KR20230134845A - Method for producing polyalphaolefin, and polyalphaolefin produced thereby, and reaction apparatus therefor - Google Patents

Abstract

The present invention relates to a method for producing polyalphaolefin using a reaction apparatus, wherein the reaction apparatus comprises: a continuous reactor; and a loop reactor which receives a reactant from a lower-end discharge part of the continuous reactor and re-supplies the reactant to the continuous reactor through a circulation pump and a circulation pipe. The method comprises the steps of: injecting a raw material containing alpha-olefin into the continuous reactor; injecting a catalyst containing BF_3 gas into the loop reactor; and injecting a complex compound of a BF_3-complexing agent or a cocatalyst containing a complexing agent into the continuous reactor, wherein the molar ratio of complexing agent/BF_3 in the catalyst and cocatalyst is less than 1. According to the present invention, the residence time of BF_3 gas in a reactor can be increased.

Description

Method for producing polyalphaolefin, polyalphaolefin produced thereby, and reaction apparatus therefor {Method for producing polyalphaolefin, and polyalphaolefin produced thereby, and reaction apparatus therefor}

The present invention relates to a method for producing polyalphaolefin, polyalphaolefin produced thereby, and a reaction device therefor.

Generally, lubricants consist of base oil and additives to improve physical properties, and lubricant base oils are typically divided into mineral oil and synthetic oil.

In general, mineral oil refers to naphthenic oil produced during the process of separating and refining crude oil, and synthetic oil refers to poly-alpha-olefin (PAO) produced by polymerizing alpha-olefin produced during the petroleum refining process. ) says.

Previously, mineral oil was mainly used as a lubricating base oil, but recently, demand for synthetic oils with characteristics such as low temperature fluidity, high viscosity index, low volatility at high temperatures, and high shear and thermal stability has been increasing.

Compared to general mineral oil, synthetic oil has a small viscosity change due to temperature changes and maintains excellent lubricating performance even under seasonal changes. This not only contributes to improving the quietness and fuel efficiency of automobiles, but also has excellent durability and stability, has a long lifespan, and reduces sludge. It has the advantage of being environmentally friendly due to the small amount of waste oil generated. In addition, engine oil using conventional mineral oil has insufficient thermal, physical and mechanical properties when applied to recent engines that have become smaller and more efficient, especially in fields such as engine oil, gear oil and grease that require high quality. , the use of synthetic oil is increasing.

Conventionally, the reactor for producing polyalphaolefin is continuously stirred in one or two continuous reactors. In this case, as the size of the reactor increases, heat exchange efficiency decreases, and the ratio of boron trifluoride (BF ₃ ) to alcohol, water, and ethyl acetate cannot be greater than 1, so there is a disadvantage in that the ratio cannot be adjusted. Additionally, there is a problem in that the reaction efficiency is lowered due to the small reaction contact area.

To solve this problem, a bus loop reactor method is used, but since boron trifluoride (BF ₃ ) gas is used as a catalyst, it is difficult to continuously inject it at a constant pressure and the “complexing agent/BF ₃ ” molar ratio is used. There is a limit where the time when has a value less than 1 is limited to the upper part of the booth loop reactor.

Meanwhile, Republic of Korea Patent Publication No. 10-0904967 is presented as a similar prior document.

Republic of Korea Patent Publication No. 10-0904967 (2009.06.22)

The object of the present invention is to produce a method for producing polyalphaolefin that can produce a high content of trimer, tetramer, and pentamer of alphaolefin without performing a simple distillation separation process, and to manufacture it accordingly. To provide polyalphaolefin and a reaction device therefor.

One aspect of the present invention is a continuous reactor; In the method of producing polyalphaolefin using a reaction device comprising a loop reactor that receives reactants from the bottom discharge of the continuous reactor and re-supplies the reactants to the continuous reactor through a circulation pump and circulation pipe, alpha olefin Injecting raw materials containing the raw materials into the continuous reactor; Injecting a catalyst containing BF ₃ gas into the loop reactor; and injecting a complex of BF ₃ -complexing agent or a cocatalyst containing a complexing agent into the continuous reactor, wherein the molar ratio of complexing agent/BF ₃ in the catalyst and cocatalyst is less than 1. It relates to a method for producing polyalphaolefin.

