RU2163507C2 - Method of preparing heat-resistant catalysts and method of carrying out acid-catalyzed reactions - Google Patents

Abstract

FIELD: polymer production. SUBSTANCE: heat- resistant sulfoionite catalysts are prepared by forming cross-linking polymers or their compositions containing sulfonated aromatic groups. Method is distinguished by that aromatic group containing two sulfonic substituents are prevailing, preferably to 100%, and content of monosubstituted aromatic groups is essentially decreased. Such proportion is achieved by using for polymerization process monomer having in aromatic group at least two sulfonic substituents in H form or H-substituted form capable of being converted into H form and/or by extensive sulfonation of aromatic groups in polymer, and/or by removing at elevated temperature, preferably above 150 C, sulfonic groups from majority of monosulfonated aromatic groups contained in sulfonated polymer containing at least di- and monosulfonated aromatic groups. Reactions catalyzed by thus obtained sulfoionites are carried out at temperatures up to 180 C. EFFECT: increased heat resistance of sulfoionite catalysts. 13 cl, 1 tbl, 23 ex

Description

 The invention relates to the field of heat-resistant high-acid solid catalysts and to the field of reactions proceeding in the presence of acid catalysts.

 More specifically, the invention relates to the field of producing heat-resistant sulfonic ion catalysts and to the field of reactions proceeding in the presence of acid catalysts at elevated temperatures using solid acid catalysts.

To obtain acid sulfocationite known method [US Pat. USA 2518420, 1948], according to which polycondensation of n-phenolsulfonic acid with formaldehyde is carried out. There is also known a method [Pat. Germany 824391, 1951] to obtain acid sulfocationionites by polycondensation of dioxinaphthalene sulfonic acid with formaldehyde. The disadvantage of these methods is the low thermal stability of sulfocathionites, because at a temperature exceeding 120 ^o C, there is a cleavage of sulfo groups. This leads, on the one hand, to a rapid decrease in the activity of sulfocathionite, if used as a catalyst for chemical reactions at high temperatures, and on the other hand, to the formation of a strong corrosive medium in this case.

 The known method ["Ionites", Catalog, Cherkasy, 1980, p. 10-12] obtaining sulfocationic catalysts by sulfonation of a granular copolymer of styrene with divinylbenzene.

The disadvantage of this method is the relatively low heat resistance of the obtained ion-exchange catalysts. As indicated in the cited source (p. 10), when using cation exchange resin in aqueous solutions at a temperature of from 120 to 150-170 ^o C, the relative loss of exchange capacity due to desulfurization within 24 hours is 6.5 and 19.5%, respectively.

 In the book [N. G. Polyansky, "Catalysis by ion exchangers", M., Chemistry, 1973, S. 7-10] describes the preparation of ionic catalysts containing acidic, including sulfuric acid groups attached to the aromatic groups of the polymer by polymerization (copolymerization, polycondensation) of monomers having aromatic ring (s) with an acid group (including a sulfo group) or by sulfonation of polymers having aromatic groups. The preparation of polymers in this case is carried out by polymerization, copolymerization or polycondensation of monomers. In particular, the preparation of copolymers of styrene and divinylbenzene containing sulfo groups attached to aromatic rings is described.

 As indicated in the work [M.M. Senyavin, Ion exchange in technology and analysis of petrochemicals, M., Chemistry, 1980, p. 39], upon receipt of sulfocationite in this way, each benzene ring has one sulfo group.

The heat resistance of the sulfocationionites thus obtained is relatively low. So on p. 209 of the above book N. N. Polyansky presents data on the loss of capacity of KU-1 cation exchangers, which is a sulfonated polycondensate of phenol with formaldehyde, and KU-2 cation exchangers, which is a sulfonated copolymer of styrene and divinylbenzene, in water, alcohols and hydrocarbons. In many cases, the loss of capacity of KU-1 cation exchanger for 24 hours at 125 ^o C is up to 50-60%, and at 150 ^o C - up to 90-100%. The loss of capacity of KU-2 cation exchanger at 150 ^o C for 48 hours is up to 15-26%, which indicates the practical impossibility of their industrial use at these high temperatures.

 As a method of obtaining heat-resistant cation exchangers, a method was proposed [Autosvid. USSR N 418498, 03.03.74, Bull. N 9], according to which sulfonation of organic polymers obtained by polycondensation of anhydrides selected from the group consisting of acetic, phthalic and maleic anhydrides is carried out.

Despite the authors Autosvid. N 418498 high heat resistance, experimental data (including those given in the Autoswitch N 418498 itself) showed that at a temperature of 160 ^o C when boiling in water for 320 hours, the static exchange capacity of the catalysts (СОЕ) drops by 2 -3 times, because significant desulfurization occurs.

