阅读说明：本技术 制备链烷烃的方法 (Process for preparing paraffinic hydrocarbons ) 是由 孙成烈 崔智仙 朴赞宪 朴孝承 宋寅浃 郑宇城 崔宰硕 秋大贤 于 2018-11-09 设计创作，主要内容包括：本发明涉及一种制备链烷烃的方法,并且可以提供一种制备链烷烃的方法,所述方法包括将直链α-烯烃的制备工艺的副产物进行氢化的步骤。根据本发明的制备链烷烃的方法,可以将直链α-烯烃的制备工艺的副产物以高转化率转化为链烷烃,因此可以使副产物具有高附加值。(The present invention relates to a method for preparing paraffins, and may provide a method for preparing paraffins, which includes a step of hydrogenating byproducts of a process for preparing linear alpha-olefins. According to the method for preparing paraffin of the present invention, the by-product of the process for preparing linear alpha-olefin can be converted into paraffin at a high conversion rate, and thus the by-product can be given a high added value.)

1. A process for preparing paraffinic hydrocarbons comprising the steps of:

providing a feed comprising 30 to 100 mole percent branched olefins and 0 to 50 mole percent linear internal olefins with the balance other by-products; and

the feed is subjected to hydrogenation.

2. A process for producing paraffinic hydrocarbons according to claim 1 in which the feed is directly subjected to hydrogenation.

3. A process for producing paraffins according to claim 1, wherein said feed comprises from 60 to 95 mol% of branched olefins and from 1 to 20 mol% of linear internal olefins.

4. The process for producing paraffins according to claim 1, wherein said other by-products comprise isoparaffins, n-paraffins, naphthenes or combinations thereof.

5. The process for making paraffinic hydrocarbons according to claim 1, wherein said branched olefin is a C4 to C20 branched olefin.

6. A process for producing paraffinic hydrocarbons according to claim 1 wherein the hydrogenation step is carried out in a trickle bed reactor.

7. A process for preparing paraffinic hydrocarbons according to claim 6 wherein said feedstock flows into the reactor in the liquid phase, the Space Velocity (SV) of the feedstock flowing in being in the range of 0.1 to 4h^-1。

8. The process for producing paraffinic hydrocarbons according to claim 1, wherein said hydrogenation step is carried out in the presence of a metal catalyst at a temperature of 100-200 ℃ and 10-100kg/cm²g, the metal catalyst is selected from nickel (Ni), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Lu), and an alloy containing 2 or more of them.

9. The process for producing paraffins according to claim 1, wherein, after said hydrogenation step, a step of separating the produced paraffins is also included.

10. A process for producing paraffins according to claim 1, wherein, after said hydrogenation step, a step of separating the isoparaffins from the produced paraffins is also included.

Technical Field

The present invention relates to a method for preparing paraffins, and more particularly, to a method for preparing paraffins from byproducts of a linear alpha-olefin preparation process.

Background

Ethylene is a raw material used as a base material in the chemical industry, and the production amount and consumption amount thereof are regarded as indices of the chemical industry scale in one country. Generally, ethylene is used as a monomer for preparing polymers such as polyethylene, and Linear Alpha-olefins (LAO) having a carbon length (or carbon chain) of about C4 to C40 are prepared by adjusting the degree of polymerization according to circumstances, and thus can be used for preparing various chemicals.

In the production process of such Linear alpha-olefins, Branched olefins (Branched olefin), Linear internal olefins (Linear internal olefin), isoparaffins (iso-paraffin), n-paraffins (n-paraffin), and naphthenes (naphthene) are produced as by-products. These byproducts can be used as fuels, but their value is very low.

Therefore, there is a need for a solution that allows for high value-added by-products of the process for the production of linear alpha-olefins.

Disclosure of Invention

Technical problem to be solved

An object of an embodiment of the present invention is to provide a method for producing paraffins, in which byproducts of a process for producing linear alpha-olefins are converted into paraffins with high conversion rates, so that the byproducts have high added values, and thus economy can be improved.

Technical scheme

One embodiment of the present invention provides a process for preparing paraffinic hydrocarbons, said process comprising the steps of: providing a feed comprising 30 to 100 mole percent Branched olefins (Branched olefins) and 0 to 50 mole percent Linear internal olefins (Linear internal olefins) with the balance being other by-products; and subjecting the feed to hydrogenation (hydrogenation).

In the process for producing paraffinic hydrocarbons according to one embodiment of the present invention, the feed may be directly subjected to hydrogenation.

The feed may comprise from 60 to 95 mole percent branched olefins and from 1 to 20 mole percent linear internal olefins.

Other by-products may include isoparaffins (iso-paraffins), n-paraffins (n-paraffins), naphthenes (naphthenes), or combinations thereof.

The branched olefin may be a C4 to C20 branched olefin.

The hydrogenation step may be carried out in a trickle bed reactor (trickle bed reactor).

The feed may flow into the reactor in the liquid phase and the Space Velocity (SV) of the feed may be in the range of 0.1 to 4h^-1。

The hydrogenation step may be carried out in the presence of a metal catalyst at a temperature of 100-200 ℃ and 10-100kg/cm²g, the metal catalyst is selected from nickel (Ni), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Lu), and an alloy containing 2 or more of them.

After the hydrogenation step, a step of separating the paraffins produced may also be included.

After the hydrogenation step, a step of separating the isoparaffins from the produced paraffins may also be included.

Advantageous effects

According to the method for preparing paraffin according to one embodiment of the present invention, the by-product of the process for preparing linear alpha-olefin can be converted into paraffin with high conversion, and thus the by-product can be given high added value.

In addition, a large amount of branched olefins are contained in the by-products of the process for producing linear alpha-olefins, and therefore, by converting the by-products into paraffins, isoparaffin solvents used in various fields as commercial chemical products can be produced, and the high value-added effect of the by-products can be maximized.

Drawings

Fig. 1 is an exemplary process diagram of a process for producing isoparaffins in accordance with one embodiment of the present invention.

Fig. 2 is a schematic diagram illustrating in more detail the process 10 for the preparation of linear alpha olefins according to one embodiment of the present invention.

Detailed Description

Unless otherwise defined, all terms (including technical and scientific terms) used in the present specification may have meanings commonly understood by those skilled in the art to which the present invention belongs. Unless specifically stated to the contrary, when a portion "includes" or "includes" a constituent element is described throughout the specification, it means that other constituent elements may be included, but not excluded. Furthermore, the singular forms also include the plural forms unless otherwise specified.

Throughout this specification, "paraffinic" means a C4-C50 saturated hydrocarbon unless specifically defined otherwise.

