Distributor and reactor comprising same

Abstract

A distributor includes a main body including a plurality of holes, a protruding tube extending upward along an outer circumferential surface of the plurality of holes, and a side tube extending from a side surface of the protruding tube.

Description

Technical Field

[0001] Cross Reference to Related Applications

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2021-0159855, filed on November 18, 2021, the entire contents of which are incorporated herein by reference as a part of the specification. Technical Field

[0004] The present invention relates to a distributor, and more specifically, to a distributor that can simultaneously improve mixing and anti-scaling effects, and a reactor including the distributor. Background Technology

[0005] Alpha-olefins are important materials used in comonomers, detergents, lubricants, plasticizers, etc., and are widely used commercially. In particular, 1-hexene and 1-octene are often used as comonomers to adjust the density of polyethylene in the production of linear low-density polyethylene (LLDPE).

[0006] α-Olefins such as 1-hexene and 1-octene are typically prepared via the oligomerization of ethylene. Ethylene oligomerization is carried out using ethylene as a reactant in the presence of a catalyst via the oligomerization of ethylene (trimerization or tetramerization). During the catalytic reaction, the products generated include not only a multi-component hydrocarbon mixture (including the desired 1-hexene and 1-octene) but also small amounts of byproducts (including C20+ polymer materials). Because the products and byproducts are relatively heavy, they descend to the lower part of the reaction zone in the reactor. Therefore, scaling may occur, clogging the pores of the distributor, and products may deposit on the distributor.

[0007] Therefore, there are often maintenance costs due to scaling, and the product cannot be obtained well due to reduced mixing efficiency. Summary of the Invention

[0008] [Technical Issues]

[0009] In order to solve the problems mentioned in the background art, one object of the present invention is to provide a distributor designed to improve mixing efficiency and reduce fouling, and a reactor including the distributor.

[0010] [Technical Solution]

[0011] In one general aspect, the distributor includes: a body comprising a plurality of holes, a protruding tube extending upward along the outer peripheral surface of the plurality of holes, and a side tube extending from the side surface of the protruding tube.

[0012] In another general aspect, the reactor includes: a monomer supply line through which a gaseous monomer stream is supplied; and a distributor as described in the present invention for dispersing the gaseous monomer stream supplied through the monomer supply line.

[0013] [Beneficial Effects]

[0014] According to the distributor of the present invention, gaseous materials as reactants are supplied to the reaction zone in the reactor through protruding tubes extending upward along the outer peripheral surface of the distributor's orifices, thereby minimizing scaling phenomena where the orifices of the distributor are blocked by reaction products or heavy byproducts. Therefore, the reactor's operating cycle can be extended, and maintenance costs due to scaling can be reduced.

[0015] Furthermore, the mixing efficiency at the top of the distributor is improved by injecting gaseous material downwards through side pipes extending from the side of the protruding pipe. Therefore, reaction products can be effectively discharged to the product outlet, allowing for operation based on reaction designs such as improved conversion rates. Attached Figure Description

[0016] Figure 1 This is a plan view of a distributor according to an exemplary embodiment of the present invention.

[0017] Figure 2 This is a cross-sectional view of a distributor according to an exemplary embodiment of the present invention.

[0018] Figure 3a and Figure 3b This is a cross-sectional view of a side tube according to an exemplary embodiment of the present invention.

[0019] Figure 4 This is a reactor and process flow diagram according to an exemplary embodiment of the present invention.

[0020] Figure 5a and Figure 5b The plan view and sectional view are based on the distributor of the comparative example. Detailed Implementation

[0021] The terms and words used in the specification and claims of this invention should not be limited to having a general or dictionary meaning, but rather should be interpreted as having a meaning and concept consistent with the technical concept of this invention, based on the principle that inventors are able to appropriately define the concepts of the terms in order to best describe their own invention.

[0022] In this invention, the term "flow" can refer to a fluid flow in a process, or to the fluid itself flowing in a moving pipeline (pipeline). Specifically, "flow" can refer to the fluid itself flowing in pipes connecting various devices, or to a fluid flow. Furthermore, fluid can refer to any one or more of gases, liquids, and solids.

