KR20220087986A - Method for producing ethylene oligomer and device for producing the same - Google Patents

Abstract

The present invention relates to a method for producing ethylene oligomer and an apparatus for producing ethylene oligomer, and more particularly, the present invention relates to a method for producing ethylene oligomer from one or more ethylene injection units present at different positions depending on the progress direction of the ethylene oligomerization reaction stream. Provided are a method for producing an ethylene oligomer by additionally supplying ethylene, and an apparatus for producing the same.

Description

Method for producing ethylene oligomer and apparatus for producing the same

The present invention relates to a method for producing an ethylene oligomer and an apparatus for producing an ethylene oligomer, and more particularly, to a method for producing an ethylene oligomer and an apparatus for producing an ethylene oligomer for increasing the selectivity and conversion rate of ethylene and improving the stability of reactivity .

Among ethylene oligomers, 1-hexene and 1-octene are materials used in large quantities as comonomers in the polymerization of polyolefins such as polyethylene, and polyolefin production using homogeneous metallocene catalysts is increasing. As a result, the demand for it is steadily increasing.

Conventionally, by oligomerizing ethylene in the Shell Higher Olefin Process (SHOP) based on a nickel catalyst, various 1-alkenes having about 4 to about 30 carbon atoms are produced, and from this, 1-hexene and / Alternatively, 1-octene could be separately obtained.

Thereafter, a catalyst system capable of producing 1-hexene or 1-octene in high yield by increasing the selectivity in the ethylene oligomerization reaction was developed.

As a representative example, US Patent 7511183B2 uses a chromium trivalent compound (CrCl ₃ or Cr(acac) ₃ ), a bisphosphine ligand (iPrN(PPh ₂ ) ₂ ) and methylaluminoxane (MAO). Thus, a method for preparing a catalyst capable of selectively producing 1-octene and 1-hexene has been reported.

However, the catalyst system has to use a large amount of expensive MAO (Al/Cr = 300 to 500) to realize a commercially usable level of activity, as well as polyethylene (PE), which seriously inhibits process stability. A problem of mass production has been reported (Organometallics, 27, 5712-5716).

In addition, the oligomerization catalyst system at a high temperature decreases the catalytic activity, so the production and selectivity of olefins, especially 1-octene, decreases. This causes a serious problem in the olefin polymerization process.

Specifically, polyethylene produced as a by-product forms a polymer layer, and a polymer layer is formed again on the formed polymer layer to lower the flow rate of the fluid, and the polymer coating layer formed along the reactor wall serves as an insulator that negatively affects heat transfer. will do In other words, pipe clogging and fouling occur, and a secondary low temperature is required to remove the polymer layer, resulting in frequent process shutdown.

Therefore, there is an improved process for producing ethylene oligomers that can produce 1-hexene and 1-octene with high selectivity without reducing catalytic activity, and significantly reduce the amount of polyethylene produced that inhibits process stability. is required

US Patent 7511183B2

Organometallics, 27, 5712-5716

The present invention is intended to solve the problems of the prior art as described above, and not only can produce 1-hexene and 1-octene with high selectivity, but also significantly reduce the amount of polyethylene produced that inhibits process stability without reducing catalyst activity. Provided are a method for producing an ethylene oligomer that can be reduced and an apparatus for producing an ethylene oligomer.

The present invention provides a method for producing an ethylene oligomer having process stability by suppressing polyethylene production while maintaining improved catalytic activity.

supplying a chromium catalyst or chromium source, an organic ligand and ethylene to form an ethylene oligomerization reaction stream; and

Comprising the step of supplying additional ethylene from one or more ethylene injection units present at different positions in the progress direction of the reaction stream,

The additionally supplied ethylene is supplied in an amount satisfying Equation 1 below.

[Equation 1]

FE _n-1 > FE _n

(In Equation 1 above,

n is an integer greater than or equal to 1, and is the nth ethylene injection unit located on the reaction stream according to the direction of travel of the reaction stream;

FE _n is the amount of ethylene supplied from the nth ethylene injection section;

provided that FE ₀ is the initial feed amount of ethylene fed to the step of forming the ethylene oligomerization reaction stream.)

Preferably, the additionally supplied ethylene according to an embodiment of the present invention may be supplied in an amount satisfying Equation 2 below.

[Equation 2]

2×FE ₀ ≥

(In Equation 2 above,

FE is the ethylene feed amount additionally fed from the ethylene injection section according to the order in which they are positioned in the reaction stream in the forward direction of the reaction stream;

n is an integer greater than or equal to 1, indicating the order of the ethylene injection starting from one end of the reaction stream;

provided that FE ₀ is the initial feed amount of ethylene fed to the step of forming the ethylene oligomerization reaction stream.)

The residence time of the reaction stream between each ethylene injection unit according to an embodiment of the present invention may be 0.1 to 2 hours.

The catalyst system according to an embodiment of the present invention may further include a catalyst activator, and may be included in an amount of 10 to 1000 moles based on 1 mole of chromium in the catalyst system.

Preferably, the chromium catalyst according to an embodiment of the present invention may be a chromium compound represented by the following formula (1).

[Formula 1]

[Formula 2]

Al(R ¹¹ )(R ¹² )(R ¹³ )

(In Formulas 1 and 2,

R is C1-C60 alkyl or C6-C60 aryl;

R ¹ to R ⁴ are each independently C1-C60 alkyl or C6-C60 aryl;

X ¹ and X ² are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate, or C1-C30 hydrocarbyl comprising at least one selected from ether and amino;

A is boron or aluminum;

Y ¹ to Y ⁴ are each independently fluorine-substituted C6-C60 aryl, fluorine-substituted C6-C60 aryloxy, or fluorine-substituted C6-C60 alkoxy;

R ¹¹ to R ¹³ are each independently C1-C20 alkyl;

Alkyl or aryl of R and alkyl or aryl of R ¹ to R ⁴ are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, monoC1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 Alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, tri C6-C30 arylamino, mono C1-C30 alkylsilyl, diC1-C30 alkylsilyl, triC1-C30 alkylsilyl, mono C6-C30 aryl It may be further substituted with one or more selected from silyl, diC6-C30 arylsilyl and triC6-C30 arylsilyl.)

Preferably, the chromium source according to an embodiment of the present invention may be a chromium compound represented by the following formula (3).