In one aspect, the BF ₃ gas may be injected into the loop reactor after the circulation pump.

In one aspect, the BF ₃ gas may be added in an amount of 0.01 to 10 mol per 100 mol of raw material.

In one aspect, the complexing agent may include an alcohol compound. Specifically, the complexing agent may include an alcohol compound having 1 to 10 carbon atoms, and as a specific example, the complexing agent may be butanol.

In one aspect, the alpha-olefin may include an alpha-olefin having 6 to 14 carbon atoms, and as a specific example, the alpha-olefin may be 1-decene.

In one aspect, the polyalphaolefin may be an oligomer mixture of alphaolefins. Specifically, the oligomer mixture may have a dimer content of alpha-olefin of less than 11% by weight, and the oligomer mixture may have a pentamer content of alpha-olefin of 5% by weight or more. Additionally, the oligomer mixture may have an alpha-olefin dimer/pentamer weight ratio of 3 or less, and an alpha-olefin trimer/tetramer weight ratio may be 2 or less.

In addition, another aspect of the present invention relates to polyalphaolefin produced by the above-described method for producing polyalphaolefin, wherein the polyalphaolefin is an oligomer mixture of alphaolefins, and the oligomer mixture has a dimer content of alphaolefins. It relates to less than 11% by weight of polyalphaolefin.

In another aspect, the oligomer mixture may have an alpha-olefin pentamer content of 5% by weight or more.

In another aspect, the oligomer mixture may have a dimer/pentamer weight ratio of alpha olefin of 3 or less, and a trimer/tetramer weight ratio of alpha olefin may be 2 or less.

In addition, another aspect of the present invention is a continuous reactor; And a loop reactor that receives reactants from the bottom discharge of the continuous reactor and re-supplies the reactants to the continuous reactor through a circulation pump and circulation pipe. A reaction device for producing polyalphaolefin, comprising:

The raw material containing alpha-olefin, and the complex of BF ₃ -complexing agent or the cocatalyst containing complexing agent are directly injected into the continuous reactor, and the catalyst containing BF ₃ gas is looped through the circulation pipe after the circulation pump. It relates to a reaction device for producing polyalphaolefin, characterized in that it is injected into a reactor.

In the method for producing polyalphaolefin according to the present invention, the raw materials and cocatalyst are directly injected into a continuous reactor, and the catalyst containing BF ₃ gas is injected into a loop reactor, thereby increasing the reactor residence time of BF ₃ gas and ignition. By adjusting the molar ratio of agent/BF ₃ to less than 1, the dimer content of alpha-olefin in the loop reactor is lowered, and the trimer, tetramer, and pentamer commonly used in lubricating oils are reduced. production can be maximized. This can provide low molecular weight polyalphaolefins with thermal and oxidation stability, low volatility, low pour point, and high viscosity index required in lubricating oils.

In particular, the method for producing polyalphaolefin according to the present invention can increase the residence time of BF ₃ gas in the reactor by injecting a catalyst containing BF ₃ gas into the loop reactor through the circulation pipe after the circulation pump, and thereby ignition. The molar ratio of agent/BF ₃ can be adjusted to less than 1.

1 is a diagram of a reaction apparatus used in the production of polyalphaolefin.

Advantages and features of the embodiments of the present invention and methods for achieving them will become clear by referring to the embodiments described in detail below along with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and may be implemented in various different forms. The present embodiments are merely provided to ensure that the disclosure of the present invention is complete and to be understood by those skilled in the art. It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

In describing embodiments of the present invention, if a detailed description of a known function or configuration is judged to unnecessarily obscure the gist of the present invention, the detailed description will be omitted. The terms described below are terms defined in consideration of functions in the embodiments of the present invention, and may vary depending on the intention or custom of the user or operator. Therefore, the definition should be made based on the contents throughout this specification.

One aspect of the present invention is a continuous reactor; In the method for producing polyalphaolefin using a reaction device comprising a loop reactor that receives reactants from the bottom discharge of the continuous reactor and re-supplies the reactants to the continuous reactor through a circulation pump and circulation piping, alpha olefin Injecting raw materials containing the raw materials into the continuous reactor; Injecting a catalyst containing BF ₃ gas into the loop reactor; and injecting a complex of BF ₃ -complexing agent or a cocatalyst containing a complexing agent into the continuous reactor, wherein the molar ratio of complexing agent/BF ₃ in the catalyst and cocatalyst is less than 1. It relates to a method for producing polyalphaolefin.

