SU426984A1 - - Google Patents

Description

The invention relates to a process for the simultaneous production of higher. Olefins by catalytic oligomerization of propylene.

Ivbsten opaoba dime (p01b and trimers of propylenemethylpentane and dimethylheptene catalytic olntherization of propylene in the presence oftB | I. and 1 catalytic system - the salt of nickel, phosphorus and alimine haloalkyl (aryl) aluminiunium glyphs, phosphorus phylamine and haloalkyl (aryl).

A disadvantage of the known method is low selectivity for the desired 2-methyl-1-pentene (yield 10%).

In order to simplify the trodass and increase the selectivity for the target products, it is proposed to carry out a recovery, in the presence of a catalyst containing iso-hexyl groups.

To reduce catalyst consumption, 2,4-aimethyl-1-h0pten is usually distilled from the catalyst under a vacuum at a temperature not higher than .110 ° C.

A scheme of the process of olitherization of propylene according to the proposed method is shown in the drawing. In the apparatus / suspension of alum. And | N. of a bulk powder in 2-1 methyl-1-pentenium with the addition of an activator, for example, small amounts of aluminum aluminum or alkyl halide, is added to the acid 2, 2-Meth. Il-1penten and serves hydrogen. Reaction mixture

It is passed through a centrifuge 3 to remove unreacted aluminum and the resulting solution of the organoaluminum compound in propylene dimer (catalizer) is fed to

the mixer 4 is mixed with sawn wood, and then through the heater 5 is introduced into the tubular reactor 6, 1 napr, and a coil immersed in a boiling organic coolant. The reaction mixture from the reactor is throttled.

to the 7 "olon distillate, where the propylene dimer, together with, unreacted propylene, is separated from the catalyst. Part of the cube residue from column 7 is returned to the oligomer to mixer 4, and another part, for example, to the separation of propylene trimer to column 8. The overhead stream from column 7 is fed to column 9, where unreacted propylene and other light boils hydrocarbons are separated from the propylene dimer. Vat

the residue from this column is sent to distillation column 10, and the overhead stream to kolo. H | Well and. From the top of the column L, propylene is taken and sent for oligomerization to mixer 4, from the column / 7

1product waste is removed (water-boiling Cz-SB carbon steel. In coloin 10, propylene dimer is rectified to obtain concentrated 2-methyl-1-pentene, which is taken as top product.

the residue from the column / f / containing hexenes,

heavier hydrocarbons and some amount of catalyst are connected to the stream directed to column 8.

In the column-8, the propylene trimer, together with a small amount of lighter carbohydrate-10-Sb-Cd, distillate the 1OT1 catalyst under a vacuum and temperature, the structure in the column is not (110 ° C). The bottom residue from this column B1031 is rectified and oligomeri: 3a1c 4) A small part of the bottom residue is withdrawn as a production waste, a small amount of fresh catalyst is added to the mixer 4, from a centrifuge 3. Top; from the COLUMN 8 is sent to column 1; 2 to distill lightly boiling hydrocarbons. - Cd from trimer lropilen.a. Upper Bogan and Returned from the column 12 to the column 10 to isolate additional amounts of 2-methyl-, 1-pentene, and the bottoms residue from the column JQ are fed to the column .13 a clear rectification for the separation of the condensed 2,4-dimethyl-, 1- (ge1Ptena. Cn.nolonna 13 is withdrawn | 2,4-dimethyl-1-heptane, and from the cube in the form of waste - other Cd-carbonvodorada.

Example 1. 3.5 kg of aluminum cloudberries, 30 kg of 2-methyl-1-Å; pentene and 2 / рии of tri-13-butyl-aluminum are loaded into the reactor with a stirrer and hydrogen is introduced to a pressure of 60 atm and the reaction is carried out at 130 ° C for 14 hours dilute the content of the reactor with 2-methyl-1-pentene and centrifuged followed by settling to remove unreacted aluminum. 228 l of a solution of an aluminum-organic compound in H-methyl 1-pentene with a concentration of 36.8 g 1 l (calculated as aluminum) are obtained.