 As high-acid catalysts with high heat resistance, [Pat US N 4503263, 03/05/1985, Pat US N 5364976, 11/15/1994] catalysts containing perfluoroalkenesulfonic groups were proposed. These catalysts are really heat-resistant, but they have not found wide industrial application because of the complexity of their preparation and extremely high cost exceeding the cost of catalysts obtained by sulfonation of styrene-divinylbenzene copolymers by 50-100 times.

Known and closest to our proposed invention, the method described in US Pat. SU N 1075499, A1, 02.27.95. According to it, an ion-exchange molded catalyst containing a sulfonated styrene-divinylbenzene copolymer is obtained by molding a styrene-divinylbenzene copolymer or a sulfonated styrene-divinylbenzene copolymer in a mixture with polyethylene and subsequent sulfonation of the molded product with a sulfonating agent at an elevated temperature, and 90- 100% sulfuric acid and a temperature of 80-110 ^o C. Alternatively, the sulfonation process is carried out in the presence of dichloroethane, which improves n pellet swelling. After sulfonation, the catalyst is washed with distilled water. The examples describe the preparation of catalyst samples having a static exchange capacity (SOE) of 3.5 and 4.0 mEq H + / g.

 When copolymerization of styrene with divinylbenzene, which is a "cross-linking" agent, "cross-linked" polymers are formed. Crosslinking is necessary to maintain the shape of the catalyst during subsequent use.

The main disadvantage of this method is the relatively low thermal stability of the resulting catalysts, not exceeding 120 ^o C. Above 120 ^o C there is a significant desulfurization of the catalyst.

We propose (independent claim 1 of the claims) a method for producing heat-resistant sulfonic ion catalysts by forming cross-linked polymers or their compositions containing sulfonated aromatic groups, which consists in the predominance of, preferably up to 100%, aromatic groups among sulfonated aromatic groups, having at least two groups -SO ₂ OH, and eliminate or substantially reduce the content of aromatic groups having one group -SO ₂ OH, by use in the preparation of the polymer monomer and eyuschego in the aromatic group of at least two sulfo groups in the H ⁺ or H-substituted form, followed by transfer of the latter in the form -SO ₂ OH, and / or by deep sulfonation of aromatic groups in the polymer and / or deletion in the sulphonated polymer containing at least di - and mono-sulfonated aromatic groups, sulfo groups from at least most aromatic groups containing one sulfo group at an elevated temperature, preferably at a temperature above 150 ^o C.

As one of the options, a method is proposed, which consists in the fact that during the formation of the polymer and / or after it crosslinking of the polymer chains is carried out by any suitable agent or method, eliminating the dissolution or excessive swelling of the polymer matrix and sulfonated catalyst in water, hydrocarbons, alcohols, ethers, mixtures thereof and solutions of sulfuric acid and SO ₃ , for example using compounds with two vinyl groups, aldehydes or radiation crosslinking.

Alternatively, a method is proposed that consists in (co) polymerizing and / or polycondensing derivatives of styrene and / or phenol containing at least two —SO ₂ OH and / or H-substituted sulfo groups in each or in most aromatic groups.

Alternatively, a method is proposed that consists in the predominant incorporation of two —SO ₂ OH groups into a crosslinked styrene or alkyl styrene polymer and / or a styrene and / or alkyl styrene copolymer with divinylbenzene or alkadiene-1,3.

Alternatively, a method is proposed, which consists in the predominant introduction of two —SO ₂ OH groups into the aromatic groups of a crosslinked (co) polymer or polycondensate deposited on the surface of porous solid granules or other forms with a developed surface.

Alternatively, a method is proposed that consists in the predominant introduction of two —SO ₂ OH groups into aromatic groups of porous granules or other forms containing a crosslinked (co) polymer of a vinyl aromatic compound mixed with a molding polymer material, for example polyethylene and / or polypropylene.

Alternatively, a method is proposed, which consists in additional sulfonation of sulfonic ion catalysts containing at least aromatic groups having one —SO ₂ OH group or —SO ₂ OX group, where X is a metal or other neutralizing substituent.

Alternatively, a method is proposed that consists in the use of moist SO ₃ and / or sulfuric and / or chlorosulfonic acid and / or solutions of SO ₃ in said acids, or solutions of said sulfonating agents in organic solvents, and sulfonation is carried out at 50-200 ^o C preferably with a gradual increase in temperature.

Alternatively, a method is proposed that consists in the fact that in a catalyst containing at the same time aromatic groups with one and two —SO ₂ OH groups, desulfurization of aromatic groups containing one —SO ₂ OH group is carried out.

