, preferably 2 to 30 wt.%, moreover, the heteropoly compound obtained from one or more oxides of elements of groups III to VI and from one or more metal salts with the general formula
(Me) x (XO ₄ ) y,
where Me is a metal of groups III, IV;
x = 1 - 2, y = 2 - 3;
X is sulfur or phosphorus,
taken in a molar ratio of oxides to salts of 0.5 to 20, preferably 1.5 to 10, or from compounds forming these oxides and salts in the preparation of the heteropoly compound, the composition of the heteropoly compound in terms of oxides is described by the empirical formula
Me _k X _m O _n ,
where Me are elements selected from the series Ga, B, Al, Ti, Zr, Sn, or mixtures thereof;
X - elements selected from the series P, S, or mixtures thereof;
k = 1 - 80, m = 1 - 100, n = 100 - 400,
and the acidity of the heteropoly compound determined on the Hammett scale in the pKa range (-5.6) - (-12.7).  3. The method according to claims 1 and 2, characterized in that the temperature of the reagents in the section of the source of boron trifluoride is set above the decomposition temperature of the metal tetrafluoroborate, and the temperature of the reagents in the section of the absorber of boron trifluoride is set below the decomposition temperature of the metal tetrafluoroborate.  4. The method according to PP. 1 and 2, characterized in that the inversion of the functions of the sections of the source and absorber of boron trifluoride is carried out by changing the temperature of the reactants in these sections.  5. The method according to claims 1, 2 and 4, characterized in that the inversion of the functions of the sections of the source and absorber of boron trifluoride is carried out with a degree of decomposition of metal tetrafluoroborate in the source section of boron trifluoride of not more than 95 wt. %  6. The method according to PP.1 and 2, characterized in that use tetrafluoroborate and metal fluoride of groups I, II, III and IV.  7. The method according to claims 1 and 2, characterized in that inorganic, or organic, or carbon materials are used as a porous carrier for tetrafluoroborate and metal fluoride.  8. The method according to claims 1, 2, 6 and 7, characterized in that the metal tetrafluoroborate is applied to the porous carrier in an amount of 0.1 to 90 wt.%, Preferably 30 to 70 wt.%, And the metal fluoride is applied to the porous carrier in an amount of 0.1 to 90 wt.%, preferably 20 to 50 wt.%. 9. The method according to claims 1 and 2, characterized in that the organic raw materials capable of undergoing alkylation and the alkylating agent are contacted with a catalytic complex containing a heteropoly compound with acidity on a Hammett scale in the range of pKa (-5.6) - (-11, 4) at a temperature of 0 - 200 ^o C, a pressure of 1 - 200 ATM and contact time, providing a sufficient depth of conversion of the alkylation feedstock.  10. The method according to claims 1, 2 and 9, characterized in that the organic alkylation feed contains isoparaffin hydrocarbons with 4 to 6 carbon atoms and olefin hydrocarbons with 2 to 8 carbon atoms, in a molar ratio of 2 to 200.  11. The method according to claims 1, 2 and 9, characterized in that the organic feed for alkylation contains aromatic hydrocarbons with 6 to 12 carbon atoms and olefinic hydrocarbons with 2 to 20 carbon atoms in a molar ratio of 2 to 200. 12. The method according to claims 1 and 2, characterized in that the organic raw material for isomerization is contacted with a catalytic complex containing a heteropoly compound with acidity according to the Hammett scale in the range pKa (-11.4) - (-12.7) at a temperature of 20 - 300 ^o With a pressure of 1 to 200 atmospheres and contact time, providing a sufficient depth of conversion of the raw material isomerization.  13. The method according to claims 1, 2 and 12, characterized in that the organic raw material for isomerization contains paraffin hydrocarbons with 4 to 30 carbon atoms.  14. The method according to claims 1, 2 and 12, characterized in that the organic raw material for isomerization contains aromatic hydrocarbons with a carbon number of 8 to 30. 15. The method according to PP.1 and 2, characterized in that the organic raw materials for polymerization are in contact with a catalytic complex containing a heteropoly compound with acidity on a Hammett scale in the range pKa (-5.6) - (-11.4) at a temperature of 10 - 300 ^o With a pressure of 1 - 200 ATM and contact time, providing a sufficient depth of conversion of the polymerization feed.  16. The method according to PP.1, 2 and 15, characterized in that the organic raw materials for polymerization contains olefinic hydrocarbons with a number of carbon atoms of 2 to 20.  17. The method according to claims 1, 2 and 15, characterized in that the organic polymerization feed contains oxygen-containing compounds with a number of carbon atoms of 2 to 20.  18. The method according to claims 1, 2 and 15, characterized in that the organic polymerization feed contains halogen-containing organic compounds with a carbon number of 2 to 20. 19. A catalyst for the processing of organic raw materials, comprising an active component containing boron trifluoride, characterized in that the active component is a supported catalyst complex of boron trifluoride and a heteropoly compound with a molar ratio of boron trifluoride to heteropoly compound of 0.1-5, preferably 0 5 to 2, in an amount of 0.1 to 55 wt.%, Preferably 2 to 30 wt.%, The heteropoly compound being obtained from one or more oxides of elements of groups III to VI and from one or more metal salts in the general formula
(Me) x (XO ₄ ) y,
where Me is a metal of groups III, IV;
x = 1 - 2, y = 2 - 3;
X is sulfur or phosphorus,
taken in a molar ratio of oxides to salts of 0.5 to 20, preferably 1.5 to 10, or from compounds forming these oxides and salts in the preparation of the heteropoly compound, the composition of the heteropoly compound in terms of oxides is described by the empirical formula
Me _k X _m O _n ,
where Me are elements selected from the series Ga, B, Al, Ti, Zr, Sn, or mixtures thereof;
X - elements selected from the series P, S, or mixtures thereof;
k = 1 - 80, m = 1 - 100, n = 100 - 400,
and the acidity of the heteropoly compound determined on the Hammett scale in the pKa range (-5.6) - (-12.7).  20. The catalyst according to claim 19, characterized in that its active component further includes an excess of boron trifluoride entering the catalytic section with a stream of processed organic materials in an amount of 5 to 50,000 ppmw, preferably 10 to 200 ppmw. 21. The catalyst according to PP.19 and 20, characterized in that the heteropoly compound is synthesized on the surface of a porous carrier at a temperature of 150 - 550 ^o C. 22. The catalyst according to PP.19 and 20, characterized in that as a porous carrier using organic, or inorganic, or carbon material having an average pore radius of at least 30

the total pore volume is not less than 0.55 cm ³ / g, the surface is not less than 170 m ² / g, including group VIII metal in an amount of 0.1 - 1.0 wt.%.  23. The catalyst according to PP.19 and 20, characterized in that for carrying out the processes of alkylation and polymerization using a catalytic complex containing a heteropoly compound with acidity according to the Hammett scale in the interval pKa (-5.6) - (-11.4).  24. The catalyst according to PP.19 and 20, characterized in that for carrying out the isomerization process using a catalytic complex containing a heteropoly compound with acidity according to the Hammett scale in the range pKa (-11.4) - (-12.7).

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