[0023] In this invention, "C#", where "#" is a positive integer, represents all hydrocarbons having # carbon atoms. Therefore, the term "C10" represents a hydrocarbon compound having 10 carbon atoms. Furthermore, the term "C#+" represents all hydrocarbon molecules having # or more carbon atoms. Therefore, the term "C10+" represents a mixture of hydrocarbons having 10 or more carbon atoms.

[0024] In the following text, reference will be made to Figures 1 to 4 The invention is described in order to provide a better understanding of it.

[0025] First, refer to Figure 1 and Figure 2 , Figure 2 Based on Figure 1 A longitudinal sectional view along line A-A'. The distributor 100 according to the invention may include: a body including a plurality of holes 130, a protruding tube 110 extending upward along the outer peripheral surface of the plurality of holes, and a side tube 120 extending from the side surface of the protruding tube.

[0026] According to an exemplary embodiment of the present invention, the distributor 100 is provided, for example, at the lower part of the reactor 200, so that the gaseous monomer flow supplied to the reactor 200 can be dispersed upward, while the liquid reaction medium in the reactor 200 can be mixed to improve the conversion rate of the monomer.

[0027] The main body of the distributor 100 can be freely designed according to the shape of the reactor 200. For example, the main body of the distributor 100 can be formed into a disc shape, and its outer peripheral surface has the same structure as the inner surface of the reactor 200. Here, the outer peripheral surface of the main body can be designed to be tightly attached to the inner surface of the reactor 200.

[0028] The body may have a diameter of, for example, 100mm to 1500mm, 100mm to 1000mm or 100mm to 500mm, and a thickness of, for example, greater than 0mm and less than 100mm, 1mm to 50mm or 10mm to 30mm.

[0029] According to an exemplary embodiment of the present invention, the main body of the distributor 100 may include holes 130 formed through the upper and lower surfaces of the main body of the distributor 100. Multiple holes 130 may be formed at equal intervals around the center of the main body. Specifically, gaseous material, such as a monomer stream, supplied from the bottom of the reactor can be uniformly injected into the reaction zone inside the reactor 200 where the reaction medium is disposed, through the holes 130 formed at equal intervals around the center of the main body.

[0030] When the body has a disc shape, the diameter of the orifice 130 can be 1% to 50%, 1% to 30%, or 1% to 10% of the body diameter. When the diameter of the orifice 130 is within this range, the reactor can be prevented from shutting down due to scaling in the distributor, and the mixing efficiency in the reactor is also increased to minimize dead volume. Therefore, the effect of improving the reaction conversion rate can be obtained.

[0031] Multiple orifices can have the same diameter and can include orifices with relatively large diameters and orifices with relatively small diameters. When the orifice diameters are formed in such a different manner, portions of gaseous material that do not mix with gaseous material passing through orifices with relatively large diameters can mix with gaseous material passing through orifices with small diameters, thus improving the mixing efficiency of the liquid reaction medium in reactor 200.

[0032] Furthermore, according to an exemplary embodiment of the present invention, the distributor 100 may include a protruding tube 110 extending upward along the outer peripheral surface of each of the plurality of holes 130. The outer peripheral surface may refer to the outer peripheral surface of the opening formed by the holes 130 in the upper surface of the body of the distributor 100. Therefore, the body of the distributor 100 and the protruding tube 110 may be integrally formed. Also, "upward" may refer to "towards the reaction zone in the reactor 200 where the reaction medium is disposed."

[0033] Gaseous material, such as a gaseous monomer stream, supplied from the lower part of the distributor 100 through orifice 130, is supplied by passing through the orifice through the body of the distributor 100 and being dispersed in the reaction zone via protruding pipe 110. The flow of the gaseous material in... Figure 2 The middle is represented by a dashed line.

