JPS59110629A - Manufacture of linear alpha-olefin using tank growth reactor - 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 production of α-olefins with a carbon skeleton structure free of side chains and terminal unsaturation has been practiced for many years. The advent of the tri-organometallic compounds triethylaluminum and tri-n-butylaluminum led to large-scale commercial production. The first and desired product is CI2-C1 for detergents.
8 α-olefins and 0 lower carbon atom compounds that are CIO+α-olefins for synthetic lubricating oils, i.e. C6-C
8 compounds have recently found use in the polymer field and therefore their recoveries are increasing.

U.S. Pat. No. 4,314,090 provides for the production of increased amounts of 04-CIO alpha-olefins using a long coiled growth reactor, such as the one known from U.S. Pat. No. 2,971,969. The method is described. However, due to longevity, these reactors require approximately 10
:1 olefin:aluminum alkyl ratio is required.

2 to 1 mole of aluminum alkyl by using a tank reactor with a relatively rapid external recirculation rate.
It has been discovered that it is possible to use 6 moles of α-olefin to obtain the desired hexene-1 and octene-1 ratios after displacement reaction comparable to systems using coil reactors. .

Additional advantages of the present invention are reduced amounts of fracture energy and lower capital equipment costs by using a lower proportion of olefins. In fact, no excess olefin is required, thus eliminating costly recycling compaction.

The growth promoting conditions used in the tank reactor are 100-15
A temperature of 115-125°C, a pressure of 1.5-19 MPa, preferably 2.2-10.5 MPa, and a temperature of 15-60 minutes, preferably 30-40 minutes. This is the liquid residence time.

The contents of the growth reaction zone are recycled into the external heat transfer zone at a recirculation rate such that the contents of the reaction zone are completely recycled in a time sufficient to remove the heat of reaction and maintain a substantially constant temperature. can be recirculated. Preferably, this recirculation time is 0
The time is 1 to 60°0 minutes, and the most preferred time is 0.5 to 30 minutes.

A further aspect of the invention is the use of a displacement reaction zone containing a static mixer with 6 to 60 stationary elements to speed up the displacement reaction.

The present invention will be described in more detail with reference to the accompanying drawings.

Referring to the attached drawings, (1) ethylene, propylene or butene which has been appropriately purified to remove moisture and oxygen.
1 is preferably a supply line that supplies ethylene. Reference numeral (12) is a compressor υ in which the lower olefin feed is pressurized to a pressure of about 4.9 MPa. The compressed olefin is then passed from line (14) to line (16).
) where it joins the recycled catalyst from line (18) and passes through the heat exchanger (17), pump (19) and recycle line (21) to the reactor inlet (22).
is circulated.

The pressurized tank or growth reactor (20) is equipped with two gas outlets for unreacted gas, which is passed through the line (25) to the heat exchanger (26) and the line (2).
The combined liquid feed from line (30) and the gas feed from line (28), which are recycled through line (28) to the displacement reaction feed line (60), are thus combined to form the displacement reactor (32). constitutes the supply to. Pressure reducing valves (24, 27) are equipped to maintain high pressure in the reactor (20).

In the displacement reactor (32), the liquid propagation material is reacted with a displacement reaction gas to produce a C4 to C20 propagation alpha-olefin and recover the organometallic catalyst. This reactor (62) is a conventional static mixer.

The contents of the displacement reactor (32) are fed via line (34) to an extraction column (36) where lower olefin-stacked ethylene is slipped from the reaction mixer and removed via outlet (42) and line (48). . Recycle line (
46), condenser (44) and recycle inlet (40)
The system is equipped with a gas tank that removes high-grade gases and returns them as liquid reflux. Line (48) carries the lower olefins to a compressor (50) where the gas is brought back to the appropriate pressure and introduced through line (52) into the recycle line (28).

The bottom fraction from the extraction column (36) is removed from the outlet (6) and sent via line (39) from the inlet (53) to the column (54).
will be introduced in Similar to column (36), higher olefins such as butene gas are stripped via outlet (64), condenser (6) and inlet (62), and passed through line (68).
Butene gas is removed from the tank and sent to the take-off valve (70) and the transfer line (72). If desired, some or most of the butene can be withdrawn from valve (70) and used as an intermediate. The remaining butene is recycled from line (72) to line (48) and reused as a displacement reaction gas.

