KR102354499B1 - Ethylene oligomerization method and apparatus thereof - Google Patents

Abstract

It is an object of the present invention to provide a method for ethylene oligomerization that effectively removes scale by reaction by-products generated inside the reactor in the linear alpha olefin (LAO) process, facilitates maintenance and repair of the reactor, and minimizes installation costs will be. The ethylene oligomerization method according to an embodiment of the present invention includes a first step of injecting a solution and ethylene into a reactor, a second step of performing an ethylene oligomerization reaction while staying in the reactor for a set time, setting After a period of time, the solution and the reaction solution containing ethylene are discharged from the reactor to circulate the outside of the reactor to remove heat. A fourth step of mixing with the medium solution, and a fifth step of discharging the reaction-completed solution that has completed the reaction from the reactor, wherein the fourth step is passing the reaction medium solution through a mixing eductor mixed and introduced.

Description

Ethylene oligomerization method and apparatus {ETHYLENE OLIGOMERIZATION METHOD AND APPARATUS THEREOF}

The present invention relates to an ethylene oligomerization method and an apparatus therefor, and more particularly, to an ethylene oligomerization method for producing alpha olefins according to a Schulz-Flory distribution during ethylene oligomerization reaction and the same It's about the device.

As is known, the Linear Alpha Olefin (LAO) process using the ethylene oligomerization reaction is a process that includes all monomers 1-hexene (1-C6) and 1-octene (1-C8). It is a process for producing alpha olefins. All alpha olefins, including 1-hexene (1-C6) and 1-octene (1-C8), are important raw materials for synthetic lubricants and alcohol plasticizers.

In the ethylene oligomerization reaction, due to the temperature imbalance inside the reactor, selectivity changes and reaction by-products such as long-chain polymers are generated. Therefore, complete mixing of the solution is required to maintain the temperature balance inside the reactor.

For this purpose, a continuous stirred reactor (CSTR) is used in the linear alpha olefin process. In this case, the ethylene oligomerization reaction by-product may generate scale inside the reactor and cause fouling of the agitator. Therefore, when using the stirrer, it is difficult to maintain and repair the reactor, and the power consumption by the motor driving the stirrer and the installation cost of the device increase.

Republic of Korea Patent Publication 2017-0028203 (published on March 13, 2017)

It is an object of the present invention to provide a method for ethylene oligomerization that effectively removes scale by reaction by-products generated inside the reactor in the linear alpha olefin (LAO) process, facilitates maintenance and repair of the reactor, and minimizes installation costs will be. It is an object of the present invention to provide an apparatus for synthesizing alpha olefins by the ethylene oligomerization method.

The ethylene oligomerization method according to an embodiment of the present invention includes a first step of injecting a solution and ethylene into a reactor, a second step of performing an ethylene oligomerization reaction while staying in the reactor for a set time, setting After a period of time, the solution and the reaction solution containing ethylene are discharged from the reactor to circulate the outside of the reactor to remove heat. A fourth step of mixing with the medium solution, and a fifth step of discharging the reaction-completed solution that has completed the reaction from the reactor, wherein the fourth step is passing the reaction medium solution through a mixing eductor mixed and introduced.

The fourth step is a nozzle step in which the solution in reaction passes through the nozzle of the mixing eductor, a diffuser step in which the solution in reaction passes through the nozzle passes through the diffuser of the mixing eductor at high speed, and a high-speed flow An additional mixing step in which the solution in reaction is introduced into the inside of the reactor at a faster rate as the solution in the reaction is further drawn into the inside of the diffuser and is further mixed in the inside of the diffuser in the reactor. can

In the first step, an upward flow is formed by injecting a solution and ethylene from the lower part of the reactor upward, and the fourth step is additionally mixed while passing through the eductor installed downward from the upper part of the reactor. By forming a downward flow in which the solution in the reaction flows downward from the upper part of the reactor, the upward flow and the downward flow may be mixed in the center of the reactor.

The first step forms the upward flow inside the internal reactor installed inside the reactor, and the fourth step forms a downward flow inside the internal reactor, so that it can be mixed in the center of the internal reactor have.

In the fourth step, the reaction solution rising from the outside of the internal reactor may be rapidly injected into the mixing eductor.