An embodiment of the present invention provides a method for preparing paraffin, in which paraffin is prepared from a byproduct of a process for preparing linear alpha-olefin, the method comprising the step of hydrogenating the byproduct of the process for preparing linear alpha-olefin.

As described above, in the production process of linear α -olefins, branched olefins, linear internal olefins, isoparaffins, normal paraffins, and naphthenes are produced as by-products, and although they can be used as fuels, their values are very low, and therefore it is necessary to make the by-products have high added values.

According to the method for preparing paraffin according to one embodiment of the present invention, by-products of such a process for preparing linear alpha-olefins are used as a feed, and paraffin is produced through a hydrogenation process, so that the by-products can be given high added values.

Specifically, the by-products of the process for the preparation of linear alpha-olefins may comprise 30 to 100 mole% branched olefins, 0 to 50 mole% linear internal olefins and 0 to 30 mole% other by-products comprising isoparaffins, n-paraffins, naphthenes and the like, relative to the total 100 mole% of the by-products.

More specifically, the by-products of the process for the preparation of linear alpha-olefins may comprise 40 to 95 mole%, 50 to 95 mole%, or 60 to 95 mole% branched olefins, and may comprise 1 to 40 mole%, 1 to 30 mole%, or 1 to 20 mole% linear internal olefins, and may comprise the balance other by-products comprising isoparaffins, n-paraffins, naphthenes, and the like.

Since the by-products of such a process for producing linear alpha-olefins are hydrogenated to produce paraffins, and the produced branched isoparaffins and linear paraffin products can be used as raw materials in various industrial fields, the by-products can be given high added values.

The thus produced paraffin is a material that can be used in a very wide range of fields, and therefore, a high added value can be achieved as compared with when a byproduct of a production process of linear alpha-olefins is used as a fuel.

In addition, branched olefins by-products may include C4 to C20 branched olefins, and more particularly, C6 to C20 branched olefins, and isoparaffin solvents prepared by hydrogenation of such branched olefins may have higher added value as commercial chemical products for various fields such as adhesives, paints, coating agents, reaction solvents, agricultural chemical fields, and the like.

In the hydrogenation step of the method for preparing paraffinic hydrocarbons according to one embodiment of the present invention, the by-products of the process for preparing linear alpha-olefins may be directly hydrogenated.

Herein, "directly performing hydrogenation" may mean that the by-product generated in the process for preparing linear alpha-olefins is subjected to a hydrogenation step itself without further treatment process in which a chemical reaction such as isomerization (isomerization) or the like occurs.

As described above, the by-product of the process for producing linear alpha-olefins contains branched olefins of 30 mol% or more, more specifically, contains a large amount of branched olefins of 40 mol% or more, 50 mol% or more, or 60 mol% or more, and contains linear internal olefins of 50 mol% or less, more specifically, contains linear internal olefins of 40 mol% or less, 30 mol% or less, or 20 mol% or less, and thus hydrogenation can be directly performed without a separate isomerization process, whereby higher added value can be achieved, and an isoparaffin product that can be directly used industrially can be produced.

Of course, in one embodiment of the present invention, the separation and removal of linear internal olefins by a simple separation process or the like that does not chemically react prior to the hydrogenation process is not excluded.

In the process for producing paraffinic hydrocarbons according to one embodiment of the present invention, the hydrogenation step may be carried out in the presence of a hydrogenation catalyst at a temperature of 100 ℃ and 200 ℃ and a pressure of 10 to 100kg/cm²g under pressure. However, the present invention is not limited thereto.

The hydrogenation step is not limited to a specific reactor type, and may be performed using various reactors such as a batch reactor (batch reactor), a Continuous Stirred Tank Reactor (CSTR), a continuous Plug Flow Reactor (PFR), a fixed bed reactor (fixed bed reactor), and a trickle bed reactor (trickle reactor).

In one embodiment of the specific hydrogenation step, for example, the by-product of the process for producing linear alpha-olefins may be continuously injected in a liquid phase into a reactor filled with a catalyst to perform hydrogenation, wherein the above pressure is maintained by hydrogen supplied into the reactor, but is not limited thereto.

In a more specific embodiment, the by-product of the liquid phase of the process for the preparation of linear alpha-olefins can be continuously injected in a counter-current direction or a co-current direction into a trickle bed reactor packed with catalyst and hydrogen for the hydrogenation. In the trickle bed reactor, the packed catalyst can be well contacted with the by-product in the liquid phase, with the advantage of excellent reaction efficiency.

Further, more than 2 reactors may be provided as necessary, but this is only an example and is not intended to limit the present invention.

Wherein the Space Velocity (SV) of the liquid phase by-product inflow can be 0.1-4h^-1More specifically, it may be 0.5 to 3 hours^-1Or 1-2h^-1. The space velocity of the by-product in the present specification can be determined by the inflow velocity (m) of the by-product³H) divided by the reaction volume in the reactor (m)³) The reaction volume is calculated to mean a space in the reactor where by-products other than the space filled with the catalyst can flow. Within the above range, the hydrogenation reaction efficiency is excellent, and the yield of isoparaffin can be increased.

More specifically, as the hydrogenation catalyst, a catalyst in the form of a metal catalyst supported on a carrier contributing to catalytic activity may be used.

Wherein the metal catalyst may be nickel (Ni), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Lu) or an alloy containing 2 or more of them such as a platinum-palladium alloy, and the support may be alumina (Al)₂O₃) Silicon dioxide (SiO)₂) Titanium dioxide (TiO)₂) Zirconium dioxide (ZrO)₂) Zeolite, clay material, or combinations thereof, but is not limited thereto.

Further, as an example, the supported amount of the metal catalyst supported on the carrier may be 10 to 40% by weight, more specifically, 15 to 30% by weight, relative to 100% by weight of the catalyst in which the metal catalyst is supported on the carrier.

In the method for producing paraffins according to an embodiment of the present invention, after the hydrogenation step, a step of separating the produced paraffins may be further included.

This step may be a step of hydrogenating a by-product of the process for preparing linear alpha-olefins to prepare paraffins, and then separating the prepared paraffins from reaction additives such as a catalyst, and the remaining reactants of the process for preparing linear alpha-olefins contained in the obtained product, a catalyst deactivator for terminating the reaction, a remaining reactant of the hydrogenation step, a catalyst, and the like.

The specific method for performing this step is not limited to one specific method by which the produced paraffins can be separated, and may be appropriately selected from distillation, adsorption, crystallization, extraction, or a combination thereof according to the embodiment of the process.

In addition, in the method for preparing paraffins according to an embodiment of the present invention, after the hydrogenation step, a step of separating isoparaffins from the produced paraffins may be further included.

This step may be a step of separating isoparaffin that may have higher added value from a paraffin product in which straight-chain paraffins and the like are mixed with isoparaffin.

