EP0993443A1

EP0993443A1 - Method for producing 4,4' dihalogendiphenylsulfone

Info

Publication number: EP0993443A1
Application number: EP98934947A
Authority: EP
Inventors: Stefan Beckmann; Helmut Reichelt; Karl Beck; Klaus Friedrich; Eugen Gehrer; Thomas Plesnivy; Walter Opper
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1997-06-24
Filing date: 1998-06-10
Publication date: 2000-04-19
Also published as: AU8437998A; WO1998058907A1; CA2283894A1; KR20010020308A

Abstract

The invention relates to a method for producing 4,4'-dihalogendiphenylsulfone by reacting halogenated benzene with 4-halogenphenylsulfonyl chloride in a liquid phase at high temperature, in the presence of a solid catalyst having acid centers. The method is characterized in that the reaction of 4-halogenphenylsulfonyl chloride with formula (I), in which X is chlorine, bromine or fluorine, with chlorobenzene, bromobenzene, or fluorobenzene, is carried out in the presence of a catalyst which is selected from one of the following groups: K1) catalysts consisting of essentially stratified silicates not having Lewis acids and having proton-saturated negative layer loads, or containing these as a basic component; K2) catalysts consisting of zeolites in the acid H form, or containing these as a basic component; and K3) catalysts consisting of mixed oxides having acidic centres, or containing these as basic components. The mixed oxides consist of a combination of (a) titanium, circonium, hafnium, tin, iron or Cr(III) oxides on the one hand, and (b) vanadium, chromium(VI), molybdenum, wolfram or scandium oxides on the other hand; or the mixed oxides are sulfatized or phosphatized oxides of the group (a), and said mixed oxides are calcined after combination, at temperatures of 450 to 800 °C.

Description

Process for the preparation of 4, 4 '-dihalodiphenyl sulfone

description

The invention relates to a process for the preparation of 4,4'-dihalodiphenyl sulfone by reacting halogenobenzene with p-halogenosulfonyl chloride in the presence of

layered silicates having acidic centers, but essentially free of Lewis acids,

Zeolites in the acid H form or

mixed oxides containing acidic centers

as catalysts.

The preparation of 4, 4'-dichloridephenyl sulfone from chlorobenzene and 4-chlorophenyl sulfonyl chloride according to the reaction equation

catalyst

Cl - / <// w ^\ ) + cιso ₂ - / (/ '^ Z - ci W _τ

is from numerous references, e.g. US 2,224,964; DE 701 954; GB 926 291; U.S. 3,334,146; US 3,673,259 and WO 83/04251.

In all of these cases, a homogeneous Friedel-Crafts catalyst, for example AICI ₃ or FeCl ₃ , was used in at least a molar amount, which cannot be recovered during processing, but must be decomposed. This leads to problems of disposal of the hydrolyzed aluminum or iron chloride, which are toxic or corrosive waste.

It has therefore already been proposed on sheet 25 of the leaflet "Envirocats Supported Reagents" (Contract Chemicals Ltd. Penrhyn Road, Knowsley Industrial Park South Prescot, Merseyside, England L34 9HY) to use the catalyst E VIROCAT® EPZG for the above-mentioned reaction . According to analysis, this catalyst is a montmorillonite catalyst, which is doped with substantial amounts of Lewis acids. This catalyst, which can be used in heterogeneous catalysis, can be recovered from the reaction mixture by filtration. However, the yields obtainable with it are unsatisfactory. Furthermore, the hydrogen halide formed in the reaction leads to the "bleeding" of the doped Lewis acid.

It is also known from WO 96/26787 that heterogeneous catalysts based on acidic "clays", which term also includes the oxides of aluminum, silicon, zirconium or titanium, can be used for alkylations. However, these catalysts only contain the "clays" as supports on which aluminum chloride has been applied, and their use for sulfonylations is neither described nor suggested.