The liquid bottoms of the butene column (54) are recycled via the outlet (56), the reboiler (58) and the inlet (6). This bottoms fraction is passed from the line (59) to the inlet (74) of the vacuum column (76). where the desired α-olefin (
C4-C20) are separated from the catalyst mixture. This vacuum column (7) has a vacuum line (9) that performs the necessary pressure reduction.
8) is equipped.

The bottom fraction from the vacuum column (76) is withdrawn from the outlet (84) and sent to the reboiler (80) by indication (82).
through the inlet (78) and returned to the tower (76) for circulation.

A portion of the vacuum column bottoms fraction is recycled via line (86) back to the growth reactor (20). The reflux circuit of the vacuum column (76) includes a line (90), a condenser (92) and an inlet (9
4). A barge line (57) is equipped to periodically remove C12 and high molecular weight materials.

The overhead product of the vacuum column is removed from the outlet (88) and sent to a heat exchanger (96) for further separation into the desired alpha-olefins.

According to the present invention, lower olefins such as ethylene after being pressurized to a range of 2.2 to 7.0 MPa have a pressure of 1.5 to 15
．． The olefin is fed to a tank reactor maintained at a pressure of 9 MPa and a temperature of 100° C. to 150° C., where the olefin is converted into a trialkylaluminum growth material, i.e. triethylaluminum or tributylaluminum, preferably a mixture thereof (high content of triethylaluminum).
I was forced to react. This reactor can contain 5-90% of reaction reagent.
It is of a size that allows contact for 30 to 40 minutes, preferably 30 to 40 minutes. Due to the exothermic reaction, the pressurized tank reactor is equipped with an external heat transfer device to keep the content of the reaction zone between 0.25 and 5.
Complete recirculation is achieved within a time period of preferably 0.5 to 3 minutes. The product withdrawn from the growth reactor is cooled to ensure that the growth products and unreacted growth material remain in liquid form, while unreacted olefins or ethylene are separated and recycled into the growth reaction as olefins. It can be returned to the container.

The cooled liquid growth product and unreacted growth material are then treated with a displacing gas such as a mixture of olefins of 2 to 4 carbon atoms, preferably ethylene and butene-1, to displace the feed material in less than 6 seconds. Mix in a static mixer displacement reactor of the same size. The displacement gas is preheated so that its temperature when mixed with the liquid feed stream in the displacement reactor is 200°C.
The temperature is such that it is in the range of 250°C to 280°C, preferably 250°C to 280°C. The pressure of the reactor is 01-7.
0 MPa, preferably in the range of 0.79 to 1.48 MPa. The static mixer has 3 to 50 elements, preferably 6 to 12 elements, and has a relatively short contact time with the gas in the range of 0.1 to 5 seconds, preferably in the range of 0.5 to 1.0 seconds. and liquid to achieve complete mixing. The molar ratio of the substitution gas to each alkyl group of the trialkylaluminium is in the range of 10:1 to 50:1, preferably 25:1 to 30:1.

The displacement products, olefins and tri-lower alkyl aluminum products, are rapidly cooled to below about 150°C and sent to a separator (66) where the displacement gas and olefins are removed and the second stage separator (54) ) and the remaining liquid product is sent to the sixth stage separator. The gaseous product sent to the second stage separator is further cooled, the displacement gas removed, recompressed, heated and recycled to the displacement reactor feed stream. The liquid bottoms product from the second stage separator is the desired olefin (in this case 04-CI
α-olefin of O), which can be further separated into its constituent components.

The sixth stage separator strips residual alpha-olefins from the tri-lower alkyl aluminum grown feedstock, and the alpha-olefins are combined with the alpha-olefins from the second stage separator; The compound is recycled to the growth reactor.

Examples 1-16 below demonstrate the effectiveness of a tank reactor zone with recirculation, its conditions and its results.

All percentages in these examples are by weight. Example 1 A 2500C tank reactor was charged with the following materials.