[Formula 3]

Cr(Z) _n (A) _m

(In Formula 3,

Z is each independently any one of a halogen group, an acetylacetonate group, or a carboxylate group,

A is an ether or acetonitrile having 2 to 20 carbon atoms;

n and m are each independently 0 or 3, except when n and m are 0 at the same time.)

Preferably, the organic ligand according to an embodiment of the present invention may be a bisphosphine ligand represented by 4.

[Formula 4]

(In Formula 4,

R is C1-C60 alkyl or C6-C60 aryl;

R ¹ to R ⁴ are each independently C1-C60 alkyl or C6-C60 aryl;

Alkyl or aryl of R and alkyl or aryl of R ¹ to R ⁴ are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, monoC1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 Alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, tri C6-C30 arylamino, mono C1-C30 alkylsilyl, diC1-C30 alkylsilyl, triC1-C30 alkylsilyl, mono C6-C30 aryl It may be further substituted with one or more selected from silyl, diC6-C30 arylsilyl and triC6-C30 arylsilyl.)

Preferably, the catalyst activator according to an embodiment of the present invention may be one or two or more selected from compounds represented by the following Chemical Formulas 11 to 13.

[Formula 11]

-[Al(R ₂₁ )-O] _c -

[Formula 12]

D(R ₂₂ ) ₃

[Formula 13]

[LH] ⁺ [Q(E) ₄ ] ^-

(In Formulas 11 to 13,

R ₂₁ is halogen, C1-C30 hydrocarbyl, or C1-C20 hydrocarbyl substituted with halogen, c is an integer of 2 or more,

D is aluminum or boron, R ₂₂ is C1-C20 hydrocarbyl or C1-C20 hydrocarbyl substituted with halogen,

L is a neutral Lewis base, [LH] ⁺ is a Bronsted acid, Q is boron or aluminum in the oxidation state of +3, E is independently of each other C1-C30 hydrocarbyl or halogen, alkyl, alkoxy or phenoxy C1-C30 hydrocarbyl substituted with

Preferably, in the step of preparing the ethylene oligomer according to an embodiment of the present invention, the pressure of ethylene is 0 to 100 kgf/cm ² , and the reaction temperature may be 0 to 150°C.

In addition, the present invention provides an apparatus for producing ethylene oligomer, the apparatus for producing ethylene oligomer of the present invention,

a body including a tubular reaction unit in which a solvent is injected and flowed, and a catalyst system selectively introduced therein and ethylene react;

a solvent inlet formed at one end in the longitudinal direction of the body and into which the solvent is introduced; and

a reactant inlet which is selectively located in the longitudinal direction of the body and injects a catalyst system including a chromium catalyst or a chromium source, an organic ligand, and ethylene; and

It is formed in the longitudinal direction of the body, and includes one or more ethylene injection parts into which ethylene is additionally injected;

Ethylene additionally injected from the ethylene injection unit is supplied in an amount satisfying Equation 11 below.

[Equation 11]

FE _n-1 > FE _n

(In Equation 11 above,

n is an integer greater than or equal to 1, and is an n-th ethylene injection unit located in the longitudinal direction of the body along the longitudinal direction of the body;

FE _n is the amount of ethylene supplied from the nth ethylene injection section;

However, FE ₀ is the initial amount of ethylene supplied to the reactant inlet.)

Two or more ethylene injection units according to an embodiment of the present invention are formed to be spaced apart from each other in the longitudinal direction of the body, and ethylene is injected from the ethylene injection unit, respectively.

Preferably, ethylene according to an embodiment of the present invention may be supplied in an amount satisfying Equation 12 below.

[Equation 12]

2×FE ₀ ≥

(In Equation 12 above,

FE is the ethylene supply amount additionally supplied from the ethylene injection unit according to the order located in the longitudinal direction of the body;

n is an integer greater than or equal to 1, and represents the order of the ethylene injection portion starting from one end in the longitudinal direction of the body;

However, FE ₀ is the initial amount of ethylene supplied to the reactant inlet.)

Preferably, the tubular reaction unit according to an embodiment of the present invention is selectively positioned in the longitudinal direction of the reactant body, and may further include a catalyst activator injection unit into which the catalyst activator is injected.

In the method for producing an ethylene oligomer of the present invention, ethylene oligomer can be prepared with high catalytic activity, excellent selectivity and conversion rate by respectively introducing ethylene from ethylene injection parts located at different positions in a flowing reaction system.

In addition, the method for producing an ethylene oligomer of the present invention can significantly reduce the amount of polyethylene produced by additionally adding ethylene from different ethylene injection parts present at different positions in the flowing reaction system, so that pipe clogging and fouling do not occur. It is very economical because it can maintain stability.

In addition, the ethylene oligomer production apparatus of the present invention includes two or more ethylene injection units, so that ethylene is injected at different positions according to the reaction stream, respectively, so that the catalyst activity is not lowered and the polyethylene production amount is reduced at the same time, thereby providing excellent ethylene oligomer selectivity and ethylene conversion rate. have

1 is a graph showing the results of ¹³ P NMR, ¹ H NMR, ¹⁹ F NMR, and EPR (electron paramagnetic resonance) of Formula A prepared in Example 1 of the present invention.

Hereinafter, the present invention will be described in more detail. If there is no other definition in the technical and scientific terms used at this time, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and may unnecessarily obscure the subject matter of the present invention in the following description. A description of possible known functions and configurations will be omitted.

As used herein, the term "alkyl" (when the number of carbon atoms is not particularly limited) has 1 to 60 carbon atoms, preferably 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms in one embodiment, preferably 1 to 10 carbon atoms in one embodiment. , preferably in one aspect, refers to a saturated straight-chain or branched acyclic hydrocarbon having 1 to 7 carbon atoms. "Lower alkyl" means straight-chain or branched alkyl having 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms in one aspect. Representative saturated straight chain alkyls are -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n- contains decyl, whereas saturated branched alkyl is -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3- Methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5- Methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethyl Pentyl, 2,2-dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.

When described as "C1-C10" in the present specification, it means that the number of carbon atoms is 1 to 10. For example, C 1 -C 10 alkyl means alkyl having 1 to 10 carbon atoms.

As used herein, the terms “halogen” and “halo” refer to fluorine, chlorine, bromine or iodine.