It was therefore the task of proposing economically and ecologically advantageous heterogeneous catalysts for the preparation of 4, 4 '-dichlorodiphenyl sulfone, which allow the target product to be prepared in good yields and which are easily accessible and recoverable.

This object was achieved according to the invention with a process for the preparation of 4, 4'-dihalodiphenylsulfone, in which the halogen radicals can be the same or different, by reacting halobenzene with 4 -halophenylsulfonyl chloride in the liquid phase in the presence of a solid, acidic-centered catalyst with increased Temperature, characterized in that the reaction of 4 -halophenylsulfonyl chloride of the formula I.

in which X denotes chlorine, bromine or fluorine, with chlorine, bromine or fluorobenzene in the presence of a catalyst which is selected from one of the groups

Ki) catalysts which consist of layer silicates which are essentially not doped with Lewis acids and which have negative layer charges saturated by protons, or which contain these as an essential constituent,

K ₂ ) catalysts which consist of zeolites in the acidic H form or contain these as an essential constituent or K ₃ ) catalysts which consist of mixed oxides containing acid centers or contain these as essential constituents, the mixed oxides consisting of a combination of (a) oxides of titanium, zirconium, hafnium, tin, iron or Cr (III) on the one hand with (b) Oxides of vanadium, chromium (VI), molybdenum, tungsten or scandium on the other hand exist, or the mixed oxides are sulfated or phosphated oxides of group (a) and the mixed oxides have been calcined after their combination at temperatures of 450 to 800 ° C.

"Substantially not doped with Lewis acids" (group Ki)) means that no, or practically no, Lewis acids have been applied to the layered silicates for the purpose of generating a catalytic activity caused by them. Rather, the acidic centers of the layered silicates are said to be essentially Bronsted centers which have been produced by exchanging the metal ions for protons in the layered silicates having negative excess charges.

Accordingly, in group Ki) layered silicates essentially not doped with Lewis acids are understood to mean those silicates which contain less than 1% by weight, based on the layered silicate, of Lewis acids and in particular those which are derived from Lewis acid applied separately - transition metals are completely free.

The sheet silicates of group Ki) to be used according to the invention are above all aluminum silicates; they belong to the clay minerals and are made up of Si0 ₂ ethedron and A1 ₂ 0 ₃ octahedron layers, where part of the silicon in the tetrahedron layer is formed by trivalent cations, preferably aluminum and / or part of the aluminum in the octahedron layer by divalent ones Cations, preferably magnesium is replaced, so that negative stratified charges arise.

Layered silicates with negative charges occur naturally in the form of montmorillonites, vermiculites or hectorites or can also be synthesized.

More details are Z. M. Thomas and W. Z. Thomas, Principles and Practice of Heterogeneous-Calalysis, 1997, Vetc. ISBN 3-527-29239-8, p. 347 ff.

However, preference is given to naturally occurring montmorillonite, which is converted into the H form by acid treatment. Examples are montmorillonite

Na ₀ , 33UAlι, 67Mg ₀ , 3 ₃ ^{) (} OH ⁾ ₂ [Si ₄ Oι ₀ ] ^} with stratified charges of about 0.6 to 0.2 per formula unit.

5 For the partial or complete proton saturation of the negative layer charges, the exchangeable cations contained in the natural or synthetic layer silicates, usually alkali or alkaline earth ions, are exchanged for protons. This is done in a manner known per se, e.g. by treatment 0 with sulfuric acid or hydrochloric acid.

Since the protons are less temperature stable than layer silicates containing alkali or alkaline earth ions, so-called "pillared clays" can also be used, in which layers 5 are supported against one another. The production of such "pillared clays" is in Figuras, Catal. Rev. Be. Closely. 30 (1988) 457 and Jones, Catal. Today (2 (1988) 357. The information given there is hereby incorporated by reference and is intended to be incorporated here.

20th

In particular, layered silicates with negative layer charges, which are saturated by protons, are: montmorillonite, vermiculite and hectorite.

