SU1165454A1 - Catalyst for obtaining diarylmethane - Google Patents

Abstract

CATALYST FOR PREPARING DIARYLMETHANES by condensation of aromatic hydrocarbons with formaldehyde, including mineral acid and water, characterized in that, in order to increase the activity and selectivity of the catalyst, it contains phosphoric acid as an inorganic acid and additionally an organic additive, which is the product of the interaction of phosphoric acid with organic reagents - formaldehyde and a mixture containing diarylmethanes, triaryldimethanes and tetraaryltrimethanes, corresponding to the initial ar matic hydrocarbon volume sootnoschenii phosphoric acid and organic reagents

Description

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The invention relates to catalysts for the preparation of diarylmethanes, used as heat carriers, stabilizers of polymers, and also a raw material for the production of multi-nuclear aromatic hydrocarbons.

The purpose of the invention is to increase the activity and selectivity of the catalyst.

The organic additive is the product of the interaction of phosphoric acid with formaldehyde and a mixture containing diarylmethanes, triaryldimethanes and tetraaryltrimethanes, preferably in a 4: 2: 1 molar ratio, in composition is a hydrocarbon mass containing also oxygen and phosphorus.

The composition and structure of the substances involved in this complex product are determined by the conditions of synthesis of the additive, mainly by the ratio of reactants and catalyst, the duration of contact, the presence of impurities in formalin and their quantity, but when these conditions are observed, experience and experience are reproduced; It is not possible to indicate their characteristics as for individual substances, since they cannot be isolated in a pure form and, even more so, divided into components.

Benzene, toluene or other aromatic hydrocarbons and aqueous, for example, 37 ° / o-formal formalin or more concentrated formaldehyde are used as raw materials for the preparation of diarylmethanes.

The installation for the synthesis of diarylmethanes consists of a reactor with an efficient blender, connected to the separator, raw materials tanks for toluene and formalin, and a cooler for cooling the alkylate. From raw materials tanks, toluene and 3/3 / aqueous formalin are continuously fed to the reactor in a selected molar ratio. An emulsion consisting of alkylate, unconverted aromatic hydrocarbon and catalyst is continuously removed from the solution into the separator.

In the separator, the emulsion splits into a lower catalyst layer, which is continuously returned to the reactor during the cycle, and the alkylate. Alkylate passes through the refrigerator, then enters the silk cleaning and drying. The duration of the reaction cycle is 2-12 hours (or a continuous process).

Example 1 (for comparison). Experience in the condensation of toluene with formaldehyde is carried out at a mass ratio of toluene and phosphoric acid of 1: 0.75. The temperature in the reactor is 100 ° C. The molar ratio of toluene and formaldehyde is 8: 1. The initial concentration of Nero is 97 wt.%.

100 g of toluene (1.1 mol), 75 g (0.76 mol) of phosphoric acid, 8 g of formaldehyde in the form of

37% aqueous solution. With intensive transfer, the mixture is heated to 100 ° C, after which formalin and toluene are introduced at a constant rate for 3 hours. The catalyst layer is recycled. After the end of the supply of formalin and hydrocarbon, the flask is cooled, the hydrocarbon layer is separated from the acidic one, neutralized with a 10 / NaOH solution, and after washing with water and drying, excess toluene is distilled off. The ditolylmethane fraction is analyzed by chromatography. Receive, g: ditolylmethane (DTM) 32,7; toluene 57.7; resin 1.4; HzRO4 concentration of 63 wt./about 103,13. The yield of DTM on formaldehyde 64, 5 toluene 89.0 wt.%.

The composition of the ditolylmethane fraction, May. %:

Ditolylmethane93,3

Resins (deep condensation products) 6.7 Example 2. Synthesis of DTM is carried out using a catalyst of the following composition, May. %:

NzRO497,0

Organic Supplement0.10

5 Water2.90

The organic additive is the product of the interaction of phosphoric acid with organic reagents, formalin and a mixture containing ditolylmethane,

Q tritolyl dimethane and tetratolyl trimethane, preferably in a molar ratio of 4: 2: 1, obtained with a volume ratio of phosphoric acid and organic reagents of 3: 1 and a molar ratio of a mixture of di- and polyarylmethanes and formalin 2: 1.

The remaining reaction conditions are similar to example 1. The yield of DTM on formaldehyde is 66.0, on toluene, 90 wt.%.

The composition of the ditolylmethane fraction, May. %:

0 Ditolylmethane94,9

Resins5.1

Take, g: Receive, g:

Toluene100.0 Toluene58.1

Formaldehyde (water

 solution) 8.0 (21) DTM34.0

Catalyst 75.0 Resin1,5

Catalyst 101.0 Losses1.4

Composition of waste in the catalyst process, May. %:

NzRO464,0

Organic Supplement7.1

Water28,9

Example 3. Experience in producing DTM is carried out under the conditions of Example 1, but a catalyst of the following composition, May, is used. %:

НзР0489,0

Organic Supplement8.0

Water3.0

The organic additive is a reaction product obtained with a volume ratio of HjPO-i and organic reagents of 3: 1 and a molar ratio of a mixture of di- and polyarylmethanes and formalin 2: 1.

The output of DTM on formaldehyde 74, on toluene 95 wt.%: The composition of the ditolylmethane fraction, wt.%:

Ditolylmethane 96.3

Resins3.7

Take, g: Receive, g:

Toluene100 Toluene57.7

Formalde-DTM36,7

guide (water Resin1,4

solution) 8 (21)

Catalyst 75 Catalyst 99.1 Loss 1.1

The composition of the spent catalyst, w / o:

Phosphoric acid63,0

Organic Supplement10.0

Water27.0

Example 4. Obtaining ditolylmethane lead with the use of a catalyst of the following composition, May. %:

NzRO484,9

Organic Supplement 12.0

Water 3.1

The remaining conditions are similar to example 1.