Triethyl aluminum (TEA) 17.1
17 f-tree n-butyl aluminum (TNBA)
11.38 9 Tetradecane (n-C14)
2a45? This represents a 50 wt% aluminum alkyl feed stream. The reactor has a bottom outlet connected to a recycle pump which pumps the reactor contents into a cooling coil and back to the reactor.

A total of 31.8 r of ethylene gas was filled at 4.9 MPa.

The reactor was brought to an operating temperature of 126°C using an electric tape heater. The pump was activated and set to a liquid flow rate of 50 ccZ. This represents an exchange of reactor volume in 1-2 minutes.

The reaction was run for 60 minutes and then cooled to room temperature. The aluminum alkyl was collected and the material balance was calculated. Atsubenium alkyl gave the following olefin yields when slowly hydrolyzed.

Butene-122.0% by weight Hexene-15a7% by weight Octene-1 16.6% by weight Tecene-1
2.6% by weight C12+
0.1% by weight Example 2 Using the same reactor set up as in Example 1,
The reaction was carried out under the following conditions.

Packing material TEA 1t4S' TNBA 7.6f n-C1476,0y The solution recycle rate was set at 5 occ/min and the reactor was operated at 4.9 MPa and 113<0>C. Total 35
Three liters of ethylene were charged into the reactor during the reaction operation.

After a residence time of 30 minutes, the following yield was observed:

Butene - 189% by weight Hexene - 161,3 weight Counterfeit octene - 1 23.7 Weight percentage Decene - 1
58M quantity Cl2+
0.3% by weight Example 3 Using the same reactor set up as in Example 1,
The reaction was carried out under the following conditions.

Filling material triethyl aluminum (TEA) 2a5
f-tree n-butyl aluminum (TNBA) 1
9. Oftetradecene (n-C14)
47.5 9 Solution recycle rate was set to 5 [] CC/min. This requires a 2.5 minute reactor volume exchange. A total of 27.82 g of ethylene gas was charged and the reactor was operated at 4.9 MPa, 117° C., and a residence time of 20 minutes.

The following yields were observed.

Butene-118.9% by weight Hexene-1 669% by weight Octene-1
13.0% by weight C1□+
o, oii quantity Example 4 Using the same reactor set up as in Example 1,
The reaction was carried out under the following conditions.

Filling material TEA 16.9f TNBA 11. S? The recycling rate of the n-Cl4 28.2 f solution was set to 75 CC/min. This represents an exchange of reactor volume in 1 minute. Total 32.31F
The reactor was filled with ethylene gas of 4.9 MPa,
It was operated at 120° C. with a residence time of 60 minutes.

The following yields were observed.

Butene - 1196% by weight Hexene - 15Z4N quantity Octene - 1185 weight Weight -1 40 Weight proportion C1340,5
Weight % Example 5 Using the same reactor set up as in Example 1,
The reaction was carried out under the following conditions.

Filling material TEA 17.0f TNBA 11.31P n-C142a4? The solution recycle rate was set at 50 CC,/min. This represents a 1.5 minute reactor volume exchange. Total 198
The reactor is filled with ethylene gas of 3.6 MPa.
, operated at 120° C. with a residence time of 30 minutes.

The following yields were observed.

Butene-122,2 weight ratio Hexene-1516 weight% Octene-112.6 weight% Decene-13.5 weight ratio C12+0.5 weight ratio Example 6 Using the same reactor set as in Example 1, ,
The reaction was carried out under the following conditions.

Filling material TEA 16.8 2TNBA
1 1.2 fn-0142aOf? The solution recycle rate was set at 5 occ/min. This represents a 1.5 minute reactor volume exchange. Total 29.8
9 filled with ethylene gas, the reactor was 4.9MPa.
, operated at 110°C with a residence time of 60 minutes.

The following yields were observed.

Butene - 122,25% by weight Hexene - 160,11% by weight Octene - 115,0% by weight Thidecene - 12,34% by weight C1240,32% by weight Example 7 The same reactor set up as in Example 1 was used. hand,
The reaction was carried out under the following conditions.

Filling material TEA 5.79 TNBA 3.8 rn-C1
485,39 The recycle rate of this solution was set to 50 CC/min.