[0034] In other words, referring to the traditional distributor 140 Figure 5a and Figure 5b It was confirmed that the upper surface of the main body of the distributor 140 and the upper surface of the opening of the orifice 150 have the same or similar surface height. When gaseous material (reactant) is supplied through the distributor 140 to the reaction zone where the reaction medium is provided on the upper part of the distributor 140, the reaction products and heavy byproducts produced by the reaction have a higher density than the reaction medium and settle down. Therefore, the orifice 150 is prone to clogging (scaling). In addition, as the reaction proceeds, the reaction products and heavy byproducts are deposited on the upper surface of the main body of the distributor 140, so uniform mixing is impossible.

[0035] However, the distributor 100 according to an exemplary embodiment of the present invention is provided with a protruding tube 110, whereby the surface height of the protruding tube 110 can be formed to be higher than the surface height of the upper surface of the body of the distributor 100. Therefore, the linear velocity of the gaseous monomer flow passing through the distributor 100 and supplied to the reactor remains constant, while reducing the likelihood of fouling. Furthermore, the cycle for shutting down the reactor 200 and cleaning the interior of the reactor 200 and devices such as the distributor 100 can be extended. Moreover, in the present invention, where gaseous monomers are supplied to the reaction zone through the protruding tube 110, compared to conventional techniques, gaseous monomers can be supplied to a deeper reaction zone to ensure a larger, more uniform reaction zone, thus improving reactor performance, such as conversion rate.

[0036] Therefore, the height of the prominent tube (L) P ), that is, the difference between the surface height of the upper surface of the distributor 140 and the surface height of the protruding tube (L). P The thickness (L) of the main body of the distributor 100 B The relationship between them can satisfy the following equation 1:

[0037] [Formula 1]

[0038] L P ≥L B

[0039] Where L P To emphasize the height of the pipe, L B The thickness of the main body.

[0040] More specifically, highlight the height of the tube (L) P It can meet 10L B ≥L P ≥L B More specifically, 5L B ≥L P ≥L B Within this range, it is possible to maximize the uniform reaction area and prevent pore scaling.

[0041] Furthermore, according to an exemplary embodiment of the present invention, the distributor 100 may include a side tube 120 extending from the side surface of the protruding tube 110. The side tube 120 may include a horizontal tube portion 121 and a downward tube portion 122, the horizontal tube portion 121 extending horizontally from the side surface of the protruding tube 110, and the downward tube portion 122 extending downward from the end of the horizontal tube portion. The end of the downward tube portion 122 and the upper end of the main body may be spaced apart.

[0042] Specifically, gaseous material (gaseous monomer) supplied from the lower part of the main body of the distributor 100 through multiple holes 130 passes through the protruding pipe 110 and moves upward. During this process, a portion of the gaseous material moving through the protruding pipe 110 can be discharged through the side pipe 120. That is, a portion of the gaseous material is sequentially sprayed onto the upper surface of the main body of the distributor 100 through the horizontal pipe portion 121 of the side pipe 120 extending in a direction parallel to the upper surface of the distributor 100 and the downward pipe portion 122 of the side pipe 120 extending downward to face the upper surface of the distributor 100.

[0043] Here, the flow rate of the gaseous material discharged through the side pipe 120 can be 5% to 15% of the flow rate of the gaseous material supplied through the orifice. That is, when the flow rate of the gaseous material discharged from the side pipe 120 is 5% or more, the mixing efficiency on the upper surface of the main body of the distributor 100 can be improved, and when the flow rate is 15% or less, the gaseous material can be fully transferred to the reaction zone through the protruding pipe 110 and the reaction zone is maximized, thereby achieving, for example, an improved conversion rate.

[0044] As described above, since the reaction products and heavy byproducts produced by the reaction have relatively high densities, they may sink into or deposit on the distributor 100. The reaction products and heavy byproducts can be mixed by means of the flow of gaseous material discharged and sprayed through the downward pipe section 122, which improves the mixing efficiency to minimize the dead volume, and on the other hand, can achieve the effect of increasing the reaction conversion rate.

