DE1668937C - Continuous process for the manufacture of o sec butyl phenol - Google Patents

Description

1 2

The invention relates to a continuous process in which the molar ratio of butene to phenol is

for the production of o-sec-butyl-phenol by kata- 0.96. The gaseous mixture is then left in

Lytic alkylation of phenol with η-butene. an absolute pressure of a technical atmosphere

The alkylation of phenols by flowing into a reaction vessel made of quartz, the sphere

with olefins in the liquid phase under pressure is known. 5 is heated to 275 ⁰ C and in which as a catalyst

You can use as catalysts proton-containing sator in a solid layer of 40 cm ³ (17.5 g) of grains

Acids such as phosphoric acid, sulfuric acid, hydrochloric acid, 2 to 3 mm thick from freshly activated y-aluminum

acidic salts or Lewis acids such as oxyd are located. The resulting dwell time

Use aluminum chloride, boron fluoride. This Ka- 2.6 seconds.

catalysts show a number of disadvantages, such as io After the reaction product has cooled down and strong corrosive effect, difficult separation of the separation of the unreacted butene collects of the reaction mixture obtained and especially one per hour 72.5 g of a mixture, the 53.8 Geeinen Lack of selectivity because when they are used, weight percent phenol, 39.4 weight percent o-sec.-mostly Mixtures of positional isomers contain butyl phenol, 2.6 percent by weight p-sec-butyl phenol, will. 15 0.9 percent by weight 2,6-Oi- (sec-buty!) - phenol and

Selective catalysts for ortho-alkylation contains 1.3 percent by weight of 2,4-di- (sec-butyl) -phenol,

of the phenols are the metal phenates, especially those which have a conversion of 35% of the phenol and

Aluminum phenate. These are less corrosive to a molar yield of 85.6% of o- ^ ek.-butyl-

ding, but their separation from the reaction product corresponds to phenol. The composition of the alky-

requires a series of decomposition operations with ao lated product was by gas-liquid-chromato-

Acids and successive washes; graphy noted,

In addition, the acids used here can be used in Example 2
also an undesirable isomerizing effect

to have. Using the same device and

Another group of selective catalysts 35 conducts the same working method as in example t

Form the y-aluminum oxide and certain metal-one over 25 cm ³ y-aluminum oxide-Kalalysator in

oxides such as chromium trioxide, molybdenum trioxide, 35.5 g phenol and 8.51 n-butene (38.7%

Vanadium pentoxide as such or on a carrier butene-1, 33.4% trans-butene-2 and 26.4% cis-butene-2);

made of aluminum oxide, silicates or activated carbon. here the molar ratio of butene to phenol is 0.94.

Although these catalysts are not corrosive 30. The temperature in the reactor is at 260 ⁰ C

act and easily kept out of the reaction mixture, the resulting residence time is

Let them separate by filtration, they show at 2.8 seconds. 44 g of product are obtained per hour,

Alkylation of phenols in the liquid phase Disadvantages, the 49.3% phenol, 45.7% o-sec-butylphenol, 2%

because the reaction only takes place at higher temperatures and p-sck.-butyl-phenol, 1% 2,6-di- (sec-butyl) -phenol

correspondingly increased pressures in the vicinity of 35 and 1.5 percent by weight of 2,4-di- (sec-butyl> phenol

of 100 atm so that the process conditions contain what is a molar conversion of the phenol

are difficult to maintain in the system; also is of 38.9% and a molar yield of 91.2%

a device for working under increased pressure on o-sec-butyl-phenol corresponds,

necessary. . .