Alternatively, a method is proposed that desulfurization of aromatic groups containing one -SO ₂ OH group each is carried out by treating the catalyst with water and / or alcohol (s) and / or hydrocarbons at elevated temperatures, preferably at temperatures above 160 ^o C .

 The terms "polymer (s)" and "polymer" (chains) are used in the formula and description of the invention in a generalizing sense, regardless of the method of preparation: polymerization, copolymerization or polycondensation of the original monomer (s), i.e. include the concepts of the actual polymer and copolymer and polycondensate, which is widely practiced in the literature, unless there is a special need to emphasize the specifics.

The effect of thermal stability in our method is achieved due to the fact that the addition of the second (and third) —SO ₂ OH group to the aromatic ring sharply increases the stability of bonds between the corresponding carbon atoms and sulfur atoms of the —SO ₂ OH groups, reducing their polarization.

 The term “composition” in the claims and the description of the invention is understood as any combination of cross-linked sulfonated polymers with each other and / or with other compounds, for example, by mixing with non-sulfonated polymers and / or applying a sulfonated polymer to the surface of a solid (ceramic, silica gel, metal oxides, etc. .P.).

The term “X” referred to in paragraph 7 in principle means any substituent (element or group) capable of being replaced by hydrogen (H +) under the action of sulfonating agents, preferably in the presence of water. This substituent can be, in particular, metals of groups I and II of the Mendeleev’s Periodic System, iron, ammonia, alkenes and other substances and basic elements that replace hydrogen in sulfo groups and form salts with —SO ₂ OX. Substituents can also be unsaturated organic compounds that attach to the —SO ₂ O group and are capable of being replaced by hydrogen under the action of sulfonating agents.

 The sulfonating agents indicated in claim 8 of the claims do not exhaust the range of possible sulfonating agents and other agents may be used if they provide the necessary sulfonation effect and at the same time do not lead to destruction in the polymer matrix. It is possible to carry out sulfonation, starting with a relatively low concentration of sulfonating agent in the solvent (which eliminates catalyst overheating during sulfonation as a result of the rapid release of a large amount of reaction heat), followed by an increase in the concentration or strength of the sulfonating agent.

 To carry out acid-catalyzed reactions, a known method [N. G. Polyansky, "Catalysis by ion exchangers", M., Chemistry, 1973, p. 103-186], according to which acid sulfocathionites are used as a catalyst. At the same time, the use of acid sulfocationites for the catalysis of hydration reactions of unsaturated compounds, including alkenes [ibid., p. 104-119), elimination, including dehydration of alcohols to obtain alkenes and / or esters [ibid., P. 120-129], the synthesis of esters from acids and alcohols [ibid, p. 129-140], alkylation [ibid., P. 140-157], polymerization and isomerization of organic substances, including alkenes (including their dimerization) [ibid, p. 157-166], hydrolysis of organic compounds [ibid, p. 103-109], condensation of organic compounds [ibid., P. 166-183], addition reactions, incl. for preparing alkyl tert-alkyl esters from tert-alkenes and alcohols [ibid., p. 185] and other acid-catalyzed reactions.

The described reactions are designed to use conventional (well-known) cation exchange catalysts containing monosulfonated (with one group -SO ₂ OH) aromatic groups, the thermal stability of which is officially limited to a temperature of 120 ^o C. In fact, gradual cleavage is already observed at temperatures above 100 ^o C sulfo groups. In the cited book, N.G. Polyansky mainly described reactions that occur at a temperature not exceeding 100 ^o C [S. 104, para. 3; from. 110, para. 4, etc.], in particular, hydration, dimerization, polymerization, alkylation reactions using tert-alkenes.

Carrying out the corresponding reactions with non-tretic alkenes requires higher temperatures (usually more than 120 ^o C), at which there is a significant desulfurization of sulfocationite. For example, in ["Ionites", Catalog, Cherkasy, 1980, C. 10], it is stated that for the KU-2-8 cation exchange resin, which is a sulfonated copolymer of styrene with divinylbenzene, at a temperature of 120 to 150-170 ^o C, relative losses exchange capacity due to desulfurization within 24 hours are respectively 6.5 and 19.5%. It is clear that in this case the known method cannot be used for the purposes of continuous industrial production, but can only be used briefly for preparative purposes. Moreover, it is possible that in this case, and possibly prevails, catalysis is not caused by sulfocathionite, but formed as a result of cleavage with free sulfuric acid (which is associated with severe corrosion of the equipment).

We propose (independent claim 11 of the claims) a method for carrying out acid-catalyzed reactions at temperatures up to 180 ^o C, which consists in the use of a sulfonic ion catalyst containing a cross-linked polymer with sulfonated aromatic groups, in which among sulfonated aromatic groups there are substantially, preferably up to 100%, aromatic groups predominant having at least two —SO ₂ OH groups.

