SU954382A1 - Method of producing alkylnaphtalines - Google Patents

Description

The invention relates to the chemistry of aromatic hydrocarbons, more specifically to a method for producing elkilnaphthalenes of the general formula Q, (jH-, R, where C is CpH ,,, C (, 13, which are used as a raw material in the preparation of dyes, surfactants, lubricant additives and in other areas.

A known method of producing isopropyl naphthalene by alkylation of naphthalene with propylene in an organic solvent medium in the presence of a catalyst is complex A 1 C 1 with diisopropyl naphthalene, taken in an amount of 0.5-0.8% on A 1 C 1 c. The yield of the target product reaches 97% U.

The disadvantages of this method are the considerable consumption of the catalyst that is not regenerated, the difficulty of preparation, the corrosion of the apparatus and the need to wash the obtained target product, resulting in its loss and the formation of harmful wastewater.

The closest to the proposed technical essence is the method of producing alkyl naphthalenes by alkylation of naphthalene with olefins containing from b to 8 carbon atoms in the presence at 2025 ° C and a naphthalene to olefin ratio of 1: 1.5. The yield of the target product reaches 60% 2.

This method is characterized by a low yield of the target products, the presence of byproducts of sulfonation, the need for washing the obtained alkylate, high consumption of the catalyst and its non-recoverability.

The purpose of the invention is to simplify the process technology by reducing gum formation, catalyst consumption and eliminating leaching of alkylation products.

This goal is achieved by alkylation of naphthalene with olefins in the presence of an aluminosilicate catalyst containing 140-220 ° C and a molar ratio of naphthalene to olefin from 1: 1 to 5: 1. The yield of alkylnaphthalenes reaches 85%, and the selectivity is up to 90%.

five

The following olefins were used for the alkylation of naphthalene: decene-1, tetradecene-1, hexadecene-1, and tetracosene-1.

industrial aluminosilicate zeolite catalysts of the brand CEOKAR2, and LShNTs-3, designed for the cracking of petroleum fractions.

According to TU 38 101438-77 used catalysts have the following composition and properties (tab. 1)

Appearance

Bulk density, g / cm

Content of target fraction 2.5-5 mm%, not less

Content of whole and mechanical durable balls,%, not less

Stable activity on gasoline output,

The catalysts used are easily regenerated, do not lose their activity after repeated use, provide a high yield (up to 85%) of alkyl naphthalenes, and the resulting alkylate does not need to be pre-washed with water. The process is carried out at 140-220 ° C, the molar ratio of naphthalene to olefins is 1: 15: 1, the amount of catalyst is $ 102% by weight of the initial components, the contact is 2-4 hours.

Example. A mixture of 38.4 g of naphthalene and 10 g of catalyst in a flask with reflux is heated to. 140 ° C and with constant stirring are added over 3 hours, 22.4 g of hexadecene-1 (molar ratio of naphthalene to hexadecene-1 is 3: 1), after which the mixture is stirred at this temperature for another 1 hour. At the end, the alkylate is dissolved in benzene, Table 1

Porcelain Balls 0.64-0.70 0.62-0.70

94.0

94.0 75.0 86.0

SALT catalyst and after distillation of benzene is subjected to distillation in a vacuum. Get 56 g of the alkylate of the following composition, wt.%: Naphthalene 55,9; Hexalecen-1 24.1; monohexadecylnaphthalene 16.6; di- and polyalkylnaphthalenes 1.7; loss 1.7. The yield and selectivity of monohexadecylnaphthalenes are 27.5 and 90.7%, and the conversion of olefin is 37.5%.

PRI mme R 2. Analogously to example 1, but at 160 ° C, receive 58.5 g of alkylate of the following composition, wt.%: Naphthalene 52.6; hexadecene-1,15, O; monohexadecylnaphthalene 26.1; di- and polyalkylnaphthalenes 5.0; loss of 1.3. You; {od and the selectivity of monohexadecylnaphthalene is 43.5 and 84%, the conversion of olefin is 60.7%.

Talin 49,9-f Hexadecene-1 7.5; monohexadecylnaphthalene 36.3; di- and polyalkylnaphthalenes 3.9; loss of 2.4, entry and selectivity of monohexadecylnaphthalene is 60.8% and 91.1% conversion of olefin is 80.8%.

Example4. 33.4 g (0.3 mol) of naphthalene and 10 g of catalyst CEOKAR-2 are loaded into a stirred reactor equipped with a reflux condenser and a thermometer. The mixture is heated to 200 ° C and hexadecene is fed for 2 hours, 4 g (0.1 mol) (naphthalene: hexadecene-1 molar ratio 3: 1). After feeding hexadecene-1, the reaction mixture was additionally stirred for 1 h at the same reaction temperature, after which the hydrocarbon layer was subjected to distillation in vacuo without washing with water to isolate individual fractions. The yield of monohexadecylnaphthalene, counted as hexadecene-1, taken and reacted. is 81.0 and 84.8%, respectively. The output of polyhexadecylnaphthalene from the calculation of dihexadecylnaphthalene 13, 9% of theoretical. Conversion of hexadecene-1 94.6%, the selectivity of the reaction on monohexadecylnaphthalene 87,71.

