SU1211249A1 - Device for oligomerization of ethylene to higher alpha-olefins - Google Patents

Description

one

The invention relates to the technique of oligomerization of ethylene to higher alpha-olefins under the action of a catalytic system consisting of an organoaluminum compound and a compound of the predose metal, and can be used in industry for creating production of higher alpha-olefins, as well as in the processes of producing alkyl aromatic compounds synthetic oils based on ethylene oligomerization.

The aim of the invention is to increase the economics of the process by increasing the yield of oligomers, reducing the loss of olefins, reducing the yield of olefins C, reducing operating costs, and improving the quality of alpha-olefins.

The drawing shows a schematic diagram of the installation of ethylene oligomerization.

I

The installation works as follows:

at once.

The catalyst in the solvent (toluene) from the tank 1 through the pipeline 2 is fed to the lower part of the reactor 3. It is also continuously circulating through the apparatus system 3 cooled ethylene through the pipeline 8. The pressure in the reactor 3 is maintained at 20-30 atm, temperature 80-90 , ethylene velocity in the free section of 0.03-0.1 m / s. Saturated with olefin vapors and ethylene solvent from the top of reactor 3 through line 9 enters the first water-cooled refrigerator-condenser 4. In the refrigerator 4, the solvent is separated, which is returned to the reactor 3 via line 10. Solvent-free ethylene with olefin vapors. fed through line 11 to the cooler-condenser 5 cooled with brine.

After separation in the cooler-condenser 5, the gas, combined with the fresh portion of ethylene fed through line 12, enters the inlet of the circulation compressor 6 and, cooled down in the heat exchanger 7, returns through line 8 to the reactor 3. Condensed condenser 5 in the refrigerator 5 C4 olefins -C5 is supplied through line 12 to feed rectification column 13.

211

ten

15

20

25

thirty

35

40

45

50

55

2492.

Liquid oligomerization products from the reactor 3 are supplied via conduit 14 to apparatus 15, where at 70-80 ° C and a pressure of 2 atm, the catalyst is deactivated by a deactivating agent (aqueous alkali solution, acid, water, ammonia, etc.) fed through the pipeline. sixteen.

The resulting mixture is filtered at 50-60 ° C from the solid products on filter 17, where it is fed through line 18, washed with water in apparatus 19, and separated into fractions in rectification column 13, where it is fed through line

20. The solvent separated from the reaction products after purification returns to the reaction by pipeline

21, where a fresh portion of the catalyst is fed through line 22. Solid precipitate from the filter 17 is withdrawn through line 23.

The invention is illustrated by the following examples.

Example 1. Toluene from the tank 1 is fed to the lower part of the reactor 3. This is continuously fed with ethanol cooled down through the apparatus system 3-7 and the catalytic complex from the reactor 3. The pressure in the reactor 3 is maintained at 20-30 atm, the temperature is 80-, the contact time is 1 h, the rate of ethylene in the free section of 0.03-0.1 m / s. Saturated with olefin vapors and ethylene solvent from the top of reactor 3 enters the first refrigerator 4, where the temperature of the atmosphere is 18-20 C. In the refrigerator 4, the solvent is separated, which returns to reactor 3. Ethylene with olefins vapor is fed to the refrigerator-condenser 5, where the temperature is 10-12 s, the pressure is 2030 atm.

one

At the outlet of the apparatus 5, the gas phase enters the circulating circuit, and the liquid enters the column 13. At the outlet of both streams, throttling devices are installed.

Liquid oligomerization products from the reactor 3 enter the apparatus 15, where at 70-80 ° C and pressure

2 atm, the catalyst is deactivated with an alkali solution, then passed through the filter 17, washed with water in the apparatus 19 and fed

The content of linear alpha-olefins, wt.%

99.1 99.0 98.3 97.5 96.6 95.5 94.1 93.2 90.5

. . 1060 99.3

108 .100

. .

4.9 0.3.

.

,

106073.9

4.0 8.7 2.9 6.3

39.1 83.0 FROM 99.4 1301.

4.3 0.4 20013.9

3.0 0, Z 231.7

Total 1064.9 "00 toa too 46.0 100 113.7 100 1433 I oo

A "CjH, CI,

Toluene 130 60.6 1130 37.4

Olefins.

30 16.4 40 1.9

Opefins

With, and vym 6, 3,3 800 39,9

Solid product

13.0 0.8 13.0 100

: Total 186 100 2003 100 13.0 100 1569.9 100 127.6 100

h - -.

Table i

Table e

Prodotv ks

803.9 31.2 7.0 3.3

120.6 94.3 776.0 48.8

rectification into apparatus 13. A solvent separated from the reaction products is returned to recycling.

The material balance of the main process streams is given in Table 1 in Table 2 - the composition, distribution and quality of products.

Example 2. The process is carried out according to the scheme described in example 1, but with the following apparatus mode: temperature 20-40 s, pressure 20-25 atm.

The material balance of the main process flows is given in table 3, in table 4 - the composition, distribution and quality of products.

Thus, in the proposed installation, the operational performance is improved by reducing

t030 99.S

107,100

5. tS 0,3

T epdmy 1FO- dukt

Total

"035.1 100 107 100 20.35 tOO 905.7 tOO 1340 100

100 85.5 900 51.2

Olefn n, 10 8.5 36 2.0 7 6.0 810 46, g

Olefish C,

10.0 0.6 10 "00

. 117 too 1756 100 10100, 5 "00 123,5.100

211249

the volume of the apparatus of a number of nodes (by 8-10%) by withdrawing the C4-CJ fraction from the oligomerization reactor directly to rectification.

5 Operation of the proposed installation allows reducing the content of light fractions by 30-60%, heavy fractions by 10%. Such a decrease in heavy fractions with

To work the installation by a known method leads to a decrease in the yield of the detergent fraction C, -C, g to 8%. Work on a new technology, in addition, reduces the consumable cost (5 ethylene consumption from 263 to

1137 kg / rj increases the quality of the detergent fractions C, C | g most commonly used in the homogeneity of the C, C | g fractions from 86-94 to 93-96% (in terms of

20 linear olefins).

t in per liter - 1

t03076, and

12.3 2.7

85 900 9V

3.2 0.3 18013.4

2.5 0.3 302.3

Continued on. I

894 53.7 6 4.9 117.5 95.1

770.5 46.3

Indicators

h Cj

Distribution, wt.%

Contents of linear alpha olefins, May. %

3.8 15.3 23.1 19.0 16.3 8.3 7.1 3.0

98.8 98.8 97.9 97.5 96.8 95.0 93.0 92.2 90.0

Table 4

TO)

and

:, 4 | с, б | с, в, с, „and

above

Claims (1)

PLANT FOR OLIGERIZING ETHYLENE TO HIGH O-OLEFINS, including an oligomerization reactor, a separator, a catalyst decomposition column, a polymer separation filter, a washer, and rec-. a casing column, characterized in that, in order to improve operational performance, reduce losses and improve the quality of α-olefins, the reactor is equipped with an additional pipe for withdrawing C ₂ -C ₆ -olefins and solvent from the top of the reactor connected to the refrigerator, which has a solvent return pipe into the reactor and the pipeline for supplying a mixture of C ₂ -C ' -olefins to a condenser cooler, which has a pipe for returning ethylene to the reactor • and a pipeline for supplying a C ₄ -C ₆ -olefins to a distillation column. ^eleven