Alternatively, a method is proposed that the acid-catalyzed reactions are the reactions of the conversion of non-tertiary and / or tertiary alkenes by dimerization, codimerization, oligomerization, isomerization with a multiple bond shift, hydration, interaction with alcohols, carboxylic acids and aldehydes, alkylation , including aromatic compounds, moreover, during the conversion of non-tertiary alkenes maintain a temperature of from 100 to 180 ^o C, and during the conversion of tertiary alkenes preferably support from 50 to 100 ^o C.

 Alternatively, a method is proposed that consists in the fact that the acid-catalyzed reactions are the reactions of dehydration of alcohols, decomposition of esters, dioxanes and transesterification.

Alternatively, a method is proposed that consists in initially conducting reactions at temperatures below 150 ^o C, preferably below 130 ^o C, in the presence of a catalyst containing simultaneously aromatic groups with two and one groups - SO ₂ OH, possibly followed by neutralization of the separated from catalyst of the reaction mass, and then after the removal of the -SO ₂ OH groups from at least most of the monosulfonated aromatic groups of the catalyst, it is used to carry out reactions at temperatures up to 180 ^o C.

In the presence of catalysts obtained by the proposed method, can be carried out any reactions catalyzed by strong acids, proceeding at temperatures up to 180 ^o C (including at relatively low temperatures), in particular, reactions involving both tertiary and non-tertiary, e.g. normal, alkenes: positional (by multiple bond position) isomerization, dimerization, codimerization and oligomerization, alkylation (including aromatic compounds), hydration, interaction with alcohols and carboxylic acids, p reactions of dehydration of alcohols and decomposition of esters and esters, interactions with aldehydes and decomposition of dioxanes, intermolecular dehydration of alcohols, transesterification, etc.

The preferred temperature range for the reactions of transformation of tert-alkenes in this case is the region of 50-100 ^o C, for the reaction of conversion of non-tertiary alkenes (including n-alkenes) is the region of 100-180 ^o C.

 The implementation of the proposed methods for the production of heat-resistant soufionic catalysts and the carrying out of reactions occurring in the presence of acid catalysts at elevated temperatures is illustrated by examples 1-17 and 18-23, respectively.

 These examples do not exhaust all possible embodiments of the invention and it is possible to use other technical solutions while observing the essence of the invention set forth in the claims.

 Examples.

 In all the examples below, the same methods were used to determine the static exchange capacity (SOE) of the catalysts and to check their thermal stability (preservation of sulfo groups at high temperatures).

 Before determining the SOE, the catalysts were thoroughly washed with distilled water until there was almost complete absence of free sulfonating agents, as well as other water-soluble impurities.

 SOE by sulfo groups was determined by treating a weighed portion of the catalyst 01N with an aqueous NaCl solution, followed by titration of the liberated acid with a 0.1N aqueous NaOH solution. The SOE values found in this way and given below are expressed in mEq H + / g dry weight of the catalyst.

The thermal stability of the catalysts at a given temperature was checked by mixing with 10 times (relative to the weight of the catalyst) amount of distilled water for 24 hours, and then again with 10 times the amount of distilled water for 24 hours (total 48 hours), followed by separation the resulting aqueous solution, thoroughly washing the catalyst with distilled water at room temperature and determining its SOE. Further for comparison, data on the thermal stability of the catalysts at 160 ^o C.

 Example 1

The phenol disulfonic acid disodium salt was polycondensed with formaldehyde (in a 1: 1.4 molar ratio) in the presence of NaOH at a temperature of 90 ^° C, followed by cooling, aqueous washing of porous granules, treatment with dilute sulfuric acid and thorough washing with distilled water.

 The resulting cross-linked sulfopolycondensate (catalyst) had a static exchange capacity of SOE = 3.0 mEq H + / g. It contained practically only disulfonated aromatic groups.

 The test results of the thermal stability of the catalyst are shown (in comparison with other catalysts) in table. 1.

 Example 2

Porous particles (0.035 - 1 mm) of a cross-linked styrene copolymer (88%) and divinylbenzene (12%) were suspended in a suspension with a wet mixture of nitrogen (60%) and SO ₃ (40%) at a temperature of 70-90 ^o C for 2 hours. The particles were then purged with nitrogen and then thoroughly washed with distilled water to remove the free sulfonating agent.

 The SOE of the resulting catalyst was 5.5.

The relative content of disulfonated (with two groups -SO ₂ OH) aromatic groups (DS), monosulfonated (with one group -SO ₂ OH) aromatic groups (MS) and non-sulfonated aromatic groups (HC) was respectively (relative%): DS ~ 50, MS ~ 20, NS ~ 30.