The propylene oligomerization is carried out in a 12-liter flow-type reactor (pipe made of stainless steel, length 15 m, internal diameter 4: 8 mm) equipped with an electric heater of the initial propylene mixture with a catalyst to the reaction temperature and jacket. They are served with a transformer: matorny oil to remove heat, exuding us, and its reaction.

Technical liquid propylene (concentration 98-99%) was continuously introduced into the reactor at a rate of 6 l / h, CKopiOCTb catalyst feed 4 l / h, reaction temperature 195-300 ° C, pressure 200 atm. In 57 hours, 450 l of the reaction mixture is obtained, which is distilled at a packed tower with an efficiency of 1.0 t. with reflux number -1. 160 kg of dimers of propylene are recovered, containing 84.1 IPS. % 2 -methyl-1-pentene, 7.6 wt. % Hexea, 8.2 wt. % | 2-methylpentane and 0.1 weight. % propylene. The bottom residue after isolation of the dimer is reused for carrying out ol.omerization of propylene.

For 17 CYCLES of catalyst reuse, 2400 kg of propylene dimer are obtained, containing 86% of i2-methyl-1-pentene, 455 l of a slaughter residue, preserving catalytic activity in the oligomerization of propylene. Additional rectification of dimer-syrtsa on a column with an efficiency of 25 tons. 95-99%, 2-1methyl-1-penten are obtained.

The bottom residue is distilled under vacuum on a column with an efficiency of 10 mt. at

a residual pressure of 70–95 mm and a temperature in the cube of 85–110 ° C, 82 l of propylene oligomers with a specific gravity of 0.725 kg / l are distilled off, which iHO according to GLC data contain 53.5% of 2,4-dimethyl-1-heptene ( the rest is Cg-Cg hydrocarbons). With a clear rectification of oligomers on the column with an efficiency of 60 tons. fractions, the characteristics of which are listed in the table, are isolated, and 20 kg of 93.5% of the total 2,4-dimethyl1-heptene is obtained.

The remaining bottoms, which can be used as a catalyst for the propylene oligomerization, are diluted with 2-methyl-1-penta. To the aluminum content.

30 g / l and continuously served with propylene in the reactor, the wire experience, as described above, for 90 hours. After distillation of the resulting reaction mixture, an additional 150 kg of propylene dimer is isolated. Example; 2. A pumping autoclave with a capacity of 200 ml is entrained in a stream of nitrogen with 55 ml of catalyst prepared as in Example 1 and 70 g of propylene and heated for 1.5 hours at 270 ° C. Initial pressure is 84 atm, kopeknoe is 40 atm. The reaction products are discharged from the autoclave. And the propylene dimer is distilled off on a distillation column, as a fraction 55-65 ° C. The bottom residue is analyzed for Cd hydrocarbons by decomposing the organo-aluminum compound with water, followed by chromatography of the hydrocarbon layer with n-decane added as standard column. (length 6 m, inner diameter 4 mm), filled with polyethylene glass with YuOOO column (15% on the ae. brick of brick), at a column temperature of 80 ° C and carrier gas velocity (. hydrogen) 100.

Based on the reacted propylene, the yield of propylene dimer is 69.5 wt. %, propylene trimer 30.5 wt. % Conversion proplle to 62.3%. The content of 2-methyl-1-pentene in the dimer is 70.4%, the content of 2,4-dimethyl-1-heptene in the trimer is 50.0%.

The subject “Zobrete.ni

Claims (2)

1, a method for producing 2-methyl-1-, pbntbna, and 2,4-dimethyl-1-heptene by oligomeric, isopropyl propylene to present an aluminum trading catalyst followed by isolation of the products, differing in that , in order to simplify the process and increase the selectivity for the desired products, the process is carried out in the presence of a catalyst containing isohexyl groups. 2. A method according to claim I, characterized in that, in order to reduce catalyst consumption, 2,4-dimethyl-1-heptene is distilled from the catalyst under vacuum at a temperature not higher than 110 ° C. 1 L / J