[0045] According to an exemplary embodiment of the present invention, the end of the downward tube 122 may include an inclined portion, such that the surface height of the portion adjacent to the protruding tube 110 is higher. That is, referring to... Figure 3a and Figure 3b The surface height of the lower end of the tube 122 can be made the same, such as Figure 3a As shown, or the surface height of the lower tube portion 122 is formed such that the surface height of the portion adjacent to the protruding tube 110 is higher, such as... Figure 3b As shown, the inclined portion can therefore be fully introduced. When the inclined portion is introduced into the end of the downward pipe 122, the injection intensity of the gaseous material discharged through the downward pipe 122 can be increased, thereby increasing the mixing efficiency of the upper surface of the distributor 100 body.

[0046] According to an exemplary embodiment of the present invention, the angle between the horizontal tube 121 and the downward tube 122 can be 75° to 135°. As described above, the distributor 100 may include a plurality of holes 130 formed circumferentially at the center of the main body. For example, when the position of the holes 130 is adjacent to the circumference of the main body of the distributor 100, that is, when the holes 130 are adjacent to the sidewall of the reactor, the angle between the horizontal tube 121 and the downward tube 122 can be formed to be greater than 90°. Therefore, gaseous materials are more directly injected and dispersed onto / into reaction products, heavy by-products, etc. deposited on the part where the reactor sidewall and the distributor 100 are connected, thereby further improving the mixing efficiency.

[0047] Similarly, the number of side tubes 120 extending from a protruding tube 110 can be 2 to 4. For example, when the spacing between the holes 130 of the distributor 100 is narrow, the number of side tubes 120 extending from a protruding tube 110 can be 2, and when the spacing between the holes 130 is large, the number can be 4, thereby improving the mixing efficiency according to the gaseous material injection.

[0048] Furthermore, according to the present invention, a reactor 200 including a distributor 100 is provided. Specifically, as shown... Figure 4 As shown, reactor 200 may include monomer supply line 210 through which a gaseous monomer stream is supplied; and a distributor 100 according to the invention for dispersing the gaseous monomer stream supplied through monomer supply line 210.

[0049] According to an exemplary embodiment of the present invention, reactor 200 can be a reactor suitable for continuous processes. For example, reactor 200 may include any one or more reactors selected from continuous stirred tank reactors, plug flow reactors, and bubble column reactors. As a specific example, reactor 200 may be a bubble column reactor. Therefore, monomers can react continuously.

[0050] According to an exemplary embodiment of the present invention, reactor 200 can be used to produce oligomers by oligomerizing monomers in the presence of a catalyst and a solvent.

[0051] In other words, referencing Figure 4 The catalyst, co-catalyst, and solvent can be supplied from the side of reactor 200 to the reaction zone within the reactor via each supply line 220. For example... Figure 4 As shown, the catalyst, co-catalyst, and solvent can be supplied to each individual supply line 220. The catalyst can be mixed with the solvent, and the co-catalyst can be mixed with the solvent and supplied to both supply lines.

[0052] The monomer may include ethylene. Specifically, a gaseous monomer stream including ethylene monomer is introduced into reactor 200 through a monomer supply line 210 located at the bottom of reactor 200. The gaseous monomer stream is dispersed by distributor 100 and oligomerizes in the reaction medium in reactor 200, thereby producing the desired α-olefin product.

[0053] According to an exemplary embodiment of the present invention, an injection section extending from and disposed of on the monomer supply line 210 may also be included. Gaseous ethylene monomer delivered through the monomer supply line 210 may be injected through the injection section and pass through the distributor 100.

[0054] The injection section can be formed to extend from the monomer supply line 210 and branch into multiple pipes, with nozzles formed at each end of the branched pipes. Specifically, gaseous ethylene monomer delivered through the monomer supply line 210 can be introduced into the reactor 200 through the nozzles of the injection section. Thus, the gaseous ethylene monomer introduced into the reactor 200 can be sprayed upwards through the distributor 100. Because of the injection section, additional equipment such as conventional deflectors is unnecessary, and the difficulty of maintaining a constant linear velocity of the gaseous monomer flow when using conventional deflectors is solved. As a result, the linear velocity of the gaseous monomer flow remains constant, thereby maintaining a uniform dispersion of the reaction solution and byproducts in the reactor and preventing byproducts from agglomerating on one side.