25 The zeolites used for use as a group K) catalyst are, for example, those of the acid H form of the structure types MFI, MEL, BOG, BEA, EMT; MOR, FAU, MTW, LTL, NES, CON or MCM-22 according to the structure classification from WM Meier, DH Olson, Ch. Baerlocher, Atlas of Zeolithe Structure Types, Elsevier, 4 ^th ed.,

30 1996.

The acidic H form of 12-ring zeolites of the structure type BETA, Y, EMT and mordenite, and 10-ring zeolites of the Pentasil type are preferred. In addition to the elements aluminum 35 and silicon, the zeolites can also contain boron, gallium, iron or titanium in the framework. They can also be partially exchanged with elements of the IB, IIB, IIIB, IIIA or VIIIB group, as well as with the elements of the lanthanides.

40 In particular come the zeolites ZBM-20, Fe-H-ZSM5, Sn-beta zeolite, beta zeolite, Zr-beta zeolite, H-beta zeolite, H-mordenite, USY, Ce-V zeolite , HY zeolite, Ti / B beta zeolite, B beta zeolite or ZB-10.

45 zeolites in the acid H form and their preparation are described in detail in the literature. Therefore, the summary in R. Szostak, Handbook of Molecular Sie- ves Van Nostrand Reinhold, New York, ISBN 0-442-31899-5 and hereby refers to the information provided there.

Mixed oxides of group K ₃ ) to be used according to the invention are, in particular, so-called superacid mixed oxides which have been described several times in the literature. For example, RJ Gillesie, Acc. Chem. Res. 1, (1968) 202 and RJ Gillespie and TE Peel, Adv. Phys. Org. Chem. 9 (972) 1.

Special super acidic metal oxides. suitable for the reaction according to the invention as catalysts of group K ₃ ), (for the reaction of butene and pentanes) by Kazushi Arata in Applied Catalysis A: General 146 (1996) 3-32.

Reference is made to the information in this literature reference regarding the super-acidic metal oxides and their production and they are to be considered incorporated here.

Suitable sulfated or phosphated metal oxides of group (a) are, in particular, phosphated or sulfated zirconium oxide or titanium oxide, which may also contain further elements, such as iron, cobalt or manganese.

The following are preferred as sulfated or phosphated catalysts:

Zr0S0 ₄ (S content 0.5 to 4 mol%) Zr0 ₂ P ₂ O ₅ (P ₂ 0 ₅ content 3 to 20 mol%) Fe ₂ 0 ₃ P ₂ 0 ₅ (P ₂ 0 ₅ content 3 to 20 mol%) Co / Mn / Zr0 ₂ S0 ₄ (S content 0.5 to 4 mol%);

Co / Mn content 0.1 to 5 mol%) Fe / Mn / Zr0 ₂ S0 ₄ (S content 0.5 to 4 mol%;

Fe / Mn content 0.1 to 5 mol%)

Preferred superacid mixed metal oxides of groups (a) and (b) are those which contain zirconium, titanium, iron, tin or Cr (III) on the one hand and tungsten or molybdenum on the other hand.

In particular, Ti0 ₂ W0 ₃ , Fe ₂ 0 ₃ W0 ₃ , Zr0Mo0 ₃ , Zr0 ₂ W0 ₃ , Cr ₂ 0 ₃ W0 ₃ , W0 ₃ Ti0, Ti0 ₂ W0 ₃ or Sn0W0 ₃ Si0 should be mentioned, the molar ratio of the oxides group (a) to group (b) is usually 70 to 30 to 90 to 10.

The reaction according to the invention generally takes place at temperatures of 80 to 300 ° C., preferably 110 to 220 ° C. and in particular 130 to 200 ° C. The reaction is usually carried out at normal pressure or in a closed vessel at the autogenous pressure of the reaction mixture, but elevated pressure up to 50, preferably up to 30, bar is also possible.