As used herein, the terms "fluorine-substituted aryl", "fluorine-substituted aryloxy" or "fluorine-substituted alkoxy" refer to an aryl, aryloxy or alkoxy group in which one or more hydrogen atoms are each replaced by a fluorine atom . For example, haloaryl includes —C ₆ H ₄ F, —C ₆ H ₃ F ₂ , —C ₆ HF ₄ , and the like. wherein aryl and halogen are as defined above and alkoxy is as defined below.

As used herein, the term "alkoxy" means -OCH ₃ , -OCH ₂ CH ₃ , -O(CH ₂ ) ₂ CH ₃ , -O(CH ₂ ) ₃ CH ₃ , -O(CH ₂ ) ₄ CH ₃ , -O(CH ₂ ) ₅ CH ₃ , including -O-(alkyl), and the like, wherein alkyl is as defined above.

As used herein, the term "lower alkoxy" means -O- (lower alkyl), wherein lower alkyl is as defined above.

As used herein, the term "aryl" refers to a carbocyclic aromatic group containing 5 to 10 ring atoms. Representative examples include phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, etc. including, but not limited to. Carbocyclic aromatic groups may be optionally substituted.

As used herein, the term “aryloxy” is RO—, and R is aryl as defined above. "Arylthio" is RS- and R is aryl as defined above.

The term "mono-alkylamino" as used herein is -NHCH ₃ , -NHCH ₂ CH ₃ , -NH(CH ₂ ) ₂ CH ₃ , -NH(CH ₂ ) ₃ CH ₃ , -NH(CH ₂ ) ₄ -NH(alkyl), including CH ₃ , —NH(CH ₂ ) ₅ CH ₃ , and the like, wherein alkyl is as defined above.

As used herein, the term “di-alkylamino” means —N(CH ₃ ) ₂ , —N(CH ₂ CH ₃ ) ₂ , —N((CH ₂ ) ₂ CH ₃ ) ₂ , —N(CH ₃ ) -N(alkyl)(alkyl), including (CH ₂ CH ₃ ), and the like, wherein each alkyl independently of the other is alkyl as defined above.

The term "mono-alkylsilyl" as used herein means -SiH ₂ CH ₃ , -SiH ₂ CH ₃ , -SiH ₂ (CH ₂ ) ₂ CH ₃ , -SiH ₂ (CH ₂ ) ₃ CH ₃ , -SiH ₂ -SiH ₂ (alkyl), including (CH ₂ ) ₄ CH ₃ , —SiH ₂ (CH ₂ ) ₅ CH ₃ , and the like, wherein alkyl is as defined above.

As used herein, the term "di-alkylsilyl" refers to -SiH(CH ₃ ) ₂ , -SiH(CH(CH ₃ ) ₂ )(CH ₃ ), -SiH((CH ₂ ) ₂ CH ₃ ) ₂ , - -SiH(alkyl)(alkyl), including SiH(CH ₃ )(CH ₂ CH ₃ ), and the like, wherein each alkyl independently of the other is alkyl as defined above.

As used herein, the term "trialkylsilyl" means -Si(CH ₃ ) ₃ , -Si(CH ₂ (CH ₃ )) ₃ , -Si((CH ₂ ) ₂ CH ₃ ) ₃ , -Si(CH ₃ ) ) ₂ (CH ₂ CH ₃ ), and the like, —Si(alkyl)(alkyl)(alkyl), wherein each alkyl independently of the other is alkyl as defined above.

As used herein, the terms "monoarylsilyl", "diarylsilyl" and "triarylsilyl" refer to a substituent corresponding to aryl instead of alkyl in "monoalkylsilyl", "dialkylsilyl", or "trialkylsilyl" to be.

Hereinafter, a method for producing an ethylene oligomer according to an embodiment of the present invention will be described in detail.

The method for producing an ethylene oligomer of the present invention,

chromium catalyst or chromium source; organic ligands; and ethylene to form an ethylene oligomerization reaction stream; and

supplying additional ethylene from one or more ethylene injection units located at different positions in the direction of travel of the reaction stream;

The additionally supplied ethylene is supplied in an amount satisfying Equation 1 below.

[Equation 1]

FE _n-1 > FE _n

(In Equation 1 above,

n is an integer greater than or equal to 1, and is the nth ethylene injection unit located on the reaction stream according to the direction of travel of the reaction stream;

FE _n is the amount of ethylene supplied from the nth ethylene injection section;

FE ₀ is the initial feed of the first ethylene fed to the step of forming the ethylene oligomerization reaction stream.)

In the method for producing an ethylene oligomer of the present invention, ethylene is additionally injected from different ethylene injection parts located at different positions according to the direction of progress of a reaction stream in the catalyst system. , high catalytic activity is maintained and ethylene oligomers can be prepared with high selectivity.

Moreover, by supplying ethylene to different locations in the reaction stream, the production of polyethylene can be reduced and the conversion rate of ethylene can be increased.

In the method for producing an ethylene oligomer according to an embodiment of the present invention, each ethylene is supplied into the reaction stream from different ethylene injection parts located at different positions in the progress direction of the reaction stream, as well as the amount of ethylene supplied as in Equation 1 above. By controlling

Specifically, in the method for producing an ethylene oligomer of the present invention, ethylene is supplied at different positions depending on the progress direction of the reaction stream, but the amount of ethylene supplied may be less than the amount supplied earlier.

That is, the amount of ethylene initially supplied to form the ethylene oligomerization reaction stream is FE ₀ , and may be greater than the amount of ethylene additionally supplied from the first ethylene injection unit.

Similarly, when there are two ethylene injection parts and supply of ethylene is supplied from each ethylene injection part, the amount of ethylene supplied from the second ethylene injection part is less than the amount of ethylene supplied from the first ethylene injection part.

In other words, if the supply amount of ethylene initially input to form an ethylene oligomerization reaction stream with a chromium catalyst or a chromium source and an organic ligand is defined as FE ₀ and n injection portions of ethylene, the supply amount of ethylene is expressed by the following formula can be the same

[ceremony]

FE ₀ > FE ₁ > FE ₂ > FE ₃ > FE ₄ > FE ₅ > FE ₆ > FE ₇ > FE ₈ .......> FE _n

When the supply amount of ethylene according to an embodiment of the present invention satisfies Equation 1 above, the gradient of the concentration of ethylene remaining in the reactor becomes constant, so that the stability of the process is maintained, thereby increasing the conversion rate of ethylene and reducing the formation of polyethylene. .