In the first step, a solvent and ethylene may be injected into the reactor through a sparger installed upwardly from the bottom of the reactor.

In the first step, the solvent and ethylene may be injected into the reactor through a donut portion of the sparger and a plurality of nozzles disposed at equal intervals on the donut portion.

The ethylene oligomerization apparatus according to an embodiment of the present invention includes a reactor for performing an ethylene oligomerization reaction by using an injected solution and ethylene, which is provided outside the reactor and is connected to a first pipe line, A heat exchanger for removing heat between the solution and the solution in the reaction containing ethylene, which are discharged from the reactor and circulated after staying in the reactor for a set time, and a second pipe connected to the heat exchanger and installed in the reactor, the heat exchanger It includes a mixing eductor that mixes the reaction solution inside the reactor while passing through the reaction solution after the circulation of the mixture eductor.

The mixing eductor includes a nozzle through which the solution during the reaction passes, and a diffuser through which the solution during the reaction passes through the nozzle at a high speed, wherein the diffuser allows the solution during the reaction in a high-speed flow to pass through the reactor inside the diffuser. As the surrounding reaction solution is further drawn into the diffuser and further mixed in the diffuser, it can be introduced into the reactor at a faster rate.

The reactor may further include an internal reactor installed therein to form an upward flow by injecting a solution and ethylene from the lower part of the reactor upward.

The reactor may further include a sparger installed upward from the bottom to inject a solvent and ethylene from the bottom of the reactor upward.

The sparger may include a donut unit for containing the injected solvent and ethylene as a cylinder, and a plurality of nozzles for uniformly injecting the solvent and ethylene into the reactor at equal intervals on the donut unit.

As described above, in one embodiment of the present invention, the solution in the reaction after the heat removal cycle is passed through the mixing eductor and is mixed with the solution in the reaction inside the reactor that is introduced into the mixing eductor, and then flows into the reactor and inside the reactor. Since it is mixed with the reaction solution, scale caused by reaction by-products generated inside the reactor during the process can be effectively removed.

In addition, one embodiment uses a mixing eductor without using a stirrer to effectively mix the solution in the reaction that has completed the heat removal cycle with the solution in the reaction inside the reactor, thereby facilitating the maintenance and repair of the reactor, and installation of the device cost can be minimized.

1 is a flowchart of a method for oligomerizing ethylene according to an embodiment of the present invention.
2 is a block diagram of an ethylene oligomerization apparatus according to a first embodiment of the present invention.
3 is an operation state diagram of the mixing eductor applied to FIG. 2 .
FIG. 4 is a diagram illustrating the mutual operation of the mixing eductor and the internal reactor applied to FIG. 2 .
5 is a block diagram of an ethylene oligomerization apparatus according to a second embodiment of the present invention.
6 is a perspective view of the sparger applied to FIG. 5 .

Hereinafter, with reference to the accompanying drawings, the embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein. In order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and the same reference numerals are given to the same or similar components throughout the specification.

1 is a flowchart of a method for oligomerizing ethylene according to an embodiment of the present invention, and FIG. 2 is a block diagram of an apparatus for oligomerization of ethylene according to a first embodiment of the present invention.

1 and 2, in the ethylene oligomerization method of an embodiment, the reactant is injected into the reactor 1 to proceed with the ethylene oligomerization reaction, and then the reaction-completed solution in which the reaction is completed is transferred to the reactor ( 1) is exported from For example, the reactant to be injected comprises ethylene and a solution comprising a catalyst, a cocatalyst and a solvent.

The synthesis of the alpha olefin oligomer proceeds while cooling the reactor 1 because it is an exothermic reaction as a low polymerization reaction using an alpha olefin such as ethylene as a raw material. To this end, the reactor 1 is further provided with a cooling water (or refrigerant) jacket 11 on the outside. That is, the cooling water (or refrigerant) jacket 11 cools the reactor 1 in which the exothermic reaction proceeds. And the reactor 1 is provided with a relief valve 12 at the upper portion, it is possible to safely maintain the internal pressure to the set pressure during the synthesis reaction.

