JPS61122230A - Manufacture of mixture of ethylene and butene_1 - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing mixtures of ethylene and butene-1 by selective trimerization of ethylene.

It is known from U.S. Pat. No. 4,133,944 that ethylene copolymers can be obtained using a mixture of ethylene and butene-ILv in situ in a polymerization reactor or in a separate trimerization step. There is.

Selective trimerization of ethylene to butene-1 is known from U.S. Pat. No. 4,245,131. Also, the production of mixtures of ethylene and higher α-olefins using a coil reactor is disclosed in U.S. Pat. No. 3,721,719.
Disclosed in the issue. However, the method of the present invention
It is more selective and provides a higher butene-17 trialkylaluminum ratio, ie, more product per weight of aqueous solution.

The present invention combines ethylene with an excessively diluted trialkylaluminum in a solvent with a concentration of 0.79 to 10.4! A pressure of 5 MPa, preferably 2.17-4.24 ps i g, 20
Temperature of 0° to 325°C, preferably 250° to 280°C, 200:1 to 20,000:1, preferably 4,0
Ethylene and butene were reacted at an ethylene:trialkyl aluminum weight ratio of 00:1 to 8,000:1.
1. The reaction takes place in a vertical reaction zone, and the initial contact of the ethylene with the trialkylaluminum occurs at the lower end of the reaction zone, as the reaction raises the temperature of the reactants to the boiling point of the solvent, whereby the reactants are It evaporates and condenses at the top of the reaction zone at low temperature. The solvents used are inert (hydrocarbon) solvents such as alkanes and alkenes containing 8 to 40 carbon atoms.

This reaction zone is referred to as the ebullated bed reaction zone for purposes of the present invention.

The figure is a schematic diagram illustrating the method of implementing the invention.

In the figure, ethylene gas passes through inlet 10 to preheater 1
2 and then to vertical reactor 14. It promotes the dispersion of F-ethylene gas into the gas diffuser or sparger 16 and improves its contact. Level 18 of a dilute solution of trialkylaluminum in a hydrocarbon solvent is shown. This level is maintained by liquid controller 37, associated control valve 38 and line 36.40.

If desired, a conventional heating device [15] is provided. These include electrical heating tapes, fluid heating coils, revolillers, etc.

The upper end of the vertical reactor 14 is provided with a conventional contact member 20, such as a mesh backing, ceramic ring, or other known contact member.

The mixture of ethylene and butene-1 exits reactor 14 by line 22 where it is cooled by heat exchanger 24.

The F solvent vapor is condensed into the reflux drum 26. The liquid solvent is returned to reactor 14 by line 28.

The pressure within the reactor is maintained within predetermined capacity limits by a pressure controller 31 controlled by a control valve tp.

The mixed product of ethylene and butene-1 flows from drum 26 through line 30 and control valve 32t-to outlet line 34.

The following examples are intended to illustrate the invention.

Example 1゜High purity (99,94)! Chile: y f 2.86MPa
A stainless steel pipe (length 1.37 m) with a diameter of 2.5 cm (0, D-) was injected into the bottom of the reactor through 7 liters of stainless steel at 1.5 t/min (0,32 α/s). Next. 0.4 in pre-made n-tetradecane
A wt% triethylaluminum (φEA) solution was added to the reactor so that the liquid height was maintained at 6.9 mm.

This liquid was then circulated through the supply vessel at a rate of 4 CC/min. Heat the liquid/gas mixture to 277 °C with a controlled heating tape and set it at the top of the reactor'c 7.6
A friend made to regurgitate by mesh backing of cm.

Pass the wet test needle through the Radgas system and remove it from the system.

While analyzing this gas and the 1'EA/solvent recycle using gas chromatography, the degree of TEA catalyst was determined by careful hydrolysis of the solvent portion and subsequent measurement of liberated ethane. Step 30 After a minute, a total of 120.2 F of ethylene was converted (25.7 wt.
~C8 oligomer '1lo0.5F produced friend. The product distribution shown in Table I was obtained.