Referring to FIG. 1, the reaction device used to produce polyalphaolefin of the present invention includes a continuous reactor 10 and a loop reactor 20 located at the bottom of the continuous reactor. In more detail, the reaction device for polyalphaolefin according to an example of the present invention includes a continuous reactor (10); And a loop reactor (20) that receives reactants from the lower discharge portion of the continuous reactor (10) and re-supplies the reactants to the continuous reactor (10) through the circulation pump (21) and circulation pipes, as described above. Likewise, the raw material containing alpha-olefin, and the complex of the BF ₃ -complexing agent or the cocatalyst containing the complexing agent are directly injected into the continuous reactor (10), and the catalyst containing BF ₃ gas is supplied to the circulation pump (21). ) It can be injected into the loop reactor 20 through the subsequent circulation pipe. At this time, as it is difficult to use the reactor when the gas content in the liquid phase is more than 1% by volume, the BF ₃ gas is injected into the loop reactor 20 through the circulation pipe after the circulation pump 21. It is desirable. In this way, by injecting a catalyst containing BF ₃ gas through the loop reactor, the residence time of BF ₃ gas in the reactor can be increased, and the molar ratio of complexing agent/BF ₃ is adjusted to less than 1 to prevent dimerization of alpha-olefin within the loop reactor. It can reduce dimer content and maximize the production of trimers, tetramers, and pentamers, which are commonly used in lubricating oils. This can provide low molecular weight polyalphaolefins with thermal and oxidation stability, low volatility, low pour point, and high viscosity index required in lubricating oils.

At this time, the raw material injection step, catalyst injection step, and cocatalyst injection step may be performed without particularly limiting the order.

Additionally, the continuous reactor may be a Continuous Stirred-Tank Reactor (CSTR).

Meanwhile, in one example of the present invention, the raw material may contain an alpha olefin, and specifically, for example, the alpha olefin may include an alpha olefin having 6 to 14 carbon atoms, more specifically, for example, For example, one selected from 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, and 1-tetradecene. It may be more than one, and preferably the alpha olefin may be an alpha olefin having 8 to 12 carbon atoms, particularly preferably 1-decene.

At this time, the raw material may further include one or more types selected from aliphatic hydrocarbon solvents such as pentane, hexane, and heptane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene, as a reaction solvent or diluent.

In one example of the present invention, the catalyst may include BF ₃ gas, and may be injected into the loop reactor in a gaseous state for a two-phase reaction. BF ₃ gas injected into the circulation pipe of the loop reactor is mixed with the stream containing raw materials and cocatalyst and circulated and injected into the continuous reactor. This increases the residence time of BF ₃ gas in the stream, producing low molecular weight polyalphaolefin. can be created effectively.

_Unlike the recent use of only the _complex compound of the BF ₃ -complexing agent in the _production of polyalphaolefin, in the present invention, the catalyst and The molar ratio of complexing agent/BF ₃ in the cocatalyst can be adjusted to less than 1, and through this, the formation of dimers of alpha-olefins can be suppressed and the formation of trimers, tetramers, and pentamers can be promoted. More preferably, the molar ratio of complexing agent/BF ₃ in the catalyst and cocatalyst may be 0.3 to 0.95, more preferably 0.5 to 0.9, and even more preferably 0.6 to 0.8. In this range, the production of alpha-olefin oligomers of dimers and hexamers or higher can be more effectively suppressed.

In particular, preferably, the BF ₃ gas may be added in an amount of 0.01 to 10 mol, more preferably 0.05 to 5 mol, and even more preferably 0.1 to 3 mol, per 100 mol of raw material. Within this range, the production of dimers of 1-decene can be minimized and the production of trimers, tetramers, and pentamers of 1-decene can be maximized.

Meanwhile, in one example of the present invention, the cocatalyst may include a complex of BF ₃ -complexing agent or a complexing agent. As a specific example, it is preferable to use a complexing agent that can form a stable complex with BF _3. Specifically, for example, the complexing agent may include an alcohol compound, and more specifically, for example, It may contain an alcohol compound having 1 to 10 carbon atoms. In particular, when 1-decene is used as the alpha-olefin, it may be more advantageous to use butanol (BuOH) as the complexing agent in selectively producing trimers, tetramers, and pentamers of 1-decene.