For example, the alpha olefin synthesis method includes a first step (ST1) of injecting a reactant solution and ethylene into the reactor (1), a second step (ST2) of performing an ethylene oligomerization reaction in the reactor (1), A third step (ST3) of removing heat from the reaction solution in progress through external circulation, a fourth step (ST4) of mixing the removed heat solution with the reaction solution inside the reactor (1) again (ST4), and the reactor A fifth step (ST5) of discharging the reaction completion solution and ethylene that has completed the reaction in (1) is included.

In the second step (ST2), the ethylene oligomerization reaction proceeds while the injected solution and ethylene stay in the reactor 1 for a set time. In the third step (ST3), after the set time of the second step (ST2), the solution and the solution in the reaction of ethylene are discharged from the reactor 1 to remove heat, circulating the outside of the reactor 1 do. The third step ST3 is performed in the heat exchanger 2 installed outside the reactor 1 . In the fourth step (ST4), after the circulation of the outside of the reactor 1 and the heat exchanger 2 is finished, the heat-removed reaction solution is mixed with the reaction solution inside the reactor 1 again.

In the fourth step (ST4), the internal reaction solution flowing in from the inside of the reactor 1 and the mixing eductor 3 are additionally mixed inside the mixing eductor 3 while passing the deheated reaction solution through the mixing eductor 3 . By flowing into the reactor (1), it is mixed with the reaction solution inside the reactor (1).

The heat exchanger (2) is provided outside the reactor (1) and connected to the first pipe (21) to introduce a solution during reaction to remove heat, and is connected to the second pipe (22) to remove heat from the solution in the reaction. It is fed back to the reactor (1). Also, the reaction completion solution and ethylene are discharged to the outside of the reactor 1 through a branched pipe before being introduced into the heat exchanger 2 through the first pipe 21 .

For example, in the heat exchanger 2, low-temperature cooling water flows into the first conduit 21 through which the high-temperature reaction solution flows, and the high-temperature cooling water flows toward the second conduit 22 through which the low-temperature medium reaction solution flows out. As it flows out, it acts as a heat exchange.

A strainer or filter 211 and a circulation pump 212 are installed in the first conduit 21 to filter the reaction solution in the reactor 1 through the first conduit 21 and supply it to the heat exchanger 2 . The second conduit 22 supplies the reaction medium solution, which has been removed from heat through the heat exchanger 2 by the pressure feeding of the circulation pump 212 , to the reactor 1 and the mixing eductor 3 .

The mixing eductor (3) is connected to the heat exchanger (2) by a second pipe line (22) and is installed inside the reactor (1). Therefore, the mixing eductor 3 is additionally mixed with the internal reaction solution flowing in while passing through the heat-removed reaction medium solution after the circulation of the heat exchanger 2 is completed, and injected into the reactor 1 by injecting it into the inside reaction medium solution. Finally mix.

3 is an operation state diagram of the mixing eductor applied to FIG. 2 . 1 to 3, the mixing eductor 3 is a nozzle 31 passing the solution in the reaction, and the solution in the reaction through the nozzle 31 passes at high speed to flow the solution into the reactor 1 and a diffuser 32 .

In the mixing eductor (3), the high-speed flowing solution of the reaction medium draws the solution in the reaction solution around the diffuser (32) from the inside of the reactor (1) further into the inside of the diffuser (32). Therefore, the diffuser 32 may additionally mix the solution in reaction and the solution in reaction removed from the inside, and may flow it into the reactor 1 at a higher speed.

To this end, the nozzle 31 is connected to the side of the first passage 311 and the first passage 311 for supplying the heat-removed reaction solution by connecting the diffuser 32 in the second tube 22 to the reactor. (1) It is exposed to the inside and includes a second passage 312 through which the internal reaction solution flows.

That is, the high-speed flow of the reaction solution through the first passage 311 of the nozzle 31 provides a strong suction force to the second passage 312, so that the reaction solution in the reactor 1 around the diffuser 32 is removed. In addition, the mixture is additionally mixed inside the nozzle 31 and the diffuser 32 .

The additionally mixed reaction solution is mixed with the reaction solution inside the reactor 1 while being injected into the reactor 1 at a higher speed through the diffuser 32 . The solution in the reaction injected at such a high speed meets the solution (catalyst, co-catalyst and solvent) and ethylene injected from the lower part at the center of the reactor 1 and is effectively mixed.