Therefore, the total amount of ethylene supplied is not limited, but the ethylene supply amount according to an embodiment of the present invention is less than the previously injected ethylene supply amount so that the gradient of ethylene concentration becomes constant even when the ethylene oligomerization reaction proceeds. can supply

That is, the supply amount of ethylene can be controlled so that the supply amount of ethylene also decreases as the number of times of ethylene supply increases.

Furthermore, the ethylene supplied according to an embodiment of the present invention may be supplied in an amount satisfying the following Equation 2.

[Equation 2]

2×FE ₀ ≥

(In Equation 2 above,

FE is the ethylene feed amount additionally fed from the ethylene injection section according to the order in which they are positioned in the reaction stream in the forward direction of the reaction stream;

n is an integer greater than or equal to 1 and represents the total number of ethylene injections starting from one end of the reaction stream;

provided that FE ₀ is the initial feed amount of ethylene fed to the step of forming the ethylene oligomerization reaction stream.)

)은 에틸렌 올리고머화 반응 스트림을 형성시키기위해 초기에 공급되는 에틸렌량(FE₀)의 2배와 같거나 적을 수 있다.Ethylene supply amount (

) may be less than or equal to twice the amount of ethylene initially fed to form the ethylene oligomerization reaction stream (FE ₀ ).

Specifically, when ethylene according to an embodiment of the present invention is additionally supplied twice, the sum of the amounts of ethylene additionally supplied twice is the amount of ethylene initially supplied to form an ethylene oligomerization reaction stream (FE ₀ ) may be equal to or less than twice the amount. By controlling the amount of ethylene added as described above, the catalytic activity can be maintained while the conversion of ethylene and the yield of ethylene oligomer can be increased, and the production of polyethylene can be reduced.

The ethylene oligomerization reactor according to an embodiment of the present invention may be a tubular reactor, and a plurality of ethylene injection units may be provided in the tubular reactor.

The ethylene injection portion may be equal to or greater than the number of times ethylene is injected.

Specifically, if the ethylene supply is injected three times, the ethylene may be supplied from three or more ethylene injection units, respectively.

The residence time of the reaction stream between each ethylene injection unit according to an embodiment of the present invention may be 0.1 to 2 hours, preferably 0.2 to 2 hours in terms of reducing the production of polyethylene while having improved reaction efficiency. , more preferably 0.2 to 1 hour.

The reaction stream according to an embodiment of the present invention may further include a catalyst activator, and the catalyst activator may be any material capable of activating a catalyst or a catalyst composition of a chromium source and an organic ligand, but preferably the formula 11 to 13 may be represented.

[Formula 11]

-[Al(R ₂₁ )-O] _c -

[Formula 12]

D(R ₂₂ ) ₃

[Formula 13]

[LH] ⁺ [Q(E) ₄ ] ^-

(In Formulas 11 to 13,

R ₂₁ is halogen, C1-C30 hydrocarbyl, or C1-C20 hydrocarbyl substituted with halogen, c is an integer of 2 or more,

D is aluminum or boron, R ₂₂ is C1-C20 hydrocarbyl or C1-C20 hydrocarbyl substituted with halogen,

L is a neutral Lewis base, [LH] ⁺ is a Bronsted acid, Q is boron or aluminum in the oxidation state of +3, E is independently of each other C1-C30 hydrocarbyl or halogen, alkyl, alkoxy or phenoxy C1-C30 hydrocarbyl substituted with

Preferably, in Formulas 11 to 13 according to an embodiment of the present invention, R ₂₁ is halogen, C1-C30 alkyl, or halogen-substituted C1-C20 alkyl, c is an integer of 2 or more, D is aluminum or boron; , R ₂₂ is C 1 -C 20 alkyl or C 1 -C 20 alkyl substituted with halogen, L is a neutral Lewis base, [LH] ⁺ is Bronsted acid, Q is boron or aluminum in the oxidation state of +3, E is independently of each other C1-C30 alkyl; C6-C30 aryl; C1-C30 alkyl substituted by halogen, C1-C30 alkyl, C1-C30 alkoxy or phenoxy; or C6-C30 aryl substituted with halogen, C1-C30 alkyl, C1-C30 alkoxy or phenoxy.

Specifically, the compound represented by Chemical Formula 11 according to an embodiment of the present invention may be modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane or butylaluminoxane, and the present invention The compound represented by Formula 12 according to an embodiment of , triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolyl It may be aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron or tributyl boron, and the compound represented by Formula 13 according to an embodiment of the present invention Silver triethylammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p-tolyl) boron, tripropyl ammonium tetra (p -Tolyl) boron, triethylammonium tetra(o,p-dimethylphenyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethyl Ammonium tetra(p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenyl boron, N,N-diethylaniliniumtetraphenyl boron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphoniumtetraphenylboron, triethylammonium tetraphenylaluminum, Tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammoniumtetra(p-tolyl)aluminum, triethylammonium Tetra(o,p-dimethylphenyl)aluminum, tribu Tylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum, tributylammoniumtetrapentafluorophenylaluminum, N,N-diethylaniliniumtetra Phenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentafluorophenylaluminum, triphenylphosphoniumtetraphenylaluminum , trimethylphosphonium tetraphenylaluminum, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetrapentafluoro It may be rophenylboron.

More preferably, as the activator according to an embodiment of the present invention, alkylaluminoxane or modified alkylaluminoxane may be used, and more preferably methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) may be used.

The catalyst activator according to an embodiment of the present invention may be used in an amount of 10 to 1000 moles, preferably 20 to 500 moles, and more preferably 100 to 300 moles, based on 1 mole of chromium in the catalyst system.

Preferably, the chromium catalyst according to an embodiment of the present invention may be a chromium compound represented by the following formula (1).

[Formula 1]

(In Formula 1,

R is C1-C60 alkyl or C6-C60 aryl;

R ¹ to R ⁴ are each independently C1-C60 alkyl or C6-C60 aryl;

X ¹ and X ² are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate, or C1-C30 hydrocarbyl comprising at least one selected from ether and amino;

A is boron or aluminum;

Y ¹ to Y ⁴ are each independently fluorine-substituted C6-C60 aryl, fluorine-substituted C6-C60 aryloxy, or fluorine-substituted C6-C60 alkoxy;

Alkyl or aryl of R and alkyl or aryl of R ¹ to R ⁴ are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, monoC1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 Alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, tri C6-C30 arylamino, mono C1-C30 alkylsilyl, diC1-C30 alkylsilyl, triC1-C30 alkylsilyl, mono C6-C30 aryl It may be further substituted with one or more selected from silyl, diC6-C30 arylsilyl and triC6-C30 arylsilyl.)