The specific method for performing this step is not limited to one specific method by which the produced isoparaffin can be separated, and may be appropriately selected from distillation, adsorption, crystallization, extraction, or a combination thereof according to the embodiment of the process.

In addition, the order of the step of separating the produced paraffins after the above hydrogenation step and the step of separating the isoparaffins from the produced paraffins after the hydrogenation step is not limited to a specific order, and may be performed in an order of separating the produced paraffins first and then intentionally separating the isoparaffins, or may be performed in a manner of further purifying the separated isoparaffins by separating the isoparaffins first and then performing a further purification process.

Fig. 1 is an exemplary process diagram of a process for producing isoparaffins in accordance with one embodiment of the present invention. The present invention will be further described below with reference to fig. 1. However, the present invention is not limited to the embodiment of the process of FIG. 1.

The by-product of the liquid phase having the above content is added to the hydrogenation process 20 as a by-product of the preparation process 10 of the linear alpha-olefin. In the hydrogenation process 20, the by-products are hydrogenated to produce isoparaffins. Thereafter, the reaction product containing the prepared isoparaffin is introduced into the isoparaffin purification process 30, subjected to a process of separating paraffin and/or isoparaffin in the reaction product, and finally produced. Specific embodiments of the hydrogenation process 20 and the isoparaffin purification process 30 are described above.

Fig. 2 is a schematic diagram illustrating in more detail the process 10 for the preparation of linear alpha olefins according to one embodiment of the present invention, and an exemplary embodiment of the process 10 for the preparation of linear alpha olefins is illustrated with reference to fig. 2.

First, the apparatus of the process 10 for preparing linear alpha-olefins may include: a linear alpha-olefin production reactor 40 for carrying out oligomerization reaction; an injection line 50 for injecting olefins and catalyst composition into the linear alpha olefin producing reactor 40; an effluent line 60 for flowing an oligomerization reaction product from the linear alpha olefin production reactor 40; a catalyst deactivator injection line 70 for adding a catalyst deactivator to the outflow line 60; a still 80 for separating the oligomerization product; and a recycle line 90 for recycling unreacted olefins in the effluent discharged to the effluent line 60, in which case the catalyst composition is an olefin oligomerization catalyst composition described below, and may comprise a transition metal source and a heteroatom ligand or an oligomerization transition metal catalyst prepared therefrom, a cocatalyst, and a solvent.

The linear alpha olefin producing reactor 40 may include a batch reactor, a semi-batch reactor, and a continuous reactor, but is not limited thereto.

The distiller 80 is not limited to a specific type of distiller, and the number of stages of the distillation column may be adjusted as necessary. The distillation method is not limited to a specific one, and an appropriate distillation method may be used as needed. As one example, a plurality of distillation columns including a Bottom reboiler (BTM reboiler) and a top condenser (OVHD condensor) and having the number of stages of 50 or more and 100 or less may be used.

Further, although not shown in fig. 2, when an oxygen-containing inorganic substance that is gaseous at 25 ℃ and 1 atmosphere (atm), which will be described later, is used as the catalyst deactivator, an adsorption column (not shown) may be further provided on the recycle line 90. Therefore, when recycling the unreacted olefin, most of the unreacted catalyst deactivator can be removed by adsorption.

The adsorption column (not shown) may utilize an adsorption column packed with an adsorbent that can adsorb oxygen-containing inorganic substances contained in the catalyst deactivator, which are gaseous at 25 ℃ and 1 atmosphere (atm). The number of the adsorption columns may be adjusted as necessary without particular limitation. As a non-limiting example of the adsorbent, as an adsorbent that can adsorb to remove the oxygen-containing inorganic substance, a metal oxide or zeolite adsorbent may be used, and as a specific example, CuO, Cu may be used₂Copper oxide such as O, or Zeolite 4A (Zeolite 4A).

In the specific paraffin preparation embodiment of the present invention, the by-product added from the linear alpha olefin production process 10 to the hydrogenation process 20 may be directly obtained from the linear alpha olefin production reactor 40 in the linear alpha olefin production process 10, or may be a by-product remaining after a part of the products, such as 1-hexene and 1-octene, are recovered by distillation in the distiller 80. More preferably, the high value-added product may be obtained by separating a by-product remaining after a part of the product such as 1-hexene and 1-octene is recovered by distillation, and when an isoparaffin is produced from the remaining by-product containing a large amount of branched α -olefins according to an embodiment of the present invention, the high value-added product of the whole process may be further maximized, which is preferable.

Hereinafter, a process for producing linear alpha-olefins, which is a source of by-products used in producing paraffins according to an embodiment of the present invention, will be described in more detail. However, this is an example, and the present invention is not necessarily limited thereto.

The process for preparing linear alpha-olefins may include the step of oligomerizing olefin monomers in the presence of a transition metal catalyst, a co-catalyst, and a solvent.

The solvent may be an inert solvent. That is, any inert solvent that does not react with the oligomerization transition metal catalyst, the cocatalyst, and the catalyst deactivator may be used, and the inert solvent may include an aliphatic hydrocarbon. The aliphatic hydrocarbon is a saturated aliphatic hydrocarbon containing_nH_2n+2(wherein n is an integer of 1 to 15), a straight-chain saturated aliphatic hydrocarbon represented by C_mH_2mAlicyclic saturated aliphatic hydrocarbons represented by (wherein m is an integer of 3 to 8), and saturated aliphatic hydrocarbons in which one or more lower alkyl groups having 1 to 3 carbon atoms are substituted. As a specific example, the solvent is one or more selected from the group consisting of hexane, heptane, octane, nonene, decane, undecane, dodecane, tetradecane, 2-dimethylpentane, 2, 3-dimethylpentane, 2, 4-dimethylpentane, 3-dimethylpentane, 2, 4-trimethylpentane, 2,3, 4-trimethylpentane, 2-methylhexane, 3-methylhexane, 2-dimethylhexane, 2, 4-dimethylhexane, 2, 5-dimethylhexane, 3, 4-dimethylhexane, 2-methylheptane, 4-methylheptane, cyclohexane, methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, 1, 4-dimethylcyclohexane and 1,2, 4-trimethylcyclohexane, but is not limited thereto.

The reaction temperature of the oligomerization step may be a temperature of 0 to 200 ℃, specifically 15 to 130 ℃, more specifically 40 to 100 ℃, but is not limited thereto. The reaction pressure may be a pressure of atmospheric pressure to 500 bar (bar), specifically may be a pressure of atmospheric pressure to 100 bar, and more specifically may be a pressure of atmospheric pressure to 80 bar. However, the present invention is not limited thereto.