When using a complex of the BF ₃ -complexing agent as the cocatalyst, the complex of the BF ₃ -complexing agent may be added in an amount of 0.1 to 10 mol, more preferably 0.3 to 5 mol, based on 100 mol of the raw material. Preferably, it can be added in 0.5 to 2 moles. Additionally, the molar ratio of BF ₃ /complexing agent in the cocatalyst may be 0.8 to 1.2, and preferably 1. When using a complexing agent as the cocatalyst, the complexing agent may be added in an amount of 0.1 to 10 mol, more preferably 0.3 to 5 mol, and even more preferably 0.5 to 2 mol per 100 mol of raw material. . In this range, low molecular weight polyalphaolefin can be effectively produced.

Meanwhile, in one example of the present invention, the reaction temperature of polyalphaolefin may be 30 to 70°C, more preferably 40 to 60°C, and even more preferably 45 to 55°C. The pressure within the reactor may be 1 to 5 bar, more preferably 1 to 3 bar, and even more preferably 1 to 2 bar. The reaction temperature can be controlled through the heat exchanger 22, and the pressure can be adjusted through the gas vent 31 of the BF ₃ gas separator 30.

Meanwhile, the method for producing polyalphaolefin may further include a hydrogenation process of hydrogenating the alphaolefin oligomer prepared through the oligomerization process. That is, after the oligomerization reaction of the polyalphaolefin, the double bond can be converted to a saturated state through a hydrogenation reaction to produce hydrogenated polyalphaolefin. At this time, the hydrophobization process may be performed by a conventional method, specifically, for example, using a nickel (Ni)-based catalyst; Cobalt (Co)-based catalyst; Alternatively, it may be performed using a noble metal catalyst such as palladium (Pd) or platinum (Pt).

The polyalphaolefin prepared through the above-described method may be an oligomer mixture of alpha-olefins. More specifically, the oligomer mixture may have a dimer content of alpha-olefins of less than 11% by weight and a content of hexamers or more of alpha-olefins. It may be less than 10% by weight. More preferably, the dimer content of the alpha olefin may be less than 10% by weight, the content of hexamers or more of the alpha olefin may be less than 8% by weight, and even more preferably, the dimer content of the alpha olefin may be less than 5% by weight, and the alpha olefin may have a dimer content of less than 5% by weight. The content of hexamers or more of olefin may be less than 5% by weight. In addition, the oligomer mixture may have an alpha-olefin pentamer content of 5% by weight or more, more preferably 10% by weight or more, and even more preferably 15% by weight or more. At this time, the lower limit of the dimer or hexamer content of the alpha-olefin may be 0, and the upper limit of the pentamer content of the alpha-olefin may be 25% by weight.

As such, the oligomer mixture prepared through the method for producing polyalphaolefin according to the present invention has a low content of oligomers of dimer and hexamer or higher, and has a low content of trimer, tetramer, and pentamer oligomers even without performing a simple distillation separation process. It can be used as a lubricant with high thermal and oxidation stability, low volatility, low pour point, and high viscosity index. Of course, if necessary, a simple distillation separation process may be further performed to finely control the content of each oligomer, and the present invention does not exclude this.

In addition, the oligomer mixture may have a dimer/pentamer weight ratio of alpha-olefins of 3 or less, and a trimer/tetramer weight ratio of alpha-olefins of 2 or less. More preferably, the dimer/pentamer weight ratio of alpha-olefin may be 2 or less, and the trimer/tetramer weight ratio of alpha-olefin may be 1.7 or less. At this time, the lower limit of the weight ratio of the dimer/pentamer of the alpha-olefin may be 0, and the lower limit of the weight ratio of the trimer/tetramer of the alpha-olefin may be 0.1.

Lubricating oils containing such polyalphaolefins can be used as lubricating base oils, viscosity modifiers, viscosity index improvers, lubricity additives, etc. in fields such as automobile lubricants, gear oils, industrial lubricants, and greases.

Hereinafter, the present invention will be described in detail by examples and comparative examples. The examples below are only intended to aid understanding of the present invention, and the scope of the present invention is not limited by the examples below.