According to a preferred embodiment, 4, 4'-dichlorophenyl sulfone is prepared by reacting 4-chlorophenyl sulfonyl chloride with chlorobenzene.

In general, the starting material chlorobenzene is used in excess, e.g. in a 1 to 100, preferably 5 to 20 and in particular a 5 to 15 molar excess over the amount of chlorophenylsulfonyl chloride.

The chlorobenzene serves as a solvent. Alternatively, another solvent, e.g. a hydrocarbon, preferably such a hydrocarbon may be added that e.g. the desired reaction temperature is achieved at normal pressure.

The catalytic reaction is generally carried out in the liquid phase in the suspension mode or preferably over a fixed catalyst, in a continuously flowed reactor, the hydrochloric acid liberated being drained off and the reaction mixture containing the product being drawn off for working up by distillation. After fractionation into product, unreacted chlorobenzene and optionally solvent, the latter are returned to the reaction.

The, 4 '-dichlorodiphenyl sulfone is used in a manner known per se e.g. purified by solvent crystallization from toluene, chlorobenzene or methanol. It is obtained in very good purity in yields of 50 to 95% of theory. Th. Based on p-chlorophenylsulfonyl chloride used.

Specifically, for example, the reaction according to the invention is carried out continuously as shown in FIG. 1 in such a way that the catalyst is fixed in reactor A and from below the reaction mixture from the starting materials chlorobenzene (1) and 4-chlorophenylsulfonyl chloride (2) and recycled chlorobenzene (4th ) is flowed through without pressure. The reaction temperature is, for example, 80 to 300 ° C. and the excess of chlorobenzene is 10 molar. The reaction mixture, from which the hydrogen chloride released escapes via line (5), is transferred via line (3) to a distillation column (B) and separated into the product (6) and chlorobenzene (4) to be recycled, which is still to be purified . The heterogeneous catalyst remains active over a longer period of time. It can then be reactivated, for example by burning in air at temperatures above 450 ° C. This makes the new process particularly advantageous over conventional synthesis for economic and environmental reasons.

Examples

Use of catalysts from group Ki) Example 1

0.1 mol of 4-chlorobenzenesulfonyl chloride and 1 mol of chlorobenzene were admixed with 1 g of an acid-treated (protonated) montmorillonite from Südchemie (K10) (free of separately applied Lewis acid transition metals) as a catalyst and, at a closed autoclave, at 200 ° C. heated. After a reaction time of 6 hours, the autoclave was cooled, let down and the reactor contents were filtered off from the catalyst. The excess chlorobenzene was distilled off and the residue was analyzed. When the chlorobenzenesulfonyl chloride had completely converted, the yield of 4,4'-dichlorodiphenyl sulfone was 92% of theory. Th.

Example 2

0.1 mol of 4-chlorobenzenesulfonyl chloride and 1 mol of chlorobenzene were mixed with 1 g of the KSF catalyst from Südchemie (montmorillonite impregnated with HS0) and heated to 200 ° C. in a closed autoclave. After a reaction time of 6 hours, the autoclave was cooled, let down and the reactor contents were filtered off from the catalyst. The excess chlorobenzene was distilled off and the residue was analyzed. When the 4-chlorobenzenesulfonyl chloride had completely converted, the yield of 4,4′-dichlorodiphenyl sulfone was 91% of theory. Th ..

Example 3

A tube reactor filled with the catalyst according to Example 1 was flowed through from bottom to top with a mixture of 4-chlorobenzenesulfonyl chloride and chlorobenzene in a ratio of 1:10. The released HCl gas was discharged at the top of the tubular reactor and passed through an exhaust gas scrubber. The raw reactor output was collected and the excess chlorobenzene was removed by distillation. When the 4-chlorobenzenesulfonyl chloride had completely converted, the yield was: 92% of theory. Th .. Use of catalysts from group K ₂ ) Example 4

0.1 mol of 4-chlorobenzenesulfonyl chloride and 1 mol of chlorobenzene were mixed with 1 g of beta zeolite as a catalyst and heated to 200 ° C. in a closed autoclave. After a reaction time of 6 hours, the autoclave was cooled, let down and the reactor contents were filtered off from the catalyst. The excess chlorobenzene was distilled off and the residue was analyzed. When the 4-chlorobenzenesulfonyl chloride was completely converted, the yield of 4, '-dichlorodiphenyl sulfone was 91% of theory. Th ..