The transition metal catalyst may be prepared and used as it is, or a commercially available oligomerization catalyst may be used, and the constituent components that can prepare the transition metal catalyst, i.e., the transition metal source and the heteroatom ligand, may also be used.

The transition metal source of one embodiment of the present invention may be a transition metal inorganic salt, a transition metal organic salt, a transition metal complex compound or a complex of a transition metal and an organic metal, and the transition metal of the transition metal source may be a transition metal of group IV, group V or group VI, specifically, chromium, molybdenum, tungsten, titanium, tantalum, vanadium or zirconium, and preferably, chromium.

As an example, the transition metal of the transition metal source may be combined with various organic ligands, which may be selected from the following structures.

Wherein R is⁴¹-R⁴⁵Each independently is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl group.

The organic ligand may preferably be an acetylacetonate-based ligand represented by the following chemical formula 2.

In chemical formula 2, R⁴⁶-R⁴⁸Each independently hydrogen, halogen, (C6-C20) aryl, (C6-C20) aryl (C1-C10) alkyl, (C1-C10) alkyl, halo (C1-C10) alkyl, (C6-C20) aryl (C2-C10) alkenyl, (C2-C10) alkenyl, (C6-C20) aryl (C2-C10) alkynyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6-C20) aryloxy, (C1-C10) alkylcarbonyloxy, (C2-C10) alkenylcarbonyloxy, (C2-C10) alkynylcarbonyloxy, (C3-C7) cycloalkyl, (C1-C10) alkylsilyl, (C2-C10) alkenylsilyl, fluorine substituted (C2-C10) alkynylsilyl, (C6-C20) arylsilyl, (C3-C20) heteroaryl or 5-7 membered heterocycloalkyl;

R⁴⁶-R⁴⁸aryl, arylalkyl, alkyl, arylalkenyl, alkenyl, arylalkynyl, alkynyl, alkoxy, aryloxy, cycloalkyl, heteroaryl and heteroThe cycloalkyl group may be further substituted with one or more selected from (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6-C20) aryl, (C6-C20) aryloxy and halogen.

Preferably, in chemical formula 2, R⁴⁶And R⁴⁷May each independently be hydrogen, halogen or halo (C1-C10) alkyl, R⁴⁸May be hydrogen or (C1-C10) alkyl.

The acetylacetonate-based ligand of chemical formula 2 according to one embodiment of the present invention may be selected from the following structures, but is not limited thereto.

As a specific example of the transition metal source, when the transition metal is chromium, the transition metal source may be one or more selected from chromium (III) acetylacetonate, chromium (III) chloride, chromium (III) naphthenate, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) 2,2,6, 6-tetramethylpimelate, chromium (III) octanoate, and chromium hexacarbonyl, and preferably may be chromium (III) acetylacetonate or chromium (III) chloride.

Preferably, the heteroatomic ligand according to one embodiment of the present invention may be (R)_nB-C-D(R)_mWherein B and D are independently any one selected from the group consisting of phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium and nitrogen, C is a linking group between B and D, R is the same or different and is each independently selected from the group consisting of hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl and substituted heterohydrocarbyl, N and m can each be determined by the valence and oxidation state of B or D, preferably, B and D are independently phosphorus, C is a linking group between B and D and can be alkylene or N (R ') (where R' is alkyl), R is the same or different and is each independently selected from the group consisting of hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl and substituted heterohydrocarbyl, and N and m can each be determined by the valence and oxidation state of B or D.

The heteroatom ligand may be a P-C-P main chain structure represented by the following chemical formula 3 or a P-N-P main chain structure represented by chemical formula 4, but is not limited thereto.

In chemical formulae 3 and 4, R⁵¹-R⁵⁴Each independently is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl group;

R⁵⁵and R⁵⁶Each independently is hydrocarbyl or substituted hydrocarbyl, or R⁵⁵And R⁵⁶May be joined to each other through a hydrocarbylene group, substituted hydrocarbylene group, heterohydrocarbylene group or substituted heterohydrocarbylene group to form a ring.

R in chemical formulas 3 and 4⁵¹-R⁵⁴Each independently is (C6-C20) aryl, (C6-C20) aryl (C1-C10) alkyl, (C6-C20) aryl (C2-C10) alkenyl, (C6-C20) aryl (C20-C20) alkynyl, (C20-C20) alkyl, (C20-C20) alkenyl, (C20-C20) alkynyl, (C20-C20) alkoxy, (C20-C20) aryloxy, (C20-C20) alkoxycarbonyl, (C20-C20) alkylcarbonyloxy, (C20-C20) alkenylcarbonyloxy, (C20-C20) alkynylcarbonyloxy, aminocarbonyl, (C20-C20) alkylcarbonylamino, (C20-C20) alkenylcarbonylamino, (C20-C20) alkynylcarbonylamino, (C20-C20) cycloalkylthio (C20-C20) alkyl (C20) alkenyl (C20) alkyl, Thio (C2-C10) alkynyl, (C1-C10) alkylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl, (C6-C20) arylsilyl, (C3-C20) heteroaryl, 5-7 membered heterocycloalkyl, or-NR⁶¹R⁶²，R⁶¹And R⁶²Each independently is (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C6-C20) aryl, di (C1-C10) alkylamino, di (C2-C10) alkenylamino, or di (C2-C10) alkynylamino;

R⁵⁵and R⁵⁶Each independently is (C6-C20) aryl, (C6-C20) aryl (C1-C10) alkyl, (C6-C20) aryl (C2-C10) alkenyl, (C6-C20) aryl (C2-C10) alkynyl, (C1-C10) alkyl, (C10-C10) alkenyl, (C10-C10) alkynyl, (C10-C10) cycloalkyl, (C10-C10) heteroaryl, 5-7 membered heterocycloalkyl, (C10-C10) alkoxy, (C10-C10) aryloxy, (C10-C10) alkoxycarbonyl, (C10-C10) alkylcarbonyloxy, (C10-C10) alkenylcarbonyloxy, (C10-C10) alkynylcarbonyloxy, aminocarbonyl, (C10-C10) alkylcarbonylaminocarbonyl, (C10-C10) alkenylcarbonylamino, (C10-C10) alkynylcarbonyloxy, or (C10-C10) alkynylcarbonylAmino, di (C1-C10) alkylamino, di (C2-C10) alkenylamino, di (C2-C10) alkynylamino, (C1-C10) alkylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C6-C20) arylsilyl, or R⁵⁵And R⁵⁶May be linked to form a ring via a (C3-C10) alkylene or (C3-C10) alkenylene group;

R⁵¹-R⁵⁴aryl, arylalkyl, arylalkenyl, arylalkynyl, alkyl, alkenyl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkyl, heteroaryl, heterocycloalkyl and R⁵⁵And R⁵⁶The aryl, arylalkyl, arylalkenyl, arylalkynyl, alkyl, alkenyl, cycloalkyl, heteroaryl, heterocycloalkyl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, aminocarbonyl, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, dialkylamino, dienylamino, dialkynylamino, alkylsilyl, alkenylsilyl, alkynylsilyl, or arylsilyl groups of (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6-C20) aryloxy, di (C1-C10) alkylamino, di (C2-C10) alkenylamino, di (C2-C10) alkynylamino and halogen may be further substituted with one or more than one.

