SU213820A1 - METHOD OF OBTAINING OLEFINS - Google Patents

Description

There is a well-known method of producing olefins by dimerization and sodimerization of ethylene and propylene at a temperature of about -100 ° C and a pressure of I-41 atm in a hydrocarbon solvent in the presence of a catalytic system consisting of two metal-containing compounds, one of which has the general formula RxMXyH second P-organic compound Ni in complex with triphenylphosphine, tl. R is a hydrocarbon radical; M - aluminum, gallium, indium, beryllium; X is halogen; X is an integer that varies in the limit from O to valency M; y is an integer equal to the valence of the metal M minus x.

In order to expand the range of available catalysts, a method for producing € 4 - Co olefins by dimerization and sodimerization of ethylene and propylene in a hydrocarbon solvent at a temperature from - 50 to -} - 150 ° C, pressure of 1-25 atm in the presence of a catalytic system, consisting of triphenylphosphine and two metal-containing compounds, one of which has the general formula Rm MHp, r.- R - alkyla or arylalkilya group, M - aluminum, titanium, vanadium, chromium, X - halogen, t - integer, varying from silt to magnitude valines the strength of the metal M, n is an integer equal to the valence of the metal M minus m, the second has the general formula RpMe, where

R is an organic acid residue, an allyl or diclopentadienyl group, or a halogen; Me-, cobalt, iron; p is the valence of the metal Me.

The proposed method allows the dimerization of ethylene to butenes, production to hexenes, the codimerization of ethylene to propylene to pentenes, and ethylene to bougain to g & xyi. Buteiu and penteiu can be used to get divinyl and isoprene by dehydrogenation, and hexenes to obtain diene hydrocarbons by cracking.

Example 1. Dimerization of ethylene. In a glass reactor equipped with a thermometer, a bubbler for supplying gaseous lefin II by external cooling, 50 г of ethylaluminum sesquichloride, 7.5 ml of nickel oleate in benzene with a content of 0.012, are charged with argon in a stream of argon, 50 ml of sodium sesquichloride. g / ml and a solution of tripheiylphosphine in tert-butyltoluene in a molar ratio of RgP: Ni 2: 1 is added. The reactor is placed in a cooling bath and ethylene is passed at a rate of 10 l / h at 20 ° C and atmospheric pressure for 3 hours. Received butenes with a yield of about 80 wt.%, Based on the reacted ethylene, with an ethylene conversion of 48%.

All other conditions being equal, nickel di-tert-butyl benzoate oleate gives a butene yield of 70-75% at conversion of about 40%.

Example 2. Dimerization of propylene. The reaction is carried out in a glass reactor with a shaking device equipped with a pressure gauge, a thermocouple and a cooling jacket. B. reactor under argon atmosphere was charged with 15 ml of Guoeth-butyltoluene, 15 ml of the solution (iso-SlHe) A1C1 in n-heptane with an aluminum content of 0.111 g1 ml, 10 ml of a solution of dig / e-butylbenzoate of cobalt (P) in tert-butyltoluene with a content of 0.0059 g / ml and 0.45 g of triphenylphosphine in 10 ml of 777g-butyltoluene is added. Then, at 25 ° C and stirring, propylene is introduced from a cylinder under a pressure of 6 atm for 1.5 hours. The reaction product is distilled off on a distillation column and analyzed by chromatography. Obtain 24 g of propylene dimer of the following composition, weight. %:

4-Methylpenten-2 (cis-f-trans) 37.1

2-Methylpentene-229.1

n-Hexenes 21,5

2-Methylpentene-19,6

Other olefins2.7

When using other metal-containing compounds as components of the catalytic system, the results are presented in the table.

Example 3. Sodimerization of ethylene. With propylene. The reaction is carried out according to the procedure described in Example 1. 15 ml of tert-butyltoluene, 15 ml of (Izo-C4H9) 2 A1C1, 4.5 ml of a solution of nickel oleate in tert-butyltoluene with a Ni content of 0.01 g / ml and 0.4 g (CbH3). ZP in 10 ml of tert-butyltoluene. Ethylene is simultaneously passed into the reactor at a rate of 2.6 l / h and nropylene at a rate of 5.4 l / h at 20 ° C and 1 atm for 3 hours. Conversion of ethylene about 90%, propylene 55%. The reaction product consists of 10% butenes, 40% penteiov, 30% hexenes and 20%. higher hydrocarbons.

Example 4. In the reactor described in Example 2, 20 LL of tert-butyltoluene, 0.9 ml of TiCU and 15 ml of bis-P-allyl nickel solution in tert-butyltoluene with a nickel content of 0.015 g / ml and 2 g of triphenylphosphine are loaded in a stream of argon. The dimerization of propylene is carried out as indicated in example 2 for 2 hours. A dimer is obtained with a yield of about 30 g of composition close to that of Example 2.

Example 5. The dimerization reaction is carried out in a 1 liter steel reactor, designed for a pressure of 25 atm, equipped with a siphon, a thermocouple pocket, a jacket and an internal coil, to which cooled hydrocarbon is fed from the thermostat. 100 ml of a catalyst solution prepared by mixing 50 ml of diisobutyl aluminum chloride, 50 ml of tert-butyl toluene, 7.5 ml of nickel oleate solution in t / oeth-butyl toluene containing 0,0117 g / ml nickel and 0.77 g are loaded into the reactor in a stream of argon. triphenylphosphine. The reactor is cooled to –50 ° C and 200 ml of liquid nropylene are gradually introduced from a steel burette at such a rate that the temperature in the reactor is maintained at 50 ° C and a pressure of 2 atm. From the reaction products, the propylene dimer is distilled under vacuum into a vial cooled by a mixture of solid carbon dioxide and acetone. The resulting dimer (96 g) and. Has the following composition, wt.%: 2-Methylpentene-263,6

4-Methylpenten-2 (cis + trans) 6.5

n-Hexen 20,9

2-Methylpentene-16,4

Other hexenes2,7

Example 6. The experiment was carried out as described in Example 5. The reaction temperature was held at - | - 40 ° C, pressure 8 atm. Get 83 g of the product of the following composition, wt. %:

2-Methylpentene-250,5

4-Methylpenten-2 (cis- | -trans) 19.8

n-hexenes 23.2

2-Methylpentene-14.3

Other hexenes2,2

Subject invention

The method of producing olefins by dimerization and sodimerization of ethylene and propylene at elevated pressure in a hydrocarbon solvent medium in the presence of a catalytic system consisting of triphenylphosphine and two metal-containing compounds, one of which is the general formula RxMXy, where R is a hydrocarbon radical; M - aluminum, gallium, indium, beryllium; X -

halogen; x is an integer varying from zero to valence M in the limit; y is an integer equal to the valence of M minus x, characterized in that, in order to expand the range of available catalysts, in the first metal-containing component M there may be titanium, vanadium, chromium, and as the second metal-containing component take the compound of the general formula RpMe, where R - organic acid residue, allyl or

cyclopentadienyl group or halogen; Me - nickel, cobalt, iron; p is an integer equal to the value of Me, and the process is carried out at a temperature of from - 50 to + 150 ° C.

Dimerization of propylene in the presence of various catalysts

Table

Note. R-Residue of oleic or di-tert-butylbenzoic acid. - The molar ratio (CdH5) s P to II is 2.