Table ■ Ethylene 346.0 77.5 Butene-t 95.8 21.5
95.3 Chibuten-2 1.5 0
．． 34 1.5 hexene-11,90,431
,9'Hexene-2 and Hexene-30,230,05
0,2-2-ethyl-1-butene 0.95
0.21 0.9 octene-10,080,
The unit weight ratio of butene-1 produced per t of ftTEA added to 020.08 is 159, and the total t0 is 19.7F.
The conversion product of (section 16, 4) flows into the solvent.

gAl　2～15゜ According to the method of I.11, the results shown in Tables ■ and ■ were obtained.

-! (n Example @ degree pressure ka gas band gas velocity 2 261 2.86 47
0.363 266 2.86
49 0.344 273
2.86 77 0.315
266 2.86 148 0
．． 256 273 2.86 61
0.277 268 2.90
38.6 0.548 255
2.86 37 1.49
260 2.93 39 1.
3210 250 2.86 60.
6 0.7811 250 2.86
59 0.8212 247
2.86 62.7 0.77
13 248 2.93 46
1.14 control 257 2.38 22
9 0.18(1) = Retention time (21 = Product iTr amount: Total weight of effluent gas during the entire operation '1) = Tri(71-butyl) aluminum (T
(replaced with EA) C=n-tetradecene C1o-1= Decene-1 C1o= n-decene Solvent TEA concentration 02H4 conversion Product weight (P) (P)
C,0,1172,3236,I C140,11135,6458,4 C140,28"" 194.5 375.
9C,0,10218,2241,7 C1,0,25172,4335,7 C,0,29(3) 428.6 1307
．． 4C14θ, 27 1187.2 30
39.7C1,0,101702355,8 C-10,13821,34046,3C1oO,12
265,61667,6C1゜0.2
614.3 4720.6C1oO,2
3492,92889,OC engineering, 0.25
156.3 70.6

[Brief explanation of the drawing]

The figure is a schematic diagram showing the application method of the present invention.

Claims (10)

[Claims] (1) Ethylene and trialkylaluminium are mixed in a solvent for the trialkylaluminium in an ebullated bed reaction zone at a pressure of 0.79 to 10.45 MPa, 20
A process for producing butene-1 by dimerizing ethylene with trialkylaluminium, characterized in that the reaction is carried out at a temperature of 0° to 325° C. and an ethylene/trialkylaluminium weight ratio of 200 to 20,000. (2) The solvent is an inert hydrocarbon, and the ethylene/trialkyl aluminum weight ratio is 2,500 to 10,000.
The method according to claim 1. (3) The pressure is 2.17 to 4.24 MPa and the temperature is 25
3. The method according to claim 2, wherein the ethylene/aluminum trialkyl weight ratio is 4,000 to 8,000 at a temperature of 0 DEG to 280 DEG C. (4) The method according to claim 3, wherein the trialkylaluminum is triethylaluminum. (5) The method according to claim 4, wherein the inert hydrocarbon solvent is a hydrocarbon having 8 to 40 carbon atoms. (6) Excess ethylene is diluted with trialkylaluminium in a solvent in a vertical reaction zone of 0.79 to 10.
The reaction is carried out at a pressure of 45 MPa and a temperature of 200° to 325° C. and the solvent is heated to the boiling point at the lower end of the reaction zone and cooled to a temperature below the boiling point at the upper end of the reaction zone. The method described in section. (7) Claim 1, wherein the trialkylaluminum is triethylaluminum, and the ethylene/triethylaluminum weight ratio is 2,500 to 10,000.
The method described in section. (8) The pressure is 2.17 to 4.24 MPa and the temperature is 25
8. The method according to claim 7, wherein the ethylene/triethylaluminum weight ratio is 4,000 to 8,000 at a temperature of 0° to 280°C. (9) Excess ethylene is removed in an ebullated bed reaction zone with a dilute triethylaluminum solution in an inert hydrocarbon solvent at a pressure of 2.17-4.24 MPa, 250°-280° C.
℃ and an ethylene/triethylaluminum weight ratio of 4,500 to 8,000, whereby the solvent is heated by this reaction to the boiling point at the lower end of the reaction zone and to a temperature below the boiling point at the upper end of the reaction zone. A method for producing a mixture consisting of ethylene and mainly butene-1, characterized in that the mixture is cooled to . (10) The method according to claim 9, wherein the inert hydrocarbon solvent is a hydrocarbon having 8 to 40 carbon atoms.