Preferably, in chemical formulas 3 and 4, R⁵¹-R⁵⁴Each independently is (C6-C20) aryl; r⁵⁵And R⁵⁶May each independently be a (C1-C10) alkyl group.

Specifically, in chemical formulas 3 and 4, R⁵¹-R⁵⁴Each is phenyl, benzyl, biphenyl, naphthyl, anthracenyl, mesityl, xylyl, methyl, ethyl, vinyl, ethynyl, n-propyl, isopropyl, propenyl, propynyl, n-butyl, tert-butyl, butenyl, butynyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, isopropylphenyl, isopropoxyphenyl, tert-butylphenyl, cumyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylaminophenyl, cyclopropyl, cyclobutyl, cyclopentyl, orHexyl, methylcyclohexyl, ethylcyclohexyl or isopropylcyclohexyl, dimethylamino, thiomethyl, trimethylsilyl and dimethylhydrazino;

R⁵⁵and R⁵⁶Each independently is methyl, ethyl, ethenyl, ethynyl, n-propyl, isopropyl, propenyl, propynyl, n-butyl, tert-butyl, isobutyl, butenyl, butynyl, phenyl, benzyl, tolyl, xylyl, methoxy, ethoxy, phenoxy, methylamino, dimethylamino, or R⁵⁵And R⁵⁶The linkage may be through propylene, butylene, pentylene, or butylenyl to form a 5-7 membered ring.

The ligand of the P-C-C-P backbone structure of chemical formula 3 may be selected from (phenyl)₂P-CH (methyl) -P (phenyl)₂, (4-methoxyphenyl)₂P-CH (methyl) -P (4-methoxyphenyl)₂(4-methylphenyl)₂P-CH (methyl) -P (4-methylphenyl)₂(4-ethylphenyl)₂P-CH (methyl) -P (phenyl)₂(2-ethylphenyl)₂P-CH (methyl) -P (2-ethylphenyl)₂(2-isopropylphenyl)₂P-CH (methyl) P- (2-isopropylphenyl)₂2- (methyl phenyl)₂P-CH (methyl) P- (2-methylphenyl)₂(2-ethylphenyl)₂P-CH (methyl) -P (phenyl)₂, (3-methoxyphenyl)₂P-CH (methyl) -P (3-methoxyphenyl)₂, (4-ethoxyphenyl)₂P-CH (methyl) -P (2-ethoxyphenyl)₂, (4-dimethylaminophenyl)₂P-CH (methyl) -P (4-dimethylaminophenyl)₂, (4-ethylcyclohexyl)₂P-CH (methyl) -P (4-ethylcyclohexyl)₂, (2-methoxyphenyl)₂P-CH (methyl) -P (2-methoxyphenyl)₂2- (2-ethoxyphenyl)₂P-CH (methyl) -P (2-ethoxyphenyl)₂2- (2-dimethylaminophenyl)₂P-CH (methyl) -P (2-dimethylaminophenyl)₂, (2-ethylcyclohexyl)₂P-CH (methyl) -P (2)-ethylcyclohexyl)₂(4-ethylphenyl)₂P-CH (ethyl) CH (methyl) -P (4-ethylphenyl)₂, (4-methoxyphenyl)₂P-CH (ethyl) CH (methyl) -P (phenyl)₂(2-ethylphenyl)₂P-CH (ethyl) CH (methyl) -P (2-ethylphenyl)₂(4-ethylphenyl)₂P-CH (ethyl) -P (4-ethylphenyl)₂, (phenyl)₂P-CH (ethyl) -P (phenyl)₂(2-ethylphenyl)₂P-CH (ethyl) -P (2-ethylphenyl)₂, (phenyl)₂P-CH (isopropyl) CH (methyl) -P (phenyl)₂, (4-methoxyphenyl)₂P-CH (isopropyl) CH (methyl) -P (4-methoxyphenyl)₂(4-ethylphenyl)₂P-CH (isopropyl) CH (methyl) -P (4-ethylphenyl)₂(2-ethylphenyl)₂P-CH (isopropyl) CH (methyl) -P (2-ethylphenyl)₂, (phenyl)₂P-CH (n-propyl) CH (methyl) -P (phenyl)₂, (4-methoxyphenyl)₂P-CH (n-propyl) CH (methyl) -P (4-methoxyphenyl)₂(4-ethylphenyl)₂P-CH (n-propyl) CH (methyl) -P (4-ethylphenyl)₂(2-ethylphenyl)₂P-CH (n-propyl) CH (methyl) -P (2-ethylphenyl)₂, (phenyl)₂P-CH (isopropyl) CH (ethyl) -P (phenyl)₂, (4-methoxyphenyl)₂P-CH (isopropyl) CH (ethyl) -P (4-methoxyphenyl)₂(4-ethylphenyl)₂P-CH (isopropyl) CH (ethyl) -P (4-ethylphenyl)₂(2-ethylphenyl)₂P-CH (isopropyl) CH (ethyl) -P (2-ethylphenyl)₂1, 2-bis- (P (phenyl)₂) Cyclohexane, 1, 2-bis- (P (4-methoxyphenyl)₂) Cyclohexane, 1, 2-bis- (P (4-ethylphenyl)₂) Cyclohexane, 1, 2-bis- (P (2-ethylphenyl)₂) Cyclohexane, 1, 2-bis- (P (phenyl)₂) Cyclopentane, 1, 2-bis- (P (4-methoxyphenyl)₂) Cyclopentane, 1, 2-bis- (P (4-ethylphenyl)₂) Cyclopentane, 1, 2-bis- (P (2-ethylphenyl)₂) Cyclopentane, (4-ethylphenyl)₂P-CH (dimethylamino) -P (4-ethylphenyl)₂And (2-ethylphenyl)₂P-CH (dimethyl)Alkylamino) CH (dimethylamino) -P (2-ethylphenyl)₂However, the present invention is not limited thereto.