By using the specific chromium compound represented by Formula 1 according to an embodiment of the present invention, it is possible to prepare an ethylene oligomer by exhibiting high catalytic activity without using conventional expensive methylaluminoxane.

Furthermore, in the method for producing an ethylene oligomer of the present invention, the selectivity to 1-octene and 1-hexene is high, and the reaction efficiency is excellent by using the specific chromium compound represented by Formula 1 above.

In particular, in the method for producing an ethylene oligomer according to an embodiment of the present invention, the selectivity of the ethylene oligomer is increased by using a specific chromium compound represented by Chemical Formula 1 and supplying ethylene from each ethylene injection unit located at a different location. At the same time, it suppresses the production of polyethylene.

In Formula 1 according to an embodiment of the present invention, R is C 1 -C 60 alkyl; R ¹ to R ⁴ are each independently C6-C60 aryl; X ¹ and X ² are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate or C1-C30 hydrocarbyl including ether; A is boron or aluminum; Y ¹ to Y ⁴ are each independently fluorine-substituted C6-C60 aryl, fluorine-substituted C6-C60 aryloxy, or fluorine-substituted C6-C60 alkoxy; The alkyl of R and the aryl of R ¹ to R ⁴ are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, mono C1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, triC6-C30 arylamino, monoalkylsilyl, diC1-C30alkylsilyl, triC1-C30alkylsilyl, monoC6-C30arylsilyl, diC6-C30aryl It may be one that may be further substituted with one or more selected from silyl and triC6-C30 arylsilyl,

more preferably R is C1-C30 alkyl; R ¹ to R ⁴ are each independently C6-C30 aryl; X ¹ and X ² are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate or C1-C20 hydrocarbyl including ether; A is boron; Y ¹ to Y ⁴ are each independently fluorine-substituted C6-C30 aryl, fluorine-substituted C6-C30 aryloxy, or fluorine-substituted C6-C30 alkoxy; The alkyl of R and the aryl of R ¹ to R ⁴ are C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxy, monoC1-C20 alkylamino, diC1-C20 alkylamino, triC1-C20 alkylamino, mono C6-C20 arylamino, diC6-C20 arylamino, triC6-C20 arylamino, monoC1-C20alkylsilyl, diC1-C20alkylsilyl, triC1-C20alkylsilyl, monoC6-C20arylsilyl, diC6 It may be one that may be further substituted with one or more selected from -C20 arylsilyl and triC6-C20 arylsilyl.

More preferably, in Formula 1 according to an embodiment of the present invention, R is C1-C20 alkyl; R ¹ to R ⁴ are each independently C6-C20 aryl; X ¹ and X ² are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate or acetylacetonate; A is boron; Y ¹ to Y ⁴ are each independently fluorine-substituted C6-C20 aryl, fluorine-substituted C6-C20 aryloxy, or fluorine-substituted C6-C20 alkoxy; The alkyl of R and the aryl of R ¹ to R ⁴ are C1-C10 alkyl, C6-C12 aryl, C1-C10 alkoxy, monoC1-C10 alkylamino, diC1-C10 alkylamino, triC1-C10 alkylamino, mono C6-C12 arylamino, diC6-C12 arylamino, triC6-C12 arylamino, mono C1-C10 alkylsilyl, diC1-C10 alkylsilyl, and triC1-C10 alkylsilyl and more preferably R is C1-C10 alkyl; R ¹ to R ⁴ are each independently C6-C12 aryl; X ¹ and X ² are each independently halogen; A is boron; Y ¹ to Y ⁴ are each independently C6-C12 aryl substituted with fluorine; R ¹¹ to R ¹³ are each independently C1-C7 alkyl, wherein the alkyl of R and the aryl of R ¹ to R ⁴ may be further substituted with one or more selected from C1-C7 alkyl and triC1-C7 alkylsilyl it could be

More preferably, in terms of catalyst efficiency, selectivity of ethylene oligomer, and inhibition of polyolefin production, Chemical Formula 1 may be represented by Chemical Formula 1-1 below.

[Formula 1-1]

(In Formula 1-1,

R is C 1 -C 30 alkyl or C 6 -C 30 aryl;

X ¹ and X ² are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate, acetylacetonate or C1-C20 hydrocarbyl including ether;

A is boron or aluminum;

Y ¹ to Y ⁴ are each independently fluorine-substituted C6-C30 aryl, fluorine-substituted C6-C30 aryloxy, or fluorine-substituted C6-C30 alkoxy;

R ²¹ to R ³² are each independently C1-C20 alkyl;

Alkyl or aryl of R is C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxy, mono C1-C20 alkylamino, diC1-C20 alkylamino, triC1-C20 alkylamino, mono C1-C20 arylamino, It may be further substituted with one or more selected from diC6-C20 arylamino and triC6-C20 arylamino.)

The chromium compound represented by Formula 1-1 according to an embodiment of the present invention has improved catalytic activity and ethylene oligomer selectivity by introducing a trialkylsilyl group, which is a specific substituent, to phenyl (Ph) bonded to phosphorus (P). .

Preferably, in Formula 1-1 according to an embodiment of the present invention, R is C1-C20 alkyl; X ¹ and X ² are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate, acetylacetonate; A is boron; Y ¹ to Y ⁴ may independently be fluorine-substituted C6-C20 aryl or fluorine-substituted C6-C20 aryloxy, preferably R is C1-C10 alkyl; X ¹ and X ² are each independently halogen or C1-C10 alkyl; A is boron; Y ¹ to Y ⁴ may be each independently C6-C12 aryl substituted with fluorine.

Preferably, Chemical Formula 1-1 according to an embodiment of the present invention may be represented by the following Chemical Formula 1-2.

[Formula 1-2]

(In Formula 1-2,

R is C1-C20 alkyl or C6-C20 aryl;

X ¹ and X ² are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate, acetylacetonate or C1-C20 hydrocarbyl including ether;

A is boron or aluminum;

Y ¹ to Y ⁴ are each independently fluorine-substituted C6-C20 aryl, fluorine-substituted C6-C20 aryloxy, or fluorine-substituted C6-C20 alkoxy;

R ^a to R ^d are each independently C1-C10 alkyl;

Alkyl or aryl of R may be further substituted with one or more selected from C1-C20 alkyl.)