The content of aromatic groups with three groups —SO ₂ OH (TS) did not reach 1 rel.%.

 The catalyst was tested for thermal stability, the results of which are given in table. 1.

 Example 3

The catalyst obtained in Example 2 was treated twice with stirring with a 30-fold (relative to the catalyst) amount of distilled water at 165 ^° C. for a total of 70 hours.

 After that, the catalyst was thoroughly washed with distilled water at room temperature, its SOE was determined, and then it was tested for heat resistance.

 The SOE of the catalyst was 4.9.

 The relative content of groups in the catalyst (rel.%): DS ~ 50, NS ~ 50.

 The results of the test for thermal stability are given in table. 1.

 Example 4

The porous particles of a crosslinked polymer of styrene and divinylbenzene, similar to that used in example 2, were subjected to treatment with a 20% solution of SO ₃ in concentrated sulfuric acid with a gradual increase in temperature from 80 to 100 ^o C for 2 hours. The resulting catalyst (after thorough washing with distilled water at room temperature) had a SOE = 5.8.

 The relative content of the groups was (rel.%): DS ~ 62, MS ~ 3, NS ~ 35.

 The results of the test for thermal stability - in table. 1.

 Example 5

The catalyst obtained in example 4 was twice subjected to treatment (with stirring) with a 20-fold amount of distilled water at 165 ^° C. for a total of 70 hours.

 After that, the catalyst was thoroughly washed with distilled water at room temperature. Found SOE = 5.6. The relative content of the groups (rel.%): DS ~ 62, NS ~ 38.

 The results of the test of thermal stability are given in table. 1.

 Example 6

The porous particles of a crosslinked polymer similar to that used in Example 2 were treated with 98% sulfuric acid for 6 hours at a temperature gradually increasing from 100 to 130 ^° C. After thorough washing with distilled water, the catalyst had a СОЕ = 5.6.

 The relative content of groups in the catalyst was (rel.%): DS ~ 55, MS ~ 15, NS ~ 30.

 Thermostability of the catalyst - see table. 1.

 Example 7

The catalyst obtained in example 6 was subjected to stirring twice with 30 times the amount of heptane at a temperature of 165 ^o C for 70 hours, and then thoroughly washed with distilled water at 40 ^o C.

 The SOE of the catalyst was 5.3, the relative content of the groups (rel.%): DS ~ 55, HC ~ 45.

 Thermostability - see table. 1.

 Example 8

Suspension polymerization of styrene (80%) and divinylbenzene (20%) produced a copolymer that was mixed with polyethylene (copolymer: polyethylene ratio 3: 1) and the mixture was extruded in the presence of ~ 7% water at a temperature of 170-190 ^o C.

The obtained granules in the form of rings 6 mm high with an outer diameter of 6 mm were subjected to radiation treatment to crosslink the polymer chains, then swelled in dichloroethane and treated with a 10% solution of SO ₃ in concentrated sulfuric acid with a gradual increase in temperature from 70 to 90 ^o C within 5 hours.

 After that, the catalyst was thoroughly washed with distilled water at room temperature.

 The SOE of the catalyst was 4.2.

 The ratio of groups (rel.%): DS ~ 50, MS ~ 10, NS ~ 40.

 Thermostability by sulfo groups - see table. 1.

 Example 9

The catalyst obtained in example 8 was twice subjected to treatment with 30 times the amount of water at a temperature of 160 ^o C for 70 hours, then thoroughly washed with distilled water at 30 ^o C.

 The SOE of the catalyst was 3.8.

 The ratio of groups (rel.%): DS ~ 50, NS ~ 50.

 Thermostability by sulfo groups - see table. 1.

 Example 10

The industrial sulfoionite catalyst KU-23, which was predominantly a monosulfonated copolymer of styrene (88%) and divinylbenzene (12%), had SOE = 4.0 and an approximate group ratio (rel.%): DS ~ 16, MS ~ 49, MS ~ 35 , was subjected to double treatment with 30 times the amount of water at 165 ^o C for 70 hours and then thoroughly washed with distilled water at 40 ^o C.

 The SOE of the catalyst was 2.3.

 The ratio of groups (rel.%): DS ~ 16, MC ~ 1, HC ~ 83.

 Thermostability - see table. 1.

 Example 11

The industrial sulfonic ion catalyst KU-23, similar to that used in example 10, was subjected to treatment with a 10% solution of SO ₃ in concentrated sulfuric acid at 90-105 ^o C for 2 hours.

After that, the catalyst was thoroughly washed with distilled water at 40 ^o C.

 The SOE of the catalyst was 5.7.