The ligand of the P-N-P main chain structure of chemical formula 4 may be selected from (phenyl)₂PN (methyl) P (phenyl)₂, (phenyl)₂PN (pentyl) P (phenyl)₂, (phenyl)₂PN (phenyl) P (phenyl)₂, (phenyl)₂PN (P-methoxyphenyl) P (phenyl)₂, (phenyl)₂PN (P-tert-butylphenyl) P (phenyl)₂, (phenyl)₂PN((CH₂)₃-N-morpholine P (phenyl)₂, (phenyl)₂PN(Si(CH₃)₃) P (phenyl)₂((phenyl)₂P)₂NCH₂CH₂) N, (ethyl)₂PN (methyl) P (ethyl)₂, (ethyl)₂PN (isopropyl) P (phenyl)₂(ethyl) (phenyl) PN (methyl) P (ethyl) (phenyl), (ethyl) (phenyl) PN (isopropyl) P (phenyl)₂, (phenyl)₂P (═ Se) N (isopropyl) P (phenyl)₂, (phenyl)₂PCH₂CH₂P (phenyl)₂(o-ethylphenyl) (phenyl) PN (isopropyl) P (phenyl)₂, (o-methylphenyl)₂PN (isopropyl) P (o-methylphenyl) (phenyl), (phenyl)₂PN (benzyl) P (phenyl)₂, (phenyl)₂PN (1-cyclohexylethyl) P (phenyl)₂, (phenyl)₂PN[CH₂CH₂CH₂Si(OMe₃)]P (phenyl)₂, (phenyl)₂PN (cyclohexyl) P (phenyl)₂, (phenyl)₂PN (2-methylcyclohexyl) P (phenyl)₂, (phenyl)₂PN (allyl) P (phenyl)₂2- (2-naphthyl)₂PN (methyl) P (2-naphthyl)₂, (p-biphenylyl)₂PN (methyl) P (P-biphenylyl)₂(p-methylphenyl)₂PN (methyl) P (P-methylphenyl)₂(2-Thiophenyl)₂PN (methyl) P (2-thiophenyl)₂, (phenyl)₂PN (methyl) N (methyl) P (phenyl)₂, (m-methylphenyl)₂PN (methyl) P (m-methylphenyl)₂, (phenyl)₂PN (isopropyl) P (phenyl)₂And (benzene)Base)₂P (═ S) N (isopropyl) P (phenyl)₂However, the present invention is not limited thereto.

The heteroatomic ligand constituting the transition metal catalyst of the present invention can be prepared using various methods known to those skilled in the art.

The transition metal catalyst of the present invention may be mononuclear or binuclear, and specifically may be constituted of ML¹(L²)_p(X)_qOr M₂X¹ ₂L¹ ₂(L²)_y(X)_zIs represented by, wherein M is a transition metal, L¹Is a heteroligand, L²Is an organic ligand, X and X¹Each independently is halogen, p is 0 or an integer of 1 or more, q is an integer of (the oxidation number of M-p), y is an integer of 2 or more, and z is an integer of (the oxidation number of 2 × M) -y-2.

Preferably, the transition metal catalyst according to an embodiment of the present invention may be represented by the following chemical formula 5 or chemical formula 6, but is not limited thereto.

In chemical formulas 5 and 6, R⁴⁶-R⁴⁸Each independently hydrogen, halogen, (C6-C20) aryl, (C6-C20) aryl (C1-C10) alkyl, (C1-C10) alkyl, halo (C1-C10) alkyl, (C6-C20) aryl (C2-C10) alkenyl, (C2-C10) alkenyl, (C6-C20) aryl (C2-C10) alkynyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6-C20) aryloxy, (C1-C10) alkylcarbonyloxy, (C2-C10) alkenylcarbonyloxy, (C2-C10) alkynylcarbonyloxy, (C3-C7) cycloalkyl, (C1-C10) alkylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl, (C6-C20) arylsilyl, (C3-C20) heteroaryl or 5-7 membered heterocycloalkyl;

R⁴⁶、R⁴⁷and R⁴⁸The aryl, arylalkyl, alkyl, arylalkenyl, alkenyl, arylalkynyl, alkynyl, alkoxy, aryloxy, cycloalkyl, heteroaryl and heterocycloalkyl of (C) may be further substituted with a substituent selected from the group consisting of (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6-C20) aryl, substituted heteroaryl, and substituted heteroaryl,(C6-C20) aryloxy and halogen,

R⁵¹-R⁵⁴each independently is (C6-C20) aryl, (C6-C20) aryl (C1-C10) alkyl, (C6-C20) aryl (C2-C10) alkenyl, (C6-C20) aryl (C20-C20) alkynyl, (C20-C20) alkyl, (C20-C20) alkenyl, (C20-C20) alkynyl, (C20-C20) alkoxy, (C20-C20) aryloxy, (C20-C20) alkoxycarbonyl, (C20-C20) alkylcarbonyloxy, (C20-C20) alkenylcarbonyloxy, (C20-C20) alkynylcarbonyloxy, aminocarbonyl, (C20-C20) alkylcarbonylamino, (C20-C20) alkenylcarbonylamino, (C20-C20) alkynylcarbonylamino, (C20-C20) cycloalkylthio (C20-C20) alkyl (C20) alkenyl (C20) alkyl, Thio (C2-C10) alkynyl, (C1-C10) alkylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl, (C6-C20) arylsilyl, (C3-C20) heteroaryl, 5-7 membered heterocycloalkyl, or-NR²¹R²²，R²¹And R²²Each independently is (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C6-C20) aryl, di (C1-C10) alkylamino, di (C2-C10) alkenylamino, or di (C2-C10) alkynylamino;

R⁵⁵and R⁵⁶Each independently is (C6-C20) aryl, (C6-C20) aryl (C1-C10) alkyl, (C6-C20) aryl (C2-C10) alkenyl, (C6-C20) aryl (C2-C10) alkynyl, (C1-C10) alkyl, (C10-C10) alkenyl, (C10-C10) alkynyl, (C10-C10) cycloalkyl, (C10-C10) heteroaryl, 5-7 membered heterocycloalkyl, (C10-C10) alkoxy, (C10-C10) aryloxy, (C10-C10) alkoxycarbonyl, (C10-C10) alkylcarbonyloxy, (C10-C10) alkenylcarbonyloxy, (C10-C10) alkynylcarbonyloxy, aminocarbonyl, (C10-C10) alkylcarbonylaminocarbonyl, (C10-C10) alkenylcarbonylamino, (C10-C10) alkynylaminocarbonyloxy, (C10) alkynylaminocarbonylamino, Di (C1-C10) alkylamino, di (C2-C10) alkenylamino, di (C2-C10) alkynylamino, (C1-C10) alkylsilyl, (C2-C10) alkenylsilyl, (C2-C10) alkynylsilyl or (C6-C20) arylsilyl, or R⁴⁵And R⁴⁶May be linked to form a ring via a (C3-C10) alkylene or (C3-C10) alkenylene group;