This represents a 25 minute reactor volume exchange. Total 31.
Fill the reactor with 55F ethylene gas and set the reactor to 4.9Mp.
a, operated at 115 °C with a residence time of 60 min.

The following yields were observed.

Butene-116,9% by weight Hexene-1608% by weight Octene-1 176% by weight Decene-16
9wt Bun C12” 0.8wt%Example 8 Using the same reactor set up as in Example 1,
The reaction was carried out under the following conditions.

Filling material TEA 11.4fTNBA
7.6'? n-Cl4 76.0? The solution recycle rate was set at 50 CC/min. This represents a 2.5 minute reactor volume exchange. Total 55.5
9 filled with ethylene gas, the reactor was 4.9MPa.
, operated at 113° C. with a residence time of 30 minutes.

The following yields were observed.

Butene - 188% by weight Hexene - 1/+1.3% by weight Octene - 1 23.6 non-thidecene - 1
58 weight section C12+
0.5% by weight Example 9 Using the same reactor set up as in Example 1,
The reaction was carried out under the following conditions.

Filling material TEA, 17.0r TNBA 11.39n-C142a
4 t The recycling rate of this solution was set to 50 CC, 7 minutes. This represents a 15 minute reactor volume exchange. Total 39
．． Fill the reactor with 09 ethylene gas and set the reactor to 6.3MP.
a, operated at 121 °C with a residence time of 30 min.

The following yield was expected.

Butene-14,3% by weight Hexeno-15621g Thioctene-1 26.7% by weight Decene-1
9,8wt 1 C1z+ 3.0wt%Example 10 Using the same reactor set up as in Example 1,
The reaction was carried out under the following conditions.

Filling material TEA 22.68? TNBA
15.12 f n-C1437,80? The recycle rate of this solution was set at 67 CC/min.

This represents a 1.5 minute reactor volume exchange. Total 45
Fill the reactor with 3 liters of ethylene gas and set the reactor to 4.9 MPa.
, 13 []°C with a residence time of 15 minutes.

The following yields were observed.

Butene - 1,24,2 weight% Hexene - 1551% by weight Octene - 116,4% by weight Decene - 13,5% by weight C1 + 0.6 weight ratio Example 11 Identical reaction set up as in Example 1 using a device,
The reaction was carried out under the following conditions.

Filling material TEA 22.68? TNBA
1 5.122n -CI4 37.8
0? The recycle rate of this solution was set to b7cr-7 minutes. This represents a 1.5 minute reactor volume exchange. Total 4
Fill the reactor with 5.3F ethylene gas to 4.9M.
The following yields were observed when operating at 130° C. and a residence time of 30 minutes.

Butene-12j, 2 Weight ratio Hexene-1562% by weight Octene-119.8% by weight Thecene-15.0% by weight C12+ 0. 9% by weight
Example 12 Using the same reactor set up as in Example 1,
The reaction was carried out under the following conditions.

Filling material TEA 17.049TNBA
11.36 f n-01428, 40f The recycle rate of this solution was set to 5 occ/min.

This represents a 1.5 minute reactor volume exchange. Total 12
．． Filled with Fl ethylene gas and the reaction was carried out at 2.2 MPa.
, operated at 120°C with a residence time of 30 minutes.

The following yields were observed.

Butene-119.7% by weight Hexene-175.4M Octene-14,9 Heavy base Decene-1 0.0% by weight C124
0.0 Weight Example 13 Using the same reactor set up as in Example 1,
The reaction was carried out under the following conditions.

filling material TEA 17.07f TNBA 11.38 f n-C142 & 45 f The recycling rate of this solution was set at 5 occ/min.

This represents a 1.5 minute reactor volume exchange. Total 6Z
Fill the reactor with 21 ethylene gas and set the reactor to 10.5MP.
a, operated at 120° C. with a residence time of 60 minutes.

The following yields were observed.