Preferably, in Formula 1-2 according to an embodiment of the present invention, R is C1-C10 alkyl; X ¹ and X ² are each independently halogen, C1-C10 alkyl or acetylacetonate; A is boron; Y ¹ to Y ⁴ are each independently C6-C12 aryl substituted with fluorine; R ^a to R ^d are each independently C1-C7 alkyl, and the alkyl or aryl of R may be further substituted with one or more selected from C1-C7 alkyl, more preferably all of R ^a to R ^d are the same It may be C1-C7 alkyl.

The chromium source according to an embodiment of the present invention may be represented by the following formula (2).

[Formula 2]

Cr(Z) _n (A) _m

(In Formula 2,

Z is each independently a halogen group, an acetylacetonate group, or a carboxylate group,

A is an ether or acetonitrile having 2 to 20 carbon atoms;

n and m are each independently 0 or 3, except when n and m are 0 at the same time.)

Preferably, the chromium source according to an embodiment of the present invention is chromium (III) acetyl acetonate, chromium trichloride tristetrahydrofuran, chromium (III) tri (2-ethylhexanoate), chromium (III) tris (2, 2,6,6-tetramethyl-3,5-heptanedionate), chromium (III) benzoyl acetonate, chromium (III) hexafluoro-2,4-pentaindionate, chromium (III) acetate hydroxide one selected from chromium (III) chloride tetrahydrofuran, chromium (III) acetate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) laurate, and chromium (III) stearate; or There may be more than one.

Preferably, the organic ligand according to an embodiment of the present invention may be any organic ligand used in the art, but a PNP-based ligand compound is more preferable, and may be specifically represented by Chemical Formula 3.

[Formula 3]

(In Formula 3,

R is C1-C60 alkyl or C6-C60 aryl;

R ¹ to R ⁴ are each independently C1-C60 alkyl or C6-C60 aryl;

Alkyl or aryl of R and alkyl or aryl of R ¹ to R ⁴ are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, monoC1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 Alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, tri C6-C30 arylamino, mono C1-C30 alkylsilyl, diC1-C30 alkylsilyl, triC1-C30 alkylsilyl, mono C6-C30 aryl It may be further substituted with one or more selected from silyl, diC6-C30 arylsilyl and triC6-C30 arylsilyl.)

Preferably, in Formula 3 according to an embodiment of the present invention, R is C1-C60 alkyl; R ¹ to R ⁴ are each independently C6-C60 aryl;

The alkyl of R and the aryl of R ¹ to R ⁴ may be further substituted with one or more selected from C1-C30 alkyl, triC1-C30 alkylsilyl and triC6-C30 arylsilyl.

More preferably, in Formula 3 according to an embodiment of the present invention, R is C1-C20 alkyl; R ¹ to R ⁴ are each independently C6-C20 aryl; The alkyl of R and the aryl of R ¹ to R ⁴ may be further substituted with one or more selected from C1-C10 alkyl, triC1-C10 alkylsilyl and triC6-C30 arylsilyl.

In the method for preparing an ethylene oligomer according to an embodiment of the present invention, the organic solvent is not particularly limited in its type, but may be a hydrocarbon solvent substituted or unsubstituted with halogen. Specifically, as the hydrocarbon solvent, an aliphatic hydrocarbon solvent having 4 to 20 carbon atoms, an aromatic hydrocarbon solvent having 6 to 20 carbon atoms, a mixture thereof, and the like may be used. More specifically, examples of the hydrocarbon solvent substituted or unsubstituted with halogen include toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, methylcyclohexene, cyclohexene, and the like, preferably dichloromethane. , methylcyclohexene, or cyclohexene, and when the solvents exemplified above are used, the polymerization activity is high and the separation between the products 1-hexene and 1-octene and the solvent after the oligomerization reaction is easier.

In the step of preparing the oligomer according to an embodiment of the present invention, the pressure of ethylene is 0 to 100 kgf/cm ² , and may be performed at a reaction temperature of 0 to 150° C., preferably, the pressure of ethylene is 20 to 80 kgf/cm cm ² , and the reaction temperature is 20 to 120° C., more preferably, the pressure of ethylene is 30 to 60 kgf/cm ² , and the reaction temperature may be 40 to 100° C.

The method for producing an ethylene oligomer according to an embodiment of the present invention can suppress the production of polyethylene by injecting ethylene into the catalyst system stream at multiple locations at different locations.

Therefore, the ethylene oligomer prepared according to the method for producing an ethylene oligomer of the present invention may have a polyethylene content of 1.0% by weight or less, preferably 0.9% by weight or less, and more preferably less than 0.5%.

In addition, the present invention provides an ethylene oligomer manufacturing apparatus, the ethylene oligomer manufacturing apparatus of the present invention

a body including a tubular reaction unit in which a solvent is injected and flowed, and a catalyst system selectively introduced therein and ethylene react;

a solvent inlet that is formed at one end in the longitudinal direction of the body and into which the solvent is introduced;

a reactant inlet which is selectively located in the longitudinal direction of the body and into which a catalyst system including a chromium catalyst or a chromium source, an organic ligand and ethylene is injected; and

The ethylene injection portion is formed in the longitudinal direction of the body and includes one or more ethylene injection portions into which ethylene is additionally injected;

Ethylene additionally injected from the ethylene injection unit is supplied in an amount satisfying Equation 11 below.

[Equation 11]

FE _n-1 > FE _n

(In Equation 11 above,

n is an integer greater than or equal to 1, and is an n-th ethylene injection unit located in the longitudinal direction of the body along the longitudinal direction of the body;

FE _n is the amount of ethylene supplied from the nth ethylene injection section;

However, FE ₀ is the initial amount of ethylene supplied to the reactant inlet.)

The ethylene oligomer manufacturing apparatus according to an embodiment of the present invention includes at least one ethylene injection unit formed in the longitudinal direction of the body in the longitudinal direction of the body, into which additional ethylene is injected, thereby maintaining high catalytic activity while suppressing the production of polyethylene. This can improve process stability.

Preferably, in the ethylene oligomer manufacturing apparatus according to an embodiment of the present invention, ethylene may be supplied in an amount satisfying Equation 12 below.