[Comparative Example 1]

During the oligomerization reaction, 1-decene monomer is continuously fed into the continuous reactor at a supply rate of 3200 kg/hr, while simultaneously BF ₃ -butanol complex (BF ₃ -BuOH, molar ratio 1) is fed into the continuous reactor at a supply rate of 67.9 kg/hr. did. Polymerization was carried out for 60 minutes while maintaining a temperature of 50°C and a pressure of 1.5 bar. To prevent further unwanted polymerization from proceeding, a reaction stopper (20 wt% NaOH aqueous solution) was injected to deactivate the catalyst and terminate the reaction. Deactivated catalysts and other metals were removed by washing with water. The minimum contact flow rate of the reaction stopper corresponds to 90-100% of the flow rate of the reactants (weight ratio), and the reaction was terminated by adding it to the polymer continuously discharged through a reverse pressure regulator. Next, the upper organic layer was extracted, and unreacted 1-decene and side reaction product decene isomers were removed by stripping to prepare decene oligomer (PAO).

Afterwards, hydrogenated decene oligomer was obtained by hydrogenation using a nickel-based catalyst (nickel content 21-32% by weight).

[Comparative Example 2]

During the oligomerization reaction, 1-decene monomer was continuously fed into the continuous reactor at a supply rate of 5 cc/min and butanol at a supply rate of 0.03 cc/min, while BF ₃ was continuously supplied to the top of the continuous reactor at a temperature of 50°C and a pressure of 3 bar. All processes were performed in the same manner as in Comparative Example 1 except that polymerization was maintained for 60 minutes.

[Comparative Example 3]

During the oligomerization reaction, 1-decene monomer was continuously fed into the continuous reactor at a supply rate of 5 cc/min and butanol at a supply rate of 0.035 cc/min, while BF ₃ was continuously supplied to the top of the continuous reactor at a temperature of 50°C and a pressure of 3 bar. All processes were performed in the same manner as in Comparative Example 1 except that polymerization was maintained for 60 minutes.

[Comparative Example 4]

During the oligomerization reaction, 1-decene monomer was continuously supplied to the continuous reactor at a supply rate of 5 cc/min and butanol at a supply rate of 0.03 cc/min. BF ₃ was supplied together with 1-decene monomer and butanol, and the temperature was 50°C. All processes were carried out in the same manner as in Comparative Example 1 except that polymerization was carried out for 60 minutes while maintaining a pressure of 3 bar.

[Comparative Example 5]

During the oligomerization reaction, 1-decene monomer was supplied to the continuous reactor at a supply rate of 5 cc/min and butanol at a supply rate of 0.035 cc/min. BF ₃ was supplied together with 1-decene monomer and butanol, and the temperature was 50°C and the pressure was 3. All processes were carried out in the same manner as in Comparative Example 1 except that polymerization was carried out for 60 minutes while maintaining the bar.

[Example 1]

During the oligomerization reaction, 1-decene monomer is continuously fed into the continuous reactor at a feed rate of 3200 kg/hr, while BF ₃ is fed into the loop reactor at a feed rate of 26.24 kg/hr, and butanol is continuously fed at a feed rate of 26.24 kg/hr. All processes other than injection into the reactor were performed in the same manner as in Comparative Example 1.

[Example 2]

During the oligomerization reaction, 1-decene monomer is continuously fed into the continuous reactor at a feed rate of 3200 kg/hr, while BF ₃ is fed into the loop reactor at a feed rate of 30.15 kg/hr, and butanol is continuously fed at a feed rate of 20.1 kg/hr. All processes other than injection into the reactor were performed in the same manner as in Example 1.

[Example 3]

During the oligomerization reaction, 1-decene monomer is continuously fed into the continuous reactor at a feed rate of 3200 kg/hr, while BF ₃ is fed into the loop reactor at a feed rate of 36.0 kg/hr, and butanol is continuously fed at a feed rate of 18.0 kg/hr. All processes other than injection into the reactor were performed in the same manner as in Example 1.

[Example 4]

During the oligomerization reaction, 1-decene monomer is continuously fed into the continuous reactor at a feed rate of 3200 kg/hr, while BF ₃ is fed into the loop reactor at a feed rate of 2.8 kg/hr, and BF ₃ -butanol complex (BF ₃ -BuOH) , molar ratio 1) was carried out in the same manner as in Example 1 except that the molar ratio was injected into the continuous reactor at a supply rate of 46.11 kg/hr.