The beta zeolite was obtained as follows:

220 g ß-zeolite from Jetikon (Zeokat-Beta, composition: Si0 ₂ = 91%, A1 ₂ 0 ₃ = 7.8, Na ₂ 0 = 0.5%, K ₂ 0 = 0.7%, BET- Surface area = 700 m ² / g, pore size in Ä = 7.6 x 6.7; 5.5 x 5.5, particle size 0.2 to 0.5 μm) were with 5% Walocel ^® and 230 g water Compressed in the kneader for 45 minutes. The mass was then shaped into 2 mm strands at a pressure of 70 bar. These were dried at 110 ° C and calcined at 500 ° C for 16 hours.

195 g of these strands were exchanged with 3 liters of 20% NHC1 solution at 80 ° C. for 2 hours and then washed with 10 liters of water. A second exchange was then carried out with likewise 3 1 20% NHC1 solution at 80 ° C. for 2 hours and the product was washed Cl-free. After drying at 110 ° C, the product was calcined at 480 ° C for 5 hours.

Example 5

0.1 mol of 4-chlorobenzenesulfonyl chloride and 1 mol of chlorobenzene were mixed with 1 g of Zr-beta zeolite as a catalyst and heated to 200 ° C. in a closed autoclave. After a reaction time of 6 hours, the autoclave was cooled, let down and the reactor contents were filtered off from the catalyst. The excess chlorobenzene was distilled off and the residue was analyzed. When the 4-chlorobenzenesulfonyl chloride had completely converted, the yield of 4,4'-dichlorodiphenyl sulfone was 95% of theory. Th ..

The Zr beta zeolite was obtained as follows:

50 g of beta zeolite were heated in a rotary tube furnace at 380 ° C. under nitrogen for 2 hours. The mixture was then cooled to room temperature and 8.9 g of ZrCl were added as a powder. The mixture was heated to 460 ° C. over the course of 25 minutes and this for 2 hours Temperature maintained (N ₂ - current 10 1 / h). The product was then calcined at 550 ° C. for 3 hours.

Example 6

A tube reactor filled with beta zeolite as a catalyst was flowed through from bottom to top with a mixture of 4-chlorobenzenesulfonyl chloride and chlorobenzene in a ratio of 1:10. The HCl gas released was discharged at the top of the tubular reactor. The reactor crude discharge was collected and the excess chlorobenzene was removed by distillation. With complete conversion of the 4-chlorobenzenesulfonyl chloride, the yield was: 91% of theory. Th ..

Examples 7 and 8

Table 1

If the procedure was as described in Example 4 and the catalysts indicated in Table 1 were used, the results given there were obtained.

The catalysts of Examples 7 and 8 were obtained as follows:

ZBM-20

273 kg of water glass (Wöllner) and 252 kg of 56% hexamethylenediamine solution were placed in an autoclave. A solution of 31.1 kg of iron sulfate, 20.6 kg of sulfuric acid (98% strength) and 425 kg of water was then stirred in at 50 ° C. and the mixture was stirred for 6 hours. The resulting gel was then left to age without stirring for 11 hours and heated to 160 ° C. at a stirrer speed of 30 rpm. After the temperature had been reached, the mixture was stirred at 18 rpm for a further 94 hours. The crystallized product was filtered off, washed with water, dried and calcined.