R⁵¹-R⁵⁴aryl, arylalkyl, arylalkenyl, arylalkynyl, alkyl, alkenyl, alkoxy, aryloxy, alkoxycarbonyl, heteroarylalkyl, heteroaryl,Alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkyl, heteroaryl, heterocycloalkyl and R⁵⁵And R⁵⁶The aryl, arylalkyl, arylalkenyl, arylalkynyl, alkyl, alkenyl, cycloalkyl, heteroaryl, heterocycloalkyl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, aminocarbonyl, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, dialkylamino, dienylamino, dialkynylamino, alkylsilyl, alkenylsilyl, alkynylsilyl, or arylsilyl groups of (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C10) alkoxy, (C6-C20) aryloxy, di (C1-C10) alkylamino, di (C2-C10) alkenylamino, di (C2-C10) alkynylamino and halogen;

x is halogen; and a is 0 or an integer of 1 to 3, and b and c are each independently an integer of 1 or 2.

Preferably, the transition metal catalyst may be a compound of chemical formulas 5 and 6, wherein R⁴⁶-R⁴⁸Each independently is hydrogen, (C1-C10) alkyl or halo (C1-C10) alkyl, R⁵¹-R⁵⁴Each independently is (C6-C20) aryl; r⁵⁵And R⁵⁶Each independently is (C1-C10) alkyl, or the transition metal catalyst may be a compound of formulae 5 and 6, wherein R is⁵¹-R⁵⁴Each independently is (C6-C20) aryl; r⁵⁵And R⁵⁶Each independently is a (C1-C10) alkyl group and a is 0.

The cocatalyst can be an organoaluminum compound, an organoaluminoxane, an organoboron compound, or a mixture thereof.

The organoaluminum compound may be AlR₃(wherein each R is independently (C1-C12) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C1-C12) alkoxy or halogen) or LiAlH₄However, the present invention is not limited thereto.

More specifically, the organoaluminum compound may be one or a mixture of two or more selected from Trimethylaluminum (TMA), Triethylaluminum (TEA), Triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethylaluminum sesquichloride and methylaluminum sesquichloride, but the present invention is not limited thereto.

The organoaluminoxane may be an oligomer compound prepared by adding water to trimethylaluminum, but the present invention is not limited thereto. The aluminoxane oligomer compound thus prepared may be linear, cyclic, cage (cage) or a mixture thereof.

Specifically, the organic aluminoxane may be selected from alkylaluminoxanes such as Methylaluminoxane (MAO), Ethylaluminoxane (EAO), Tetraisobutylaluminoxane (TIBAO) and Isobutylaluminoxane (IBAO), and may also be selected from modified alkylaluminoxanes such as Modified Methylaluminoxane (MMAO). The modified methylaluminoxane (manufactured by Akzo Nobel corporation) may contain a mixed alkyl group such as an isobutyl group or an n-octyl group in addition to a methyl group. However, the present invention is not limited thereto.

More specifically, the organic aluminoxane may be one or a mixture of two or more selected from Methyl Aluminoxane (MAO), Modified Methyl Aluminoxane (MMAO), Ethyl Aluminoxane (EAO), tetraisobutyl aluminoxane (TIBAO), and isobutyl aluminoxane (IBAO), but the present invention is not limited thereto.

The organoboron compound may be boroxine, NaBH₄Triethylborane, triphenylborane ammonia complex, tributyl borate, triisopropyl borate, tris (pentafluorophenyl) borane, trityl (tetrapentafluorophenyl) borate, dimethylphenylammonium (tetrapentafluorophenyl) borate, diethylphenylammonium (tetrapentafluorophenyl) borate, methyldiphenylammonium (tetrapentafluorophenyl) borate, or ethyldiphenylammonium (tetrapentafluorophenyl) borate, and these organoboron compounds may be used in combination with the organoaluminum compound or the organoaluminoxane, but the present invention is not limited thereto.

In addition, the process for preparing linear alpha-olefins may further include a step of adding a catalyst deactivator to the reaction product of the oligomerization reaction after the step of conducting the oligomerization reaction.

The catalyst deactivator is added in order to control unnecessary side reactions at the end of the reactor and terminate the reaction when preparing the linear alpha-olefin, and in one embodiment of the present invention, the catalyst deactivator may comprise: an oxygen-containing inorganic substance which is gaseous at 25 ℃ and 1 atmosphere (atm); or an organic compound containing one or more functional groups containing at least one selected from oxygen, phosphorus, nitrogen and sulfur, and having a number average molecular weight of 400 or more.

When the catalyst deactivator as described above is used in the process for producing linear alpha-olefins, separation efficiency is improved when paraffins are purified after the preparation of the paraffins of the present invention, so that process energy can be reduced.

Specifically, when the catalyst deactivator including the oxygen-containing inorganic substance that is gaseous at 25 ℃ and 1 atmosphere (atm) is used, the catalyst deactivator can be separated and removed by a simple separation process such as distillation since the difference in boiling point is large when separated and purified from paraffin.

In the case of a catalyst deactivator comprising an organic compound which contains one or more functional groups containing at least one selected from oxygen, phosphorus, nitrogen and sulfur and has a number average molecular weight of 400 or more, the catalyst deactivator is a compound having a higher boiling point than the produced paraffin, and the catalyst deactivator can be separated and removed by inputting only low energy upon distillation.

Therefore, the process efficiency of the process for producing paraffinic hydrocarbons according to one embodiment of the present invention can be further improved, and thus is preferable. However, the present invention is not necessarily limited thereto, and the separation may be performed by adding a separate separation process or changing conditions even if the boiling point of the catalyst deactivator is between the boiling points of the paraffins to be produced.

As a non-limiting example, the oxygen-containing inorganic substance may be O₂、CO₂、CO、H₂O、NO_x、SO_xOr mixtures thereof. Specifically, the oxygen-containing inorganic substance may be O₂、CO₂CO or a mixture thereof, more particularly CO₂And O₂. Further specifically, CO₂Is a substance produced as a by-product or an exhaust gas in many industrial fields, can be purchased at low cost, and is therefore preferable in terms of improvement of process economy.

Among them, the exemplary examples of NOx may be NO, NO₂、N₂O、N₂O₃、N₂O₄、N₂O₅Or mixtures thereof, but the invention is not limited thereto.

SO_xCan be SO₂、SO₃Or mixtures thereof, but the invention is not limited thereto.

Specifically, the number average molecular weight of the organic compound may be 600 or more, 700 or more, or 1000 or more.

The upper limit of the number average molecular weight of the organic compound may be 10000 or less, 5000 or less, or 2000 or less, but is not limited thereto.