[Equation 12]

2×FE ₀ ≥

(In Equation 12 above,

FE is the ethylene supply amount additionally supplied from the ethylene injection unit according to the order located in the longitudinal direction of the body;

n is an integer greater than or equal to 1, and represents the order of the ethylene injection portion starting from one end in the longitudinal direction of the body;

However, FE ₀ is the initial amount of ethylene supplied to the reactant inlet.)

The ethylene oligomer manufacturing apparatus according to an embodiment of the present invention improves the conversion rate and selectivity of ethylene by adjusting the ethylene supply amount to satisfy Equations 11 and 12, and at the same time suppresses the production of polyethylene.

Preferably, the tubular reaction unit according to an embodiment of the present invention is selectively positioned in the longitudinal direction of the body, and may further include a catalyst activator injection unit into which the catalyst activator is injected.

The ethylene oligomer manufacturing apparatus according to an embodiment of the present invention may be further provided with means within a range recognized by those skilled in the art, except as specifically mentioned.

For example, the ethylene oligomer manufacturing apparatus according to an embodiment of the present invention may further include a discharge unit for discharging the ethylene oligomer generated by the ethylene oligomerization reaction and a separation and purification unit for separating and purifying the discharged oligomer, Of course, it may further include an ethylene recovery unit capable of recovering ethylene and reintroducing it back into the tubular reactor.

The present invention will be described in more detail with reference to the following examples. However, these examples are for illustrative purposes only, and the present invention is not limited to these examples.

[Preparation Example 1] Preparation of catalyst

According to the method described in Korean Patent No. 10-2087994, a chromium compound represented by the following formula (A) was prepared.

[Formula A]

¹³ P NMR, ¹ H NMR, ¹⁹ F NMR, and EPR (electron paramagnetic resonance) results of Formula A prepared in FIG. 1 are shown in graphs, from which it can be seen that Formula A was prepared.

[Example 1] Ethylene oligomerization reaction

Catalyst prepared in Preparation Example 1 [(iPrN[P(C ₆ H ₄ -p-Si(nBu) ₃ ) ₂ ] ₂ )-CrCl ₂ ] ⁺ [B(C ₆ F ₅ ) ₄ ] ^- (1umol) And 1.2L/hr of a methylcyclohexane solution containing 200umol (Al/Cr ratio 200) of Triisobutylaluminum was injected into the inlet of a 1.2m long tubular reactor with a diameter of 2 inches. A total of 450 g/hr of ethylene as a reactant was divided and injected into the reactor at 200 g/hr at the inlet point of the reactor, 150 g/hr at 40 cm point, and 100 g/hr at 80 cm point, so that the internal pressure of the reactor was 35 kg/cm ² g, and the temperature was 40 The ethylene oligomerization reaction was performed at ℃.

Through gas chromatography analysis (GC analysis) of the produced material, the produced oligomers {1-octene (1-C8), 1-hexene (1-C6), methylcyclopentane + methylenecyclopentane (cy-C6), and C10 or higher oligomers (> C10)} was measured and the weight of the product is shown in Table 1 below. The resulting solid polyethylene was separated through filtration at room temperature, and then the weight was measured, and the weight % of polyethylene was calculated through the formula [weight of PE produced (g) / total weight of product (g)].

[Example 2] Ethylene oligomerization reaction

In Example 1, ethylene was injected in the same manner as in Example 1, except that a total of 450 g/hr was divided into the reactor at 150 g/hr at the reactor inlet point, 150 g/hr at 40 cm point, and 150 g/hr at 80 cm point. Thus, an ethylene oligomerization reaction was carried out, and the results are shown in Table 1 below.

[Comparative Example 1] Ethylene oligomerization reaction

The ethylene oligomerization reaction was carried out in the same manner as in Example 1, except that a total of 450 g / hr was added at one time for the reaction seconds instead of separately introducing the ethylene of Example 1 at different positions in the catalyst system stream. , the results are shown in Table 1 below.

ethylene
number of injections Total Ethylene Injection ethylene
Conversion rate (%) 1-C8
(g/hr) 1-C6
(g/hr) Cy-C6
(g/hr) C10+
(g/hr) PE
(g/hr) Example 1 3rd time 450 g/hr 70.9 235 33 15 36 0.6 Example 2 3rd time 450 g/hr 67.0 222 31 14 34 0.9 Comparative Example 1 1 time 450 g/hr 55.8 185 26 12 28 1.4

As shown in Table 1, the selectivity of the ethylene oligomer was significantly improved compared to Comparative Example 1 in which ethylene was injected at a time in Examples 1 and 2, in which different amounts of ethylene were injected three times at different positions on the reaction stream, and , it can be seen that the polyethylene production amount is also reduced.

In particular, as in Example 1 of the present invention, by adjusting the amount of ethylene to be supplied according to the number of injections, the conversion rate of ethylene and the yield of ethylene oligomer can be further improved, and the production of polyethylene can be further suppressed.

In Comparative Example 1, when ethylene was added at once, a gas phase of ethylene was formed, and the flow rate of the reaction stream was increased, and the residence time was reduced, thereby affecting the conversion rate of the ethylene oligomer and the production of polyethylene.

Therefore, in the method for producing an ethylene oligomer of the present invention, ethylene is injected multiple times from one or more ethylene injection parts located at different positions in the direction of the reaction stream, so that it has excellent catalytic activity and selectivity of ethylene oligomer while reducing polyethylene production. It is a very efficient and economical method.

As described above, the embodiments of the present invention have been described in detail, but those of ordinary skill in the art to which the present invention pertains can view the present invention without departing from the spirit and scope of the present invention as defined in the appended claims. The invention may be practiced with various modifications. Accordingly, modifications of future embodiments of the present invention will not depart from the teachings of the present invention.