According to the method according to the invention for producing 40 B e 1 s ρ 1 e I J

Position of o-sec-butyl-phenol eliminates this one works as in Example 1, but under the

Disadvantages by having the alkylation of the phenol under the following conditions: 14 cm * of catalyst

carries out with η-butene in the vapor phase. Sator, a temperature of 250 ⁰ C and a molar

The continuous process according to the invention applied the ratio of butene to phenol of 1.2; in

For the production of o-sec-butyl-phenol by alky- 45 of the hour, 63 g of phenol and 19.3 g of n-butene are produced

lation of phenol with n-butene in the presence of a used, the residence time is 0.8 seconds. Man

Read arranged catalyst made of y-aluminum thus receives 72.7 g of product per hour, which is the following

Oxide at elevated temperature is characterized by this- Composition: 66% Pheno », 31% o-sec.-

Leichnet that the implementation of n-butene butyl-phenol, 1.1% p-sck.-butyl-phenol, 0.5% 2,6-di-

and phenol in a molar ratio of 0.5 to 2: 1 in the so (sec-butyl) phenol and 0.9 percent by weight of 2,4-di-

Vapor phase at an absolute pressure of 1 to 5 (sec-butyl) -phenol, which leads to a conversion of the Phe-

technical atmospheres and temperatures of nols of 23.3% and a molar yield of

200 to 300 ⁰ C with a residence time of 0.5 to 93.8% o-sec-butyl-phenol corresponds.

10 seconds. · Ι &

After the reaction products have reached the catalyst 55 B e 1 s ρ 1 e I 4

If you have left the shift and cooled down, you work as in Example 1, but under the

borrowed the unreacted butene, which was returned under the following conditions: 45 cm ^{1 of} catalyst

is, and the crude product is distilled to a pure temperature of 224 ° Curd a molar »ratio

o> sec. * to obtain butyl phenol and phenol; last »butene applied to phenol of 1; in the hour

will be used again. 26.7 g of phenol and 6.91 n * butene are used.

In the following some examples of the dwell time are 7 seconds. You get 10

position of u-sec.-Butyi-phenol after the invention * in the hour 31.8 g of product, you the following «To ·

Given according to the procedure: Mmmensctzung has: 58.3% phenol, 35.5% o> tek.

•. 1. "ι _ ι ι Butyl-phenol, 0.6 · /, p-Mk.-Burvl-phenol, 2.1 · /, 2> DI ·

^With * P ^{| el l} H (Mk.-butyl) .phenoi and 1 percent by weight 2,4-DI- In a vaporizing device made of glass, the (sec. <butyl> phenot, which is a conversion of the »Phe>

is heated to 200 to 250 "C, leads continuously nols of 30.7% and a molar yield of

60 g of phenol and 14,711 fluten-2 tons per hour; 86.6% of o> wk. * Butyl «phenot corresponds.

Example 5

The procedure is as in Example I, but under the following conditions: 50 cm * catalyst, a temperature of 290 ^° C. and a molar ratio of butene to phenol of 1.9 are used; 33.2 g of phenol and 16.11 η-butene are used per hour, the residence time is 3.7 seconds. 45.1 g of product with the following composition are thus obtained per hour: 33.6% phenol, 23.6% o-sec-butyl-phenol, 15.1% p-sec-butyl-phenol, 8, l % 2,6-di- (sec-butyl) -phenol, 14.4% 2,4-di- (sec-butyl) -phenol and 3.5 weight percent 2,4, S-tri- (sec. -butyl) -phenol, which corresponds to a conversion of the phenol of 54.4% and a molar yield of 37% of o-sec-butylphenol and of 28.8% of di- and tri- (sec-butylphenol) .

After the effectiveness of the catalyst has decreased, it is placed in a stream of air at 450 to 500 ° C reacquired. ao

The method according to the invention has advantages

Reason for the fact that it is the manufacture of the Q-sec-butyl-phenol with simple technical measures enables, in particular the implementation at allows low pressures and gives good yields. This process gives conversions of 35 to 40% and yields of o-sec-butylphenol of 85 to 92%.

Claims (1)

Claim: Continuous process for the preparation of o-sec-butyl-phenol by alkylation of phenols with η-butene in the presence of a fixed catalyst of γ-aluminum oxide at elevated temperature, characterized in that the reaction of η-butene and phenol in a molar ratio 0.5 to 2: 1 in the vapor phase at an absolute pressure of 1 to 5 technical atmospheres and temperatures of 200 to 300 ⁰ C with a residence time of 0.5 to 10 seconds.