That is, the fourth step ST4 is a nozzle step in which the heat-removed reaction solution passes through the nozzle 31 of the mixing eductor 3 , and the reaction solution passed through the nozzle 31 is transferred to the mixing eductor 3 . It includes a diffuser step passing through the diffuser 32 at high speed, and an additional mixing step.

In the additional mixing step, the high-speed flow of the heat-removed solution in the reaction medium draws the solution in the reaction solution around the diffuser 32 inside the reactor 1 into the inside of the diffuser 32, and the nozzle 31 and the inside of the diffuser 32 This means that the deheated reaction solution and the inside reaction solution are additionally mixed and flowed into the reactor 1 at a faster rate.

Therefore, the mixing efficiency of the solution existing in the reactor 1 and the solution introduced after circulation is increased, and the influence of the mass transfer limitation is lowered. That is, heat removal and reaction activity of the solution inside the reactor 1 may be increased.

FIG. 4 is a diagram illustrating the mutual operation of the mixing eductor and the internal reactor applied to FIG. 2 . 2 and 4 , the reactor 1 includes an internal reactor 13 installed therein to inject a solution and ethylene from the lower part of the reactor 1 upward to form an upward flow.

1 to 4 , in the first step ST1 , an upward flow F1 is formed inside the internal reactor 13 installed inside the reactor 1 . In the fourth step (ST4), a downward flow F2 is formed in the interior of the internal reactor 13 by the mixing eductor 3, and in the reaction medium solution of an upward flow F1 from the center of the internal reactor 13. The solution in the deheated reaction medium flowing downward (F2) is mixed.

In addition, in the fourth step (ST4), the reaction medium solution of the upward flow F3 coming up from the outside of the internal reactor 13 is rapidly injected into the second passage 312 of the mixing eductor 3, and the nozzle 31 ) and implement additional mixing inside the diffuser 32 .

As such, the mixing eductor 3 facilitates the flow of the solution during the reaction inside the reactor 1, so that the temperature gradient inside the reactor 1 can be lowered, and the solution can be uniformly mixed. And since one embodiment does not use the stirrer, it is possible to prevent fouling by the stirrer in the reactor 1 .

Accordingly, the occurrence of scale in the reactor 1 can be reduced. And since it is possible to clean the reactor 1 in a short time without an additional cleaning operation, the period of stopping the apparatus may be increased. That is, the uptime of the device is increased. Since the mixing eductor 3 is simpler in structure than the stirrer, the equipment space is reduced and the equipment equipment cost is reduced.

Hereinafter, a second embodiment of the present invention will be described. Compared with the first embodiment, the same configuration will be omitted and different configurations will be described.

5 is a block diagram of an ethylene oligomerization apparatus according to a second embodiment of the present invention, and FIG. 6 is a perspective view of a sparger applied to FIG. 5 . Referring to FIGS. 5 and 6 , the reactor 51 further includes a sparger 6 installed from the bottom to the top to inject the solvent and ethylene from the bottom of the reactor 51 to the top.

For example, the sparger 6 includes a donut part 61 formed in a cylindrical shape and a plurality of nozzles 62 provided in the donut part 61 . The donut unit 61 contains the injected solvent and ethylene, and the nozzles 62 are disposed at equal intervals on the donut unit 61 to uniformly spray the injected solvent and ethylene into the reactor 51 .

In the first step (ST1), the solvent and ethylene are injected into the reactor 51 through the sparger 6 installed upwardly from the lower part of the reactor 51 . In this case, the catalyst and the promoter may be separately injected from the outside of the sparger 6 .

In the first step (ST1), the solvent and ethylene are injected into the reactor 51 through a plurality of nozzles 62 disposed at equal intervals on the donut part 61 and the donut part 61 of the sparger 6 . It can be sprayed evenly.

The sparger 6 is disposed at the lower part of the internal reactor 13 to uniformly form an upward flow F11 of solvent and ethylene in the internal reactor 13, and a downward flow by the mixing eductor 3 It can be mixed more uniformly with the solution in the deheated reaction of (F2). Therefore, it is possible to lower the temperature gradient inside the reactor (51).

Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and it is possible to carry out various modifications within the scope of the claims, the description of the invention, and the accompanying drawings, and this also It is natural to fall within the scope.