[0055] The oligomerization reaction takes place in the lower or middle part of the reaction zone of reactor 200, and the oligomerization reaction of the monomer can be carried out in a liquid state dissolved in a solvent in the presence of a catalyst and a co-catalyst.

[0056] Oligopolymerization can refer to the reaction in which monomers are oligomerized. Depending on the number of monomers to be polymerized, oligomerization can be called trimerization or tetramerization, which are collectively referred to as polymerization.

[0057] In the oligomerization reaction of the monomer, unreacted monomers and evaporated solvents in reactor 200 can be discharged to the upper part of reactor 200, where they can be recycled back into reactor 200 and reused in the oligomerization reaction of the monomer. Furthermore, oligomers produced by the oligomerization reaction of the monomer can be obtained by separation at the lower side of reactor 200.

[0058] Alpha-olefins are widely used commercially as important materials in copolymers, detergents, lubricants, plasticizers, etc., especially 1-hexene and 1-octene, which are often used as comonomers to adjust the density of polyethylene in the preparation of linear low-density polyethylene (LLDPE). Alpha-olefins such as 1-hexene and 1-octene can be prepared by trimerization or tetramerization of ethylene monomers.

[0059] The oligomerization of monomers can be carried out using reaction systems and common contact technologies, with or without solvents, through homogeneous liquid-phase reactions, slurry reactions with partially or completely insoluble catalysts, two-phase liquid / liquid reactions, or bulk phase reactions or gas-phase reactions with the product as the main medium.

[0060] Solvents, catalysts, and co-catalysts can be supplied to the lower side of reactor 200 in the liquid phase.

[0061] The catalyst may include a transition metal source. The transition metal source may be, for example, a compound selected from one or more of chromium acetylacetonate (III), chromium tetrahydrofuran chloride (III), chromium 2-ethylhexanoate (III), tris(2,2,6,6-tetramethyl-3,5-heptadecanoate)chromium (III), benzoylacetone (III), chromium hexafluoro-2,4-pentanedione (III), chromium acetate (III) hydroxide, chromium acetate (III), chromium butyrate (III), chromium valerate (III), chromium laurate (III), and chromium stearate (III).

[0062] The cocatalyst may include one or more selected from, for example, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, ethylaluminum sesquichloride, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, modified methylaluminoxane, and borate.

[0063] Solvents used for monomer oligomerization reactions may include one or more selected from n-pentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, octane, cyclooctane, decane, dodecane, benzene, xylene, 1,3,5-trimethylbenzene, toluene, ethylbenzene, chlorobenzene, dichlorobenzene, and trichlorobenzene.

[0064] Therefore, during the oligomerization of monomers in the presence of catalysts and solvents, sticky byproducts, such as polymers, are generated in addition to the oligomer products. These byproducts may clog the pores formed in the distributor 100, leading to scaling.

[0065] In this regard, the reactor 200 according to the invention uses the distributor 100 described above, thereby preventing the holes in the distributor 100 from becoming clogged due to scaling, thus extending the washing cycle of the reactor 200, preventing a decrease in output due to reduced operating time, and reducing the cost required for the washing process.

[0066] According to an exemplary embodiment of the present invention, if necessary, equipment required for oligomer production, such as valves, condensers, reboilers, pumps, cooling equipment, filters, stirrers, compressors, and mixers, may be further installed in reactor 200.

[0067] In the foregoing, a distributor and a reactor including the distributor according to the invention have been described and illustrated in the accompanying drawings; however, the description and illustrations in the drawings are merely descriptions and illustrations for understanding the core components of the invention, and processes and apparatuses not separately described and illustrated in the foregoing description and drawings may also be suitably applied and used with the distributor and the reactor including the distributor according to the invention.