Claims (13)

feeding a chromium catalyst or chromium source, an organic ligand, and ethylene to form an ethylene oligomerization reaction stream; and
Including; supplying additional ethylene from one or more ethylene injection units present at different positions in the progress direction of the reaction stream;
The method for producing an ethylene oligomer in which the additionally supplied ethylene is supplied in an amount satisfying the following formula 1.
[Equation 1]
FE _n-1 > FE _n
In Equation 1 above,
n is an integer greater than or equal to 1, and is the nth ethylene injection unit located on the reaction stream according to the direction of travel of the reaction stream;
FE _n is the amount of ethylene supplied from the nth ethylene injection section;
FE ₀ is the initial feed of the first ethylene fed to the step of forming the ethylene oligomerization reaction stream. The method of claim 1,
The method for producing an ethylene oligomer in which the additionally supplied ethylene is supplied in an amount satisfying the following formula (2).
[Equation 2]
2×FE ₀ ≥

In Equation 2 above,
FE is the ethylene feed amount additionally fed from the ethylene injection section according to the order in which they are positioned in the reaction stream in the forward direction of the reaction stream;
n is an integer greater than or equal to 1, representing the total number of ethylene injections starting from one end of the reaction stream;
with the proviso that FE ₀ is the initial feed amount of ethylene fed to the step of forming the ethylene oligomerization reaction stream. The method of claim 1,
A method for producing an ethylene oligomer wherein the residence time of the reaction stream between the respective ethylene injection units is 0.1 to 2 hours. The method of claim 1,
The reaction stream further comprises a catalyst activator. 5. The method of claim 4,
The catalyst activator is a method for producing an ethylene oligomer in an amount of 10 to 1000 equivalents based on 1 equivalent of the chromium catalyst or chromium source. The method of claim 1,
The chromium catalyst is a method for producing an ethylene oligomer, which is a chromium compound represented by the following formula (1).
[Formula 1]

In Formula 1,
R is C1-C60 alkyl or C6-C60 aryl;
R ¹ to R ⁴ are each independently C1-C60 alkyl or C6-C60 aryl;
X ¹ and X ² are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate, or C1-C30 hydrocarbyl comprising at least one selected from ether and amino;
A is boron or aluminum;
Y ¹ to Y ⁴ are each independently fluorine-substituted C6-C60 aryl, fluorine-substituted C6-C60 aryloxy, or fluorine-substituted C6-C60 alkoxy;
Alkyl or aryl of R and alkyl or aryl of R ¹ to R ⁴ are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, monoC1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 Alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, tri C6-C30 arylamino, mono C1-C30 alkylsilyl, diC1-C30 alkylsilyl, triC1-C30 alkylsilyl, mono C6-C30 aryl It may be further substituted with one or more selected from silyl, diC6-C30 arylsilyl and triC6-C30 arylsilyl. The method of claim 1,
The chromium source is a method for producing an ethylene oligomer, which is a chromium compound represented by the following formula (2).
[Formula 2]
Cr(Z) _n (A) _m
In Formula 2,
Z is each independently a halogen group, an acetylacetonate group, or a carboxylate group,
A is an ether or acetonitrile having 2 to 20 carbon atoms;
n and m are each independently 0 or 3, except when n and m are 0 at the same time. The method of claim 1,
The method for producing an ethylene oligomer, wherein the organic ligand is a bisphosphine ligand represented by the following formula (3).
[Formula 3]

In Formula 3,
R is C1-C60 alkyl or C6-C60 aryl;
R ¹ to R ⁴ are each independently C1-C60 alkyl or C6-C60 aryl;
Alkyl or aryl of R and alkyl or aryl of R ¹ to R ⁴ are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, monoC1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 Alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, tri C6-C30 arylamino, mono C1-C30 alkylsilyl, diC1-C30 alkylsilyl, triC1-C30 alkylsilyl, mono C6-C30 aryl It may be further substituted with one or more selected from silyl, diC6-C30 arylsilyl and triC6-C30 arylsilyl. 6. The method of claim 5,
The catalyst activator is a method for producing one or two or more ethylene oligomers selected from compounds represented by the following Chemical Formulas 11 to 13.
[Formula 11]
-[Al(R ₂₁ )-O] _c -
[Formula 12]
D(R ₂₂ ) ₃
[Formula 13]
[LH] ⁺ [Q(E) ₄ ] ^-
(In Formulas 11 to 13,
R ₂₁ is halogen, C1-C30 hydrocarbyl, or C1-C20 hydrocarbyl substituted with halogen, c is an integer of 2 or more,
D is aluminum or boron, R ₂₂ is C1-C20 hydrocarbyl or C1-C20 hydrocarbyl substituted with halogen,
L is a neutral Lewis base, [LH] ⁺ is a Bronsted acid, Q is boron or aluminum in the oxidation state of +3, E is independently of each other C1-C30 hydrocarbyl or halogen, alkyl, alkoxy or phenoxy C1-C30 hydrocarbyl substituted with The method of claim 1,
The manufacturing step of the ethylene oligomer is a pressure of 0 to 100 kgf / cm ² of ethylene, and a method for producing an ethylene oligomer is carried out at a reaction temperature of 0 to 150 ℃. a body including a tubular reaction unit in which a solvent is injected and flowed, and a catalyst system selectively introduced therein and ethylene react;
a solvent inlet formed at one end in the longitudinal direction of the body and into which the solvent is introduced;
a reactant inlet which is selectively located in the longitudinal direction of the body and into which a catalyst system including a chromium catalyst or a chromium source, an organic ligand, and ethylene is injected; and
It is formed in the longitudinal direction of the body, and includes one or more ethylene injection parts into which ethylene is additionally injected;
An apparatus for producing an ethylene oligomer wherein the ethylene additionally injected from the ethylene injection unit is supplied in an amount satisfying the following Equation 11.
[Equation 11]
FE _n-1 > FE _n
In Equation 11 above,
n is an integer greater than or equal to 1, and is an n-th ethylene injection unit located in the longitudinal direction of the body along the longitudinal direction of the body;
FE _n is the amount of ethylene supplied from the nth ethylene injection section;
However, FE ₀ is the initial supply amount of ethylene supplied to the reactant inlet. 12. The method of claim 11,
Ethylene oligomer production apparatus in which the ethylene additionally injected from the ethylene injection unit is supplied in an amount satisfying the following Equation 12.
[Equation 12]
2×FE ₀ ≥

(In Equation 12 above,
FE is the ethylene supply amount additionally supplied from the ethylene injection unit according to the order located in the longitudinal direction of the body;
n is an integer greater than or equal to 1, and represents the order of the ethylene injection portion starting from one end in the longitudinal direction of the body;
However, FE ₀ is the initial supply amount of ethylene supplied to the reactant inlet. 12. The method of claim 11,
The tubular reaction part is selectively positioned in the longitudinal direction of the body, and the ethylene oligomer manufacturing apparatus further comprises a catalyst activator injection part into which the catalyst activator is injected.

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