1, 51: reactor 2: heat exchanger
3: mixing eductor 6: sparger
11: coolant (refrigerant) jacket 12: relief valve
13: internal reactor 21: first pipeline
22: second conduit 31: nozzle
32: diffuser 61: donut unit
62: nozzle 211: strainer or filter
212: circulation pump 311: first passage
312: second passage F1, F11: upward flow
F2: Downflow F3: Upflow

Claims (12)

A first step of injecting the solution and ethylene into the reactor;
a second step of performing an ethylene oligomerization reaction while staying in the reactor for a set time;
a third step of circulating the solution and the reaction solution containing ethylene after a set time from the reactor to circulate the outside of the reactor to remove heat;
a fourth step of mixing the reaction solution after circulation with the reaction solution inside the reactor again; and
A fifth step in which the reaction completion solution that has completed the reaction in the reactor is discharged
includes,
The fourth step is
The solution in the reaction is mixed and introduced while passing through a mixing eductor,
The first step is
By injecting the solution and ethylene from the lower part of the reactor to the upper part,
Ethylene oligomerization method for forming an upward flow in the interior of the internal reactor installed in the interior of the reactor.
The method of claim 1,
The fourth step is
A nozzle step in which the solution in the reaction passes through the nozzle of the mixing eductor,
A diffuser step in which the solution in reaction passing through the nozzle passes through the diffuser of the mixing eductor at high speed, and
An additional mixing step in which the high-speed flowing solution in the reaction further draws the solution in the reaction around the diffuser into the inside of the diffuser from the inside of the reactor, and as it is further mixed inside the diffuser, it is introduced into the reactor at a faster rate
Ethylene oligomerization method comprising a.
The method of claim 1,
The fourth step is
Forming a downward flow in which the solution in the reaction, which is additionally mixed while passing through the eductor installed downward from the upper part of the reactor, flows downwardly from the upper part of the reactor,
A process for ethylene oligomerization comprising mixing said upward flow and said downward flow in the center of said reactor.
4. The method of claim 3,
The fourth step is
By forming a downward flow inside the inner reactor,
Ethylene oligomerization method mixed in the center of the internal reactor.
5. The method of claim 4,
The fourth step is
An ethylene oligomerization method in which a solution in the reaction rising from the outside of the internal reactor is rapidly injected into the mixing eductor.
The method of claim 1,
The first step is
An ethylene oligomerization method in which a solvent and ethylene are injected into the reactor through a sparger installed upwardly from the bottom of the reactor.
7. The method of claim 6,
The first step is
An ethylene oligomerization method of injecting the solvent and ethylene into the reactor through a donut portion of the sparger and a plurality of nozzles disposed at equal intervals on the donut portion.
a reactor for performing an ethylene oligomerization reaction with the injected solution and ethylene;
a heat exchanger provided outside the reactor and connected to a first pipe line to remove heat from the solution during the reaction including ethylene and the solution discharged from the reactor and circulated after staying in the reactor for a set time; and
A mixing eductor connected to the heat exchanger by a second pipe and installed in the reactor, mixing while passing the reaction medium solution that has finished circulation in the heat exchanger, and mixing it with the reaction medium solution inside the reactor
includes,
The reactor is
An internal reactor installed inside to form an upward flow by injecting a solution and ethylene from the lower part of the reactor upward
Ethylene oligomerization apparatus further comprising a.
9. The method of claim 8,
The mixing eductor is
A nozzle through which the solution in the reaction passes, and
A diffuser for passing the solution in the reaction through the nozzle at high speed,
the diffuser
Ethylene oligomer flowing into the reactor at a faster rate as the high-speed flow of the solution in the reaction further draws the solution in the reaction around the diffuser into the inside of the diffuser from the inside of the reactor and further mixes in the inside of the diffuser fire device.
delete 9. The method of claim 8,
The reactor is
A sparger installed from the bottom to the top to inject solvent and ethylene from the bottom of the reactor to the top
Ethylene oligomerization apparatus further comprising a.
12. The method of claim 11,
The sparger
A donut part containing the injected solvent and ethylene into a cylinder, and
A plurality of nozzles uniformly spraying the solvent and ethylene disposed at equal intervals in the donut part into the inside of the reactor
Ethylene oligomerization device comprising a.

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