The organic additive is a reaction product obtained with a volume ratio of HsRO and organic reagents of 4: 1 and a molar ratio of a mixture of di- and polyarylmethanes and formalin 3: 1.

The yield of DTM on formaldehyde is 64.9, on toluene 90% by weight.

The composition of the spent catalyst, May. %:

NzRO460,0

Organic Supplement15.0

Water25.0

The composition of the ditolylmethane fraction, May. %:

Ditolylmethane 95,8

Resins4,2

Example 5. Experience in obtaining dicumyl methane (DkumM) from cumene and formaldehyde is carried out in the presence of a catalyst according to example 3 at 140 ° C, the mass ratio of cumene and phosphoric acid is 1.0: 0.75 and the molar ratio of cumene and formaldehyde is 8: 1 .

The organic additive is obtained at a volume ratio of H3DD and organic reagents of 3: 1 and a molar ratio of a mixture of di- and polyarylmethanes and formalin 2: 1.

The output Dcum for formaldehyde 68, cumene 85 wt./o.

The composition of the spent in the catalyst process, May. %:

Hsr461

Organic Supplement13

Water26

The composition of dicumylmethane fraction, May. %:

Dicumylmethane 94,6

Resins5.4

Take, g: Receive, g:

 Kumol100 Kumol47,0

formaldehyde (water solution) 8 (21) Dicumylmethane 45.5

Catalyst 100.0

0 Catalyst 75Smola1,7

Loss1,8

Example 6. Experience in preparing diphenylmethane (DFM) from benzene and formaldehyde is carried out in the presence of the catalyst of example 3 at 75 ° C, the weight ratio of benzene and catalyst is 1: 0.75, and the molar ratio of benzene and formaldehyde is 8: 1. Output DFM on formaldehyde 60, benzene 85 wt.%:

The catalyst contains an organic do0 bank, obtained with a volume ratio of HzPO4 and organic reagents of 3: 1 and a molar ratio of a mixture of di- and polyarylmethanes and formaldehyde 2; 1.

The composition of the spent in the process of catalyst, wt.%:

5 NzRO470,4

Organic Supplement9.6

Water 20,0

The composition of the diphenylmethane fraction, May. %:

Diphenylmethane 95.1

Resins (polycondensation products) 4.9

Take, g: Receive, g:

Benzene100Benzene68,9

Formaldehyde (water 5)) 8 (21) Diphenylmethane 26.8

Catalyst 98.3

Catalyst 75Smola1,0

Loss of 1.0

Example 7. The experiment on the production of dicylyl0 methane (DKM) from g-keilol and formaldehyde is carried out in the inactivation of the catalyst according to example 3 at 130 ° C, and the ratio of g-keilol and catalyst is 1: 0.75 and the molar ratio. "- xylene and formaldehyde 8: 1. five

The catalyst contains an organic additive obtained by the interaction of HzRO4 e with an organic reagent in a volume ratio of 4: 1 and at a molar ratio of

f. emei di- and polyarylmethanes and formalin

3: 1.

The output of DCM on formaldehyde 70, on l-keilol 80 may.%.

The composition of the spent in the process of catalyst lysator, wt.%:

HdPO463,0

Organic Supplement9.0

Water28.0

Example 8. Experience in obtaining dipseudocumilmethane (DpkM) from pseudocumene and formaldehyde is carried out in the presence of the catalyst of example 3 at 140 ° C, the mass ratio of pseudocumene and phosphoric acid is 1: 0.75 and the molar ratio of pseudocumene and formaldehyde is 8: 1.

The catalyst contains an organic additive obtained by the interaction of HzRO4 with organic reagents in a volume ratio of 3: 1 and at a molar ratio of a mixture of di- and polyarylmethanes and formalin 2: 1.

The output of DPM on formaldehyde 69, pseudocumene 84 wt./o.

Composition of waste

in the process of catalyst, May. %:

NZR O460

Organic Supplement14

Water26

Fractional Composition of Dipsevdokumilmetanovoy tion, wt. ° / o: Dipsevdokumilmetan94, 8

Resins (polycondensation products) 5.2

Take, get,

Pseudoku Psevdokumol

46.0

100 mole Dipsevdoku Formalde46, 5 guide (aqueous milmetai solution) 8 (21)

solution) catalyst

101 1.5 1.0

Resin

75

Loss Catalyst

Thus, the proposed catalyst has an increased activity and selectivity, the yield of the target product increases by 8-200 / 0 while reducing the yield of by-products by 50-80 rel. ° / o.

Claims (1)

A catalyst for the production of diarylmethanes by condensation of aromatic hydrocarbons with formaldehyde, including mineral acid and water, characterized in that, in order to increase the activity and selectivity of the catalyst, it contains phosphoric acid and an additional organic additive, which is a product of the interaction of phosphoric acid with organic reagents - formaldehyde and a mixture containing diarylmethanes, triaryldimethanes and tetraaryl trimethanes corresponding to the starting aroma eskomu hydrocarbon in a volume ratio of phosphoric acid and organic reagents (3-4): 1 mole ratio mixture of diarylmethane, triarildimetanov tetraariltrimetanov and formaldehyde (2-3): 1 Zhaniya components Phosphoric acid Organic additive Water at the following sodermas.%: 84.9—97.0 0.1 - 12.0 Else