Fe-ZSM-5

100 g of H-ZSM-5 were suspended in 200 ml of water. A solution of 70 g of FeCl ₂ - ₄ H ₂ 0 in 200 ml of water was then added and the mixture was stirred at room temperature for 24 hours. The product was filtered off, washed free of chlorine, dried at 110 ° C. and calcined at 550 ° C. for 3 hours.

Use of catalysts from group K ₃ ) Example 9

a) Catalyst production

100 g of ZrOCl ₂ (MW = 178, 0.56 mol) were dissolved in 1000 ml of water. The Zr (OH) hydrate was then precipitated at room temperature with 100 ml of 25% NH ₃ solution. The precipitate was filtered off and washed neutral with water. The product was stirred with 300 ml of 1 NH ₂ S0 (0.3 mol = 0.6 val) for one hour and then filtered off. The precipitate was dried at 110 ° C. for 24 hours and then calcined in air at 625 ° C. for 2 hours.

b) implementation

0.1 mol of chlorobenzenesulfonic acid and 1 mol of chlorobenzene were mixed with 1 g of Zr0 S0 catalyst and heated to 200 ° C. in a closed autoclave. After a reaction time of 6 hours, the autoclave was cooled, let down and the reactor contents were filtered off from the catalyst. The excess chlorobenzene was distilled off and the residue was analyzed. When the 4-chlorobenzenesulfonyl chloride had completely converted, the yield of 4, '-dichlorodiphenyl sulfone was 91% of theory

Example 10

Preparation of the catalyst

A solution of 53 g of tungstic acid and 112 g of 25% NH ₃ solution was added to 200 g of TiO ₂ powder. This mixture was kneaded for 150 minutes and then dried at 120 ° C. for 12 hours. The product was then sieved and calcined at 675 ° C for 2 hours.

b) implementation

0.1 mol of 4-chlorobenzenesulfonyl chloride and 1 mol of chlorobenzene were mixed with 1 g of TiOWO ₃ catalyst according to (a) and heated to 200 ° C. in a closed autoclave. After a reaction time of 6 hours, the autoclave was cooled, let down and the reactor contents were filtered off from the catalyst. The excess chlorobenzene was distilled off and the residue was analyzed. When the chlorobenzenesulfonyl chloride had completely converted, the yield of 4,4'-dichlorodiphenyl sulfone was 90% of theory.

Example 11

A tube reactor (5 cm in diameter and 50 cm in length) filled with Zr0 ₂ S0 ₄ catalyst (produced according to Example 9) was continuously flowed through from bottom to top with a mixture of 4-chlorobenzenesulfonyl chloride and chlorobenzene in a ratio of 1:10. The released HCl gas was discharged at the top of the tubular reactor and passed through an exhaust gas scrubber. The raw reactor discharge was collected and the excess chlorobenzene was removed by distillation. With complete conversion of the chlorobenzenesulfonyl chloride, the yield was 91% of theory.

Examples 12 to 15

If the procedure of Example 11 is followed using the mixed oxides given in Table 2, similar results are obtained.

Table 2

The catalysts according to Examples 12 to 15 were produced as follows:

C0 / Mn / Zr0 ₂ S0

Amorphous Zr (OH) hydrate (preparation analogous to Example 9) was impregnated with a solution of CO (N0 ₃ ) ₂ , Mn (N0 ₃ ) and (NH) ₂ S0. The product was evaporated in a rotary evaporator and then calcined at 625 ° C. for 2 hours.

Fe0 / W0 ₃

An Fe (N0 ₃ ) ₃ solution was precipitated using NH ₃ FeO (OH). After filtering, the solution was impregnated with

(NH) ₂ W0 ₄ in water. After evaporation, calcination was carried out at 550 ° C. for 2 hours. The W0 ₃ content of the product was 20%. Zr0 / Mo0 ₃

Amorphous Zr (OH) ₄ hydrate (preparation analogous to Example 9) was impregnated with a solution of (NH ₄ ) ₂ Mo0 ₄ in water. After evaporation, the product was calcined at 600 ° C. for 2 hours. The Mo0 ₃ content was 5%.