PRI me R 5. Analogously to example 1, but at 220 ° C, get 59.6 g of alkylate, of the following composition, wt.%: Naphthalene 43,6; hexadecene-1 0,8; monohexadecylnaphthalene 46.2, di- and polyalkylnaphthalenes 8.4; loss of 1.0. The yield and selectivity of monohexadecylnaphthalene are 78.1 and 84.6% olefin conversion is 97.7%. -

Example 6: Analogously to Example 4, but with a molar ratio of naphthalene to hexadecene-1: 5: 1, 85 g of alkylate are obtained, whose composition is as follows, wt.%: Naphthalene, 61.1, hexadecene-1: 1.8; monohexalecylnaphthalene 32.4; di- and polyalkylnaphthalenes 3.5; loss 1.2. The yield and selectivity of monohexadecylnaphthalene are 78.1 and 90.1%. Olefin conversion rate 93.3%.

Example 7. Analogously to Example 4, but with a molar ratio of naphthalene to hexadecene-1-2: 1, 46.6 g of alkylate are obtained, whose composition is as follows, wt%: naphthalene 27.9 hexadecene-1 2.1; monohexadecylnaphthalene 51.5; di- and polyalkylnaphthalenes 16.1; loss of 2.4. Under these conditions, the yield and selectivity of monohexadecylnaphthalene are 68.1 and 76.2%, the conversion of olefin is 95.5%,

Example B. In analogy to Example 4, but with a molar ratio of naphthalene and hexadecene-1-1: 1, 33.5 g of alkylate are obtained, the composition of which is the following, weight 1: naphthalene 8.9;

hexadecene-1 7.5; monohexadecylnaf; talin 49.3; di- and polyalkylnaphthalene 31.3; loss of 3.0. Under these conditions, the yield and selectivity of monohexadecylnaphthalene is 46.8 and 61.1% of the olefin conversion is 68.8%.

Example 9. Analogously to Example 4 with the supply of hexadecene over. 12 h receive 59.4 g of alkylate, the composition of which is the following, wt.%: Naphthalene

0 44.6; hexadecene-1 3.4; monohexadecylnaphthalene 42.1; di- and polyalkyl-, naphthalenes 8.4; pot eri 1.5.

PRI me R 10. Analogously to Example 4, when Hexadecene-1 is fed in for 1 hour, 58.8 g of alkylate are obtained, the composition of which is as follows, wt.%: Naphthalene 45.9; hexadecene-1 3.6; monoGe-sadzylnaphthalene 40.8; di- and polyalkylnaphthalenes 6.8; loss of 2.9, Yield and selectivity of monohexade0 cilnaphthalene are 68.1 and 83.3%, conversion of olefin to 90.7%.

PRI me R 11. Analogously to example 4, but with the amount of catalyst 5 g, get 59.2 g of alkylate, the composition of which follows, wt.%: Naphthalene 45,9; hexadecene 15.1; monohexadecylnaphthalene 40.5; di- and polyalkylnaphthalenes 6.8; losses1, 7. Under these conditions, the yield and selectivity of monohexadecylnaphthalene are 68.1 and 85.7%, and the conversion of olefin is 86.6%.

Example12. The process is carried out analogously to example 4, using naph5 talin, 33.4 g (0.3 mol), decene-1. -14 g (0.1 mol), catalyst ЦЕОКАР-2 10 g, at. The yield of monodecylnaphthalene, counted on taken and reacted Decene-1, was 77.9 and 83.9%, respectively. The output of polydecylnaphthalene from the calculation of didecylnaphthalene 18, C%.

Conversion of mission-192, 8%, the selectivity of the reaction for monodecylnaphthali5 is 84.6%.

Example 13. The process is carried out analogously to example 12, but using the catalyst AShNTs-3. The yield of monodecylnaphthalene, counting at the BREAK 0 and the reacted decene-1, is 73.1 and 85.2%, respectively. The output of polydecylnaphthalene from the calculation of didecylnaphthalene 14.7%. Conversion of decene- 185, 7%, the selectivity of the reaction of 5 monodecylnaphthalene in each 86.7%.

PRI me R 14. The process is carried out analogously to example 4. The naphthalene is 38.4 g (0.3 mol), teradecene-1

19.6 g 0.1 mol, catalyst

ZEOKAR-2 10 g. The yield of monotetradecylnaphthalene, calculated on the taken and reacted tetradecene-1, is 78.4 and 83.3%, respectively. The deduction of tetralecylnaphthalene is 14.6% of the theoretical. Conversion of tetradecene-1 94.4%, the selectivity of the reaction on monotetradecylnaphthalene 86.9%. PRI me R 15. The process is carried out similarly to Example 4. Naphthalene, 38.4 g (0.3 mol), tetracosoene-1 (33.6 g (0.1 mol), and CETOCAR-2 catalysts, 10 g The yield of monotetracosylnaphthalene, calculated on the reacted tetracosen-1, was 56.0 and 87.2%, respectively. The polytetracosylnaphthalene yield was calculated as 10% of the theoretical ditetracosylnaphthalene. 86.6%. The physical constants of the synthesized alkylnaphthalenes are shown in Table 2.