 The ratio of groups (rel.%): DS ~ 58, MS ~ 10, NS ~ 32.

 Thermostability - see table. 1.

 Example 12

The catalyst obtained in Example 11 was treated twice with a 30-fold amount of water at 165 ^° C. for 70 hours and then thoroughly washed with distilled water at 40 ^° C.

 The SOE of the catalyst was 5.4, the relative content of the groups (rel.%): DS ~ 58, HC ~ 42.

 Thermostability - see table. 1.

 Example 13

An industrial sulfoionite catalyst, which was a cross-linked sulfonated copolymer of styrene (80%) and divinylbenzene (20%) with a particle size of 0.4-1 mm, having a SOE of 5.2 and an approximate group ratio: DS ~ 35, MS ~ 35, HC ~ 30 , was subjected to twice processing with a 25-fold amount of octane at 155 ^o C for 70 hours, then the catalyst was thoroughly washed with distilled water at 50 ^o C.

 The SOE of the catalyst was 4.0, the relative content of the groups (rel.%): DS ~ 35, NS ~ 65.

 Thermostability - see table. 1.

 Example 14

 We used the spent (in the synthesis of methyl tert-butyl ether from isobutene and methanol) industrial sulfonic ion catalyst KU-23, which had a residual SOE of 2.2 (before starting fresh catalyst KU-23 had SOE = 4.0), with a total content of sulfo groups in the H + form and H-substituted sulfo groups close to the content of sulfo groups in the fresh catalyst. The development (decrease in SOE) of the catalyst occurred mainly as a result of the replacement of the hydrogen atom in the sulfoxyl groups by nitrogen compounds and sodium ions, as well as iron and calcium ions.

The catalyst was treated initially with a solution of sulfuric acid at 75 ^o C for 2 hours, and then with a 5% solution of SO ₃ in concentrated sulfuric acid at 100-110 ^o C for 0.5 hours. Then the catalyst is thoroughly washed with distilled water at 40 ^o C.

 The SOE of the catalyst was 5.4, the relative content of the groups (rel.%): DS ~ 53, MS ~ 12, HC ~ 35.

 Thermostability - see table. 1.

 Example 15

The catalyst obtained in example 14 was subjected to a double treatment with a 30-fold excess of water at a temperature of 165 ^o C, and then washing with distilled water at 30 ^o C.

 The SOE of the catalyst was 5.1, the relative content of the groups (rel.%): DS ~ 53, NS ~ 47.

 Thermostability - see table. 1.

 Example 16

 The copolymerization of α-methylstyrene (80%), 1,3-butadiene (15%) and acrylonitrile (5%) on the surface of porous silica gel granules was carried out.

After washing, the obtained granules were subjected to treatment with a 5% solution of SO ₃ in concentrated sulfuric acid with a gradual increase in temperature from 80 to 95 ^o C for 2 hours. Then the granules were thoroughly washed with distilled water.

 The SOE of the catalyst was 1.65, the relative content of groups in the polymer (rel.%): DS ~ 82, MS ~ 3, HC ~ 15.

 Thermostability - see table. 1.

 Example 17

The catalyst obtained in example 16 was twice subjected to treatment with a 30-fold excess of water at a temperature of 165 ^o C, and then washed with distilled water at 50 ^o C.

 SOE of the catalyst = 1.6, the relative content of groups in the polymer (rel.%): DS ~ 82, HC ~ 18.

 Thermostability - see table. 1.

 Example 18

In the presence of a catalyst obtained according to example 5 and having a group content (rel.%): DS ~ 62, MS ~ 0, HC ~ 38, СОЕ = 5.6, propane (32%) - propene (68%) was contacted in a flow reactor %) mixtures with water at 155-160 ^o C. The initial molar ratio of propene: water was 1: 1.1, the total liquid supply of 2.5 kg / kg of catalyst per hour, the pressure in the reactor 135-140 atm.

 The propene conversion was 43%.

The reaction mixture contained (%): propane - 24.0; propene - 29.0; isopropanol - 27.0; diisopropyl ether - 3.5; water - 16.2; propene dimers - 0.3. After distillation of C ₃ hydrocarbons per 1 kg of starting materials (propane-propene mixture and water), 0.47 kg of product was obtained containing 57.5% isopropanol, 7.4% diisopropyl ether, 34.5% water and 0.6% dimers propene.

 After a 300-hour run, the reduction in SOE of the catalyst did not exceed 1%.