[0068] The present invention will be described in more detail below by way of examples. However, the following examples are provided to illustrate the present invention, and it will be apparent to those skilled in the art that various modifications and changes can be made without departing from the scope and spirit of the present invention, and the scope of the present invention is not limited thereto.

[0069] Example 1

[0070] According to the present invention Figure 1 The distributor 100 is installed in the bubble column reactor 200, such as Figure 4 As shown, an oligomerization reaction of ethylene monomer is carried out. Specifically, solvent, catalyst, and co-catalyst are supplied to the lower side of reactor 200. Gaseous ethylene monomer is supplied through monomer supply line 210 located at the lower part of reactor 200, and distributor 100 is used to disperse the flow upward to carry out the oligomerization reaction in the liquid reaction medium of reactor 200. The α-olefins produced by the oligomerization reaction are separated and obtained at the lower side of reactor 200, while unreacted monomer and vaporized solvent are discharged to the upper part of reactor 200.

[0071] At this time, the diameter of the main body of the distributor 100 is 300mm, the thickness of the main body of the distributor 100 is 20mm, the height of the protruding tube 110 is 60mm, and a side tube 120 is provided on the side of the protruding tube 110.

[0072] In this case, it was confirmed that a portion of the gaseous ethylene monomer flowed through the protruding pipe 110 of the distributor 100 and was supplied to the reaction zone, while the remaining ethylene monomer flowed through the side pipe and was sprayed onto the upper surface of the body of the distributor 100.

[0073] As a result of Example 1, the mixing efficiency of ethylene monomers was improved to increase the yield of α-olefins. Furthermore, the occurrence of scaling in distributor 100 was reduced to extend the shutdown cycle for cleaning reactor 200.

[0074] Comparative Example 1

[0075] The process is performed in the same manner as in Example 1, except that a distributor 140 without protruding tubes and side tubes is used as the distributor 140, such that the surface height of the hole 150 and the surface height of the distributor 140 body are the same, as... Figure 5a and 5bAs shown in the image.

[0076] In this case, it was confirmed that the mixing efficiency of the ethylene monomer was reduced compared to Example 1, resulting in a decrease in the yield of α-olefins and fouling. Alternatively, the rate in the distributor 140 could be increased to shorten the shutdown cycle of the cleaning reactor 200.

Claims

1. A distributor, comprising: A body comprising multiple holes; A protruding tube extending upward along the outer peripheral surface of the plurality of holes; as well as A side tube extending from the side surface of the protruding tube. The side tube includes a horizontal tube section and a downward tube section. The horizontal tube section extends horizontally from the side of the protruding tube, and the downward tube section extends downward from the end of the horizontal tube section. The distributor is configured such that gaseous material supplied from the lower part of the body through the plurality of holes passes through the protruding tube and moves upward, and a portion of the gaseous material moving through the protruding tube is discharged through the side tube, while the remaining gaseous material moving through the protruding tube is discharged through the end of the protruding tube.

2. The distributor according to claim 1, wherein, The end of the downward tube is spaced apart from the upper end of the main body.

3. The distributor according to claim 1, wherein, The end of the downward tube includes an inclined portion, such that the surface height of the portion adjacent to the protruding tube is high.

4. The distributor according to claim 1, wherein, The angle between the horizontal tube section and the downward tube section is 75° to 135°.

5. The distributor according to claim 1, wherein, The flow rate of the gaseous material discharged through the side pipe is 5% to 15% of the flow rate of the gaseous material supplied through the orifice.

6. The distributor according to claim 1, wherein, The distributor satisfies the following equation 1: [Formula 1] L P ≥L B Where L P L is the height of the protruding tube. B The thickness of the main body.

7. The distributor according to claim 1, wherein, The number of side tubes extending from a single protruding tube is 2 to 4.

8. A reactor, comprising: A single-unit supply pipeline through which gaseous single-unit flow is supplied; and The distributor as claimed in claim 1 is used to disperse the gaseous monomer flow supplied through the monomer supply line.

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