The organic compound may include one or more functional groups containing any one selected from oxygen, phosphorus, nitrogen, and sulfur, and as a specific embodiment, the organic compound may include one or more one functional group containing one of the four elements, or one or more two or more functional groups containing one of the four elements. This is exemplary, and the present invention is not limited thereto.

Specific examples of the organic compound include phosphine (phosphine) compounds having at least C31, amine (amine) compounds having at least C31, thiol (thiol) compounds having at least C31, alcohol (alcohol) compounds having at least C31, ether (ether) compounds having at least C31, ester (ester) compounds having at least C31, carboxylic acid (carboxylic acid) having at least C31, and ketone (ketone) compounds having at least C31.

More specifically, the organic compound may be a phosphine (phosphine) based compound having C31 or more, an amine (amine) based compound having C31 or more, a thiol (thiol) based compound having C31 or more, or an alcohol (alcohol) based compound having C31 or more.

Further specifically, the organic compound may be polypropylene glycol (PPG) represented by the following chemical formula 1.

In chemical formula 1, n is 11 or more and 170 or less.

More specifically, in chemical formula 1, n may be 12 or more and 150 or less, 17 or more and 130 or less, 17 or more and 110 or less, 17 or more and 35 or less, or 16 or more and 35 or less.

The catalyst deactivator of the present invention is not necessarily limited thereto, but among the alcohol compounds, such a polypropylene glycol compound has a more excellent catalyst deactivation effect than a polyethylene glycol compound, and can be easily separated from linear α -olefins in the oligomerization products of olefins, and is therefore preferable.

The olefin monomer is not particularly limited and may be, for example, ethylene, propylene or butene.

Hereinafter, preferred examples of the present invention and comparative examples are described. However, the following examples are merely preferred examples of the present invention, and the present invention is not limited to the following examples.

[ preparation examples ]

Bis [ (S, S) - (phenyl) dichloride was prepared as an oligomerization catalyst for ethylene by the following method₂PCH (methyl) CH (methyl) P (phenyl)₂Chromium (mu-chloro)](5.3μmol-Cr)。

2.1mg (5.3. mu. mol) of chromium trichloride tetrahydrofuran (CrCl)₃(THF)₃) Dissolved in 1mL of methylene chloride, and 2.4mg (5.6. mu. mol) of (S, S) - (phenyl) was slowly added to the solution₂PCH (methyl) CH (methyl) P (phenyl)₂The ligand compound was dissolved in 1mL of methylene chloride and reacted for 60 minutes. After stirring for a further 5 minutes, 1.3mg (5.6. mu. mol) of sodium hexafluoroacetylacetonate are slowly added. Subsequently, the reaction was stirred for another 3 hours and then filtered using a 0.2 μm pin filter (syringage filter). For the filtered liquidThe volatiles were removed under vacuum to give a dry dark green solid, which was used as the oligomerization catalyst in the following examples.

The catalyst is a catalyst having very excellent activity and selectivity for oligomerization of ethylene, and can be more clearly understood by referring to korean patent application No. 10-2016 0065709.

[ example 1]

A5.6L stainless steel pressure reactor was purged with nitrogen under vacuum, and then Methylcyclohexane (MCH) as a solvent was added at a rate of 2.0 kg/hr to apply 60kg/cm²g, and heating the temperature to 60 ℃. Methylaluminoxane (MAO, Albemarle, 1.2mmol/L MCH) and trimethylaluminum (TMA, Aldrich, 1.2mmol/L MCH) were added as cocatalysts, and then bis [ (S, S) - (phenyl) dichloride prepared in preparation example, was added in an amount of 2. mu. mol/L MCH₂PCH (methyl) CH (methyl) P (phenyl)₂Chromium (mu-chloro)]Then, ethylene was continuously supplied at 600 g/hr, the temperature was controlled by means of external jacket cooling (jack cooling), and hydrogen was added at a flow rate of 1g/kg of ethylene, thereby performing ethylene oligomerization reaction. At the rear end of the reactor, 10 equivalents of 2-ethylhexanol (2-ethylhexol) (Aldrich) as a catalyst deactivator were added with respect to the number of moles of aluminum in the cocatalyst added, thereby suppressing the catalytic activity so that no additional side reaction occurred.

Thereafter, the C10 or more component was first separated from the obtained product by distillation at 145 ℃ or more under normal pressure, and the polymer component was removed at 300 ℃. The separated substances were analyzed in detail for C10 component and C12 component by GC-FID and 2D-GC. The olefins (olefin) in the ingredients were classified into Branched alpha olefins (Branched alpha olefin), Branched internal olefins (Branched internal olefin), linear alpha olefins (linear alpha olefin), and linear internal olefins (linear internal olefin), and the results of quantitative analysis of the other ingredients are shown in table 1. It is known that C10 accounts for 36% by weight, C12 accounts for 45% by weight, and 80% by weight or more in total of the total composition, and the obtained product is composed of about 80 to 90 mol% of branched olefins (branched olefins), 4 to 12 mol% of linear olefins (linear olefins), 2 to 5 mol% of naphthene (naphthene) and paraffin (paraffin) components.

[ Table 1]

A15 mL stainless steel reactor was sufficiently filled with a hydrogenation catalyst (Ni/Alumina (Alumina) supporting catalyst, Ni 15 to 30 wt%), and then at 35kg/cm at 120 ℃²g was filled with hydrogen and the product obtained above was injected in the form of a trickle bed reaction at 0.4 cc/min, thereby carrying out hydrogenation. After the hydrogenation, as a result of GC analysis by the method described above, it was confirmed that no olefin component was detected and all of the olefin component was converted into paraffin.

After hydrogenation, 2-ethylhexanol (2-ethylhexanol) having a boiling point overlapping with that of the C10 substance was extracted using acetonitrile (acetonitrile) and removed. The thus obtained C10-C18 components were divided into 11 fractions (fractions) in a Distillation column of 60 stages, and as a result of measurement of Color (ASTM D156), Density (sensitivity) (ASTM D4052), Aniline point (Aniline point) (ASTM D611), Viscosity (Viscosity) (ASTM D445), Distillation (Distillation) (ASTM D86), Bromine index (Bromine index) (ASTM D1492), Aromatic content (GC-FID), it was confirmed that the spec (paraffin) specifications of commercial iso-products were satisfied as shown in table 2.

[ Table 2]

Description of reference numerals

10: process for the preparation of linear alpha-olefins

20: hydrogenation process

30: process for the purification of isoparaffins

40: reactor for preparing linear alpha-olefin

50: injection line

60: outflow line

70: catalyst deactivator injection line

80: distillation apparatus

90: recycle line