 Example 19

With the catalyst obtained according to example 7 and having a group content (rel.%): DS ~ 55, MS ~ 0, HC ~ 45, and СОЕ = 5.3, liquid-phase contacting of benzene and a mixture of 2-butenes was carried out in a flow reactor (cis - and trans isomers ~ 1: 1) at a temperature of 150 ^o C. The initial molar ratio of benzene to 2-butenes was 3.5: 1, the total fluid supply of 1.7 kg / kg of catalyst per hour.

 The conversion of n-butenes was 99.4%. The reaction mixture contained 0.1% 2-butenes, 0.6% 2-butenes dimers, 60.6% benzene, 17.8% sec-butylbenzene, 0.9% di-sec-butylbenzene.

 After a 300-hour run, the reduction in SOE of the catalyst did not exceed 1%.

 Example 20

With the catalyst obtained according to example 9 and having the form of rings with a height of 6 mm and an outer diameter of 6 mm, in which the relative content of the groups was (rel.%): DS ~ 50, MS ~ 0, HC ~ 5, SOE = 3.8 , dehydration of sec-butanol was carried out in a reactive distillation column apparatus. The catalyst in the form of two layers was located in the middle part of the apparatus, sec-butanol was fed between the catalyst layers. A mixture containing predominantly n-butenes was withdrawn from the top of the apparatus, and a stream containing mainly water was below. The temperature of 145-150 ^o C. was maintained in the catalyst bed.

 The load was 0.4 kg of starting sec-butanol per 1 kg of catalyst per hour.

 The conversion of sec-butanol was 95%.

 After a 300-hour run, the reduction in SOE of the catalyst did not exceed 1%.

 Example 21

With the catalyst obtained according to example 12 and having a group content (rel.%): DS ~ 58, MS ~ 0, HC ~ 42, SOE = 5.4, in the once-through apparatus with a heat removal system, di- and trimerization of propene into propane- propene fraction containing 70% propene mixed with 50% n-butane. The temperature in the reactor was 100-110 ^o C, the load of 1.2 kg of hydrocarbon mixture per 1 kg of catalyst per hour. The conversion of propene is 97%.

 The ratio of the formed trimers and dimers of propene 4: 1 (wt.).

 Example 22

 In the presence of the catalyst obtained in example 5 (SOE 5.6 mg / equiv H + / g cat, the relative content of the groups DS / MS / HC is 62/0/38), tert-butanol and methyl tert-butyl ether are obtained ( MTBE) from an isobutane-isobutene mixture containing 45% isobutene.

The specified hydrocarbon mixture in an amount of 1 kg / h and water in an amount of 0.1 kg / h are fed to the first reactor and the temperature is maintained at 85 ^° C at the inlet and 100 ^° C at the outlet.

 The load of 0.8 l / l of catalyst per hour.

From the reactor output mixture containing mainly C ₄ hydrocarbons and tert-butanol, hydrocarbons distilled C ₄ and output the tert-butanol in an amount of 0.39 kg / hour. A hydrocarbon mixture containing 22% isobutene distilled off in an amount of 0.71 kg / h is mixed with methanol supplied in an amount of 0.09 kg / h and contacted with said catalyst in a second reaction zone at a temperature of 50-65 ^° C.

 Load 1 l / l cat / hour.

 Unreacted hydrocarbons with an admixture of methanol are distilled off from the reaction mixture (for subsequent recovery) and 0.22 kg / h of MTBE is obtained.

 After a 300-hour run, there was no decrease in SOE of the catalyst in the reactor.

 Example 23

With an industrial sulfoionite catalyst, which is a cross-linked sulfonated copolymer of styrene (80%) and divinylbenzene (20%) with a particle size of 0.4-1 mm, СОЕ = 5.2 and the group ratio (rel.%): DS ~ 35, MS ~ 35, HC ~ 30, liquid-phase contacting of benzene and propane (35%) - propene (65%) mixture was carried out at a temperature of 125-130 ^o C (initial benzene: propene molar ratio 10: 1, propene conversion 99.5%, yield isopropylbenzene 0.93 mol / mol propene) for 4000 hours.

At the end of the run, the catalyst had SOE = 4.2 and the ratio of the groups: DS ~ 35, MS ~ 3, HC ~ 62. Then the catalyst was used for hydration and esterification of propene (into diisopropyl ether) in a similar propane-propene mixture at a temperature of 150 ^o C.

 The initial propene: water molar ratio was 1.1: 1. The total fluid supply of 1.3 kg / kg of catalyst per hour. Achieved propene conversion of 45%.

 For 1 kg / mol of converted propene, the yield of isopropanol (in the composition of the reaction mixture) was 0.84 kg mol, of diisopropyl ether 0.15 kg mol.

After a 400-hour run at 150 ^° C., the reduction in SOE of the catalyst did not exceed 5%.