Butene-113.3% by weight Hexene-15 & 14% by weight Octene-1 22.43% by weight Decene-1
5.4% by weight C1□+ 0.76 weight

[Brief explanation of drawings]

The accompanying drawings schematically show an embodiment of an apparatus for carrying out the method of the invention. In the figure: 10...Olefin supply line; 12.50...Compressor; 17.2/), 44,66.92.96...Heat exchanger; 19.82...Pump: 18 ...Growth reactor bottom outlet: 20...Growth reactor; 22...
Inlet of circulation stream; 24.27... pressure reducing valve; 32... displacement reactor; 36.54... extraction column; 5B, 56.
...Extraction tower bottom outlet; 58.80...Reboiler;
6o... Bottom circulation inlet; 40.62... Top circulation inlet; 70... Olefin gas take-off valve; 76... Vacuum column; 84... Vacuum column bottom outlet; 57... Purge 2 innia 8...Vacuum column bottom circulation inlet; 86...Return line from vacuum column to growth reactor; 94
...Vacuum tower top circulation inlet: 98...Vacuum line. Patent applicant: The Dow Chemical Company Representative: Patent attorney: Ryoji Youse Takehiko Saito

Claims (1)

[Claims] 1. producing a high molecular weight trialkylaluminum by reacting an α-olefin having 2 to 4 carbon atoms or a mixture thereof with a low molecular weight trialkylaluminium in a growth reaction zone under growth promoting conditions; and reacting an α-olefin having 2 to 4 carbon atoms or a mixture thereof with the high molecular weight trialkylaluminum described above in a displacement reaction zone under displacement conditions to produce a mixture of C4 to CtO α-olefins. ~In a process for the production of CIO α-olefins; by reacting 2 to 6 moles of α-olefin per mole of trialkylaluminum in a tank reaction zone and removing heat from the reaction zone to produce a substantially constant C4~ is tasked with providing a growth reaction zone by having a recirculation rate through the external heat transfer zone such that the contents of the reaction zone are completely recycled in a time sufficient to maintain the internal temperature. Method for producing eta α-olefin. 2. The method of claim 1, wherein the recirculation time is Q, 1 to 60.0 minutes. 6. The method according to claim 1, wherein the recirculation time is between 0.5 and 6.0 minutes. 4. Growth promoting conditions or temperature of 1.00-140℃, 1.5
2. The method of claim 1, wherein the pressure is 159 MPa and the residence time is 15 to 45 minutes. 5. Growth promotion condition is temperature of 115-125℃, 2.2-
A method according to claim 1, wherein the pressure is 1.alpha.5 MPa and the liquid residence time is 30 to 40 minutes. & A method according to claim 1, comprising the following steps. A)) 2 to 6 moles of α-olefins having 2 to 4 carbon atoms or mixtures thereof per mole of realkylaluminium in a tank reaction zone at a pressure of 1.5 to 13.9 MPa.
and at a temperature in the range of 100° C. to 150° C., and in the reaction zone, heat is removed from the reaction zone to maintain a substantially constant internal temperature, and the higher trialkyl aluminum B) having a recirculation rate through an external heat transfer zone such that its contents are recycled in a time sufficient to provide a growth product consisting of B) 2 to 4 α-olefin sweeteners having carbon atoms of
and C) recovering the produced 04-CIO α-olefin. Z. The method according to claim 1, which comprises the following steps. A) ) 2 to 6 moles of ethylene per mole of realkyl aluminum in a tank reaction zone of 1.5 to 13.9 moles of ethylene.
The reaction is carried out at a pressure of MPa and an ambient humidity of 100°C to 150°C, with an external heat transfer zone such that the reaction zone is recirculated at a time of 0.5 to 3 minutes. B) ethylene or butene-1 or a mixture thereof with the above growth product at a temperature ranging from 200°C to 350°C, thereby producing a growth product consisting of higher trialkylaluminum; temperature,
React in a displacement zone with a pressure ranging from 0.1 to 7.0 MPa and a contact time ranging from 0.1 to 5 seconds, and C) recovering the 04-CIO α-olefin produced. 8. The method of claim 7, wherein the displacement band comprises a static mixer band. 2. The method of claim 8, wherein the static mixer has from 3 to 30 fixed elements. 10. The tank reaction zone is under a pressure of 2.2 to 1α5 MPa and has a temperature in the range of 115° to 125°C, and the displacement zone is under a pressure of 0.8 to 1.5 MPa.
8. A method according to claim 7, having a temperature range of 50 DEG to 280 DEG C.