A solution of 0.25 mol SnCl ₄ in 300 ml water was added to Sn0 ₂ / Si0 ₂ / W0 ₃ 0.25 mol Si0 ₂ sol. Then 0.25 mol (NH ₄ ) ₂ WO ₄ dissolved in 200 ml of water was added. The gel was precipitated by adding 1 liter of water. The precipitate was aged for 24 h and then filtered and dried at 110 ° C. The product was calcined at 700 ° C for 5 hours.

Compared to the ENVIROCAT EPZG catalyst mentioned at the beginning, the catalysts of group K ₃ to be used according to the invention give significantly better yields.

Claims

claims

1. A process for the preparation of, 4 '-dihalodiphenylsulfone by reacting halogenobenzene with 4 -halophenylsulfonyl chloride in the liquid phase in the presence of a solid, acid-centered catalyst at elevated temperature, characterized in that the reaction of 4 -halophenylsulfonyl chloride of the formula I

in which X denotes chlorine, bromine or fluorine, with chlorobenzene, bromine or fluorobenzene in the presence of a catalyst which is selected from one of the groups

Ki) catalysts which consist essentially of layered silicates not doped with Lewis acids

Have proton-saturated negative layer charges, exist or contain them as an essential component,

K ₂ ) catalysts which consist of zeolites in the acidic H form or contain these as an essential constituent or

K ₃ ) catalysts which consist of mixed oxides containing acid centers or contain these as essential constituents, the mixed oxides consisting of a combination of (a) oxides of titanium, zirconium, hafnium, tin, iron or Cr (III) on the one hand with (b) Oxides of vanadium, chromium (VI), molybdenum, tungsten or scandium other - exist, or the mixed oxides are sulfated or phosphated oxides of group (a) and the mixed oxides have been calcined after their combination at temperatures of 450 to 800 ° C. .

2. The method according to claim 1, characterized in that an aluminum silicate is used as the catalyst of group Ki), in which part of the silicon is replaced by aluminum and / or part of the aluminum by magnesium.

Sign.

3. The method according to claim 1, characterized in that a montmorillonite is used as the catalyst of group Ki).

4. The method according to claim 1, characterized in that the catalyst of group K ₂ ) zeolites of the structure types MFI, MEL, BOG, BEA, EMT; MOR, FAU, MTW, LTL, NES, CON or MCM 22 are used.

5. The method according to claim 1, characterized in that the catalyst used in the group K ₂ ) 12-ring zeolites of the structure type BETA, Y, EMT or mordenite or 10-ring zeolites of the pentasil type.

6. The method according to claim 1, characterized in that superacid mixed oxides are used as the catalyst of group K ₃ ).

7. The method according to claim 1, characterized in that a catalyst from group K ₃ ) is used in which the molar ratio of the oxides of group (a) to group (b) is 70 to 30 to 98 to 2.

8. The method according to claim 1, characterized in that chlorobenzene is reacted with 4-chlorophenylsulfonyl chloride to give 4, 4 '-dichlorophenylsulfone.

9. The method according to claim 1, characterized in that one carries out the reaction at temperatures from 100 to 250 ° C and pressures from normal pressure to 50 bar.

10. The method according to claim 1, characterized in that one carries out the reaction under normal pressure at the boiling point of the reaction mixture.

11. The method according to claim 1, characterized in that one carries out the reaction under autogenous pressure of the reaction mixture.

12. The method according to claim 1, characterized in that one uses the halogenobenzene in excess.

13. The method according to claim 1, characterized in that one chooses a molar ratio of chlorobenzene to 4-chlorophenylsulfonyl chloride from 1 to 100.

14. The method according to claim 1, characterized in that the catalyst is arranged in a fixed bed.

15. The method according to claim 1, characterized in that the reaction is carried out continuously and the excess halobenzene is returned to the reaction.