Claims (14)

1. The method of obtaining heat-resistant sulfonate catalysts by the formation of cross-linked polymers or their compositions containing sulfonated aromatic groups, characterized in that among sulfonated aromatic groups, predominant, preferably up to 100%, aromatic groups having at least two —SO ₂ OH groups and eliminate or substantially reduce the content of aromatic groups having one group -SO ₂ OH, by use in the preparation of a polymer of a monomer having an aromatic group at least two sulfog SCP into H ⁺ or H-substituted form, followed by transfer of the latter in -SO ₂ OH-form, and / or by deep sulfonation of aromatic groups in the polymer, and / or deletion in the sulphonated polymer containing at least monosulfated di- and aromatic groups sulfo groups of at least most aromatic groups containing one sulfo group at an elevated temperature, preferably above 150 ^° C. 2. The method according to claim 1, characterized in that during the formation of the polymer and / or after it crosslinking of the polymer chains is carried out by any suitable agent or method, eliminating the dissolution or excessive swelling of the polymer matrix and sulfonated catalyst in water, hydrocarbons, alcohols, ethers, mixtures thereof and solutions of sulfuric acid and SO ₃ , for example, using compounds with two vinyl groups, aldehydes or radiation crosslinking. 3. The method according to claim 1, characterized in that (co) polymerization and / or polycondensation of the styrene and / or phenol derivatives containing at least two —SO ₂ OH and / or H-substituted sulfo groups in each or in most aromatic groups is carried out groups. 4. The method according to claim 1, characterized in that the predominant introduction of two groups of -SO ₂ OH is carried out in a cross-linked polymer of styrene or alkyl styrene and / or a copolymer of styrene and / or alkyl styrene with divinylbenzene or alkadiene-1,3. 5. The method according to claim 1, characterized in that the predominant introduction of two -SO ₂ OH groups into the aromatic groups of a cross-linked (co) polymer or polycondensate applied to the surface of porous solid granules or other forms with a developed surface is carried out. 6. The method according to claim 1, characterized in that the predominant introduction of two -SO ₂ OH groups into the aromatic groups of porous granules or other forms containing a crosslinked (co) polymer of a vinyl aromatic compound in admixture with a molding polymer material, for example polyethylene and / or polypropylene. 7. The method according to claim 1, characterized in that the sulfonation catalysts are additionally sulfonated, containing at least aromatic groups having one —SO ₂ OH group or —SO ₂ OX group, where X is a metal or other neutralizing substituent. 8. The method according to claim 1, characterized in that moist SO ₃ and / or sulfuric and / or chlorosulfonic acid and / or solutions of SO ₃ in said acids or solutions of said sulfonating agents in organic solvents are used as a sulfonating agent; sulfonation is carried out at 50 - 200 ^o With preferably with a gradual increase in temperature. 9. The method according to claim 1, characterized in that in the catalyst containing simultaneously aromatic groups with one and two groups -SO ₂ OH, desulfurization of aromatic groups containing one group -SO ₂ OH is carried out. 10. The method according to claim 1, characterized in that the desulfurization of aromatic groups containing one group of -SO ₂ OH is carried out by treating the catalyst with water and / or alcohol and / or hydrocarbons at an elevated temperature, preferably at a temperature above 160 ^o FROM. 11. A method of carrying out acid-catalyzed reactions at temperatures up to 180 ^{° C.} , characterized in that they use a sulfonate catalyst containing a cross-linked polymer with sulfonated aromatic groups, in which, among sulfonated aromatic groups, substantially, preferably up to 100%, aromatic groups prevail having at least two groups —SO ₂ OH. 12. The method according to claim 11, characterized in that the acid-catalyzed reactions are the reactions of the conversion of non-tertiary and / or tertiary alkenes by dimerization, codimerization, oligomerization, isomerization with a multiple bond shift, hydration, interaction with alcohols, carboxylic acids and aldehydes, alkylation , including aromatic compounds, moreover, during the conversion of non-tertiary alkenes, a temperature of from 100 to 180 ^{° C. is} maintained, and during the conversion of tertiary alkenes, it is preferably maintained between 50 and 100 ^° C.  13. The method according to claim 11, characterized in that the acid-catalyzed reactions are the reactions of dehydration of alcohols, decomposition of esters, dioxanes and transesterification. 14. The method according to claim 11, characterized in that the reaction is initially carried out at a temperature below 150 ^o C, preferably below 130 ^o C, in the presence of a catalyst containing simultaneously aromatic groups with two and one groups -SO ₂ OH, possibly followed by neutralization separated from the catalyst of the reaction mass, and then after the removal of the -SO ₂ OH groups from at least most of the monosulfonated aromatic groups of the catalyst, it is used to carry out reactions at temperatures up to 180 ^o C.

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