[Example 5]

During the oligomerization reaction, 1-decene monomer is continuously fed into the continuous reactor at a feed rate of 3200 kg/hr, while BF ₃ is fed into the loop reactor at a feed rate of 3.9 kg/hr, and BF ₃ -butanol complex (BF ₃ -BuOH) , molar ratio 1) was carried out in the same manner as in Example 4 except that the molar ratio was injected into the continuous reactor at a supply rate of 39.34 kg/hr.

[Example 6]

During the oligomerization reaction, 1-decene monomer is continuously fed into the continuous reactor at a feed rate of 3200 kg/hr, while BF ₃ is fed into the loop reactor at a feed rate of 5.7 kg/hr, and BF ₃ -butanol complex (BF ₃ -BuOH) , molar ratio 1) was carried out in the same manner as in Example 4 except that the feed was injected into the continuous reactor at a supply rate of 37.34 kg/hr.

[Example 7]

During the oligomerization reaction, 1-decene monomer is continuously fed into the continuous reactor at a feed rate of 3200 kg/hr, while BF ₃ is fed into the loop reactor at a feed rate of 10.1 kg/hr, and BF ₃ -butanol complex is fed at 32.57 kg/hr. All processes were carried out in the same manner as in Example 4, except that the supply amount was injected into the continuous reactor.

Injection amount BuOH/BF ₃ total molar ratio 1-decene BF ₃ BuOH BF ₃ -BuOH Example 1 3200 kg/hr 26.24 kg/hr Feed to loop reactor 26.24 kg/hr - 0.91 Example 2 30.15 kg/hr 20.1 kg/hr - 0.61 Example 3 36.0 kg/hr 18.0 kg/hr - 0.46 Example 4 2.8 kg/hr - 46.11 kg/hr 0.89 Example 5 3.9 kg/hr - 39.34 kg/hr 0.83 Example 6 5.7 kg/hr - 37.34 kg/hr 0.76 Example 7 10.1 kg/hr - 32.57 kg/hr 0.61 Comparative Example 1 - - - 67.9 kg/hr 1.0 Comparative Example 2 5 cc/min 8.055 cc/min Feed to the top of the continuous reactor 0.03 cc/min - 1.0 Comparative Example 3 9.397 cc/min 0.035 cc/min - 1.0 Comparative Example 4 8.055 cc/min Feed into continuous reactor with raw materials 0.03 cc/min - 1.0 Comparative Example 5 9.397 cc/min 0.035 cc/min - 1.0

[Characteristics Evaluation]

The decene oligomer mixture prepared through the oligomerization step was analyzed by gas chromatography-flame ionization detector (GC-FID, column Agilent HP-5HT) to determine the size of each decene oligomer (dimer C20, trimer C30, tetramer C40, and pentamer C50). , the content of hexamer or higher C60) was confirmed, and the results are shown in Table 2 below.

P.A.O.
Yield (%) Content of each decene oligomer (% by weight) C20/C50
weight ratio C30/C40
weight ratio C20 C30 C40 C50 C60 and above Example 1 81 6.6 52.5 31.2 7.4 2.3 0.89 1.68 Example 2 82 6.6 48.9 31.4 8.9 4.2 0.74 1.56 Example 3 82 7.3 51.6 30.8 8.0 2.3 0.91 1.68 Example 4 82 6.7 52.6 32.3 6.9 1.5 0.97 1.63 Example 5 82 5.7 41.6 39.6 11.2 1.9 0.51 1.05 Example 6 82 3.2 37.7 39.2 16.3 3.6 0.20 0.96 Example 7 85 3.1 31.7 40.5 19.9 4.8 0.16 0.78 Comparative Example 1 80 11.4 60.5 25.4 2.6 0.1 4.38 2.38 Comparative Example 2 83 21.96 51.28 19.81 3.90 3.05 5.63 2.59 Comparative Example 3 90 18.54 42.46 26.68 6.59 5.73 2.81 1.59 Comparative Example 4 90 13.57 43.08 27.88 8.25 7.22 1.64 1.55 Comparative Example 5 89 17.09 43.94 27.49 6.97 4.51 2.45 1.60

Referring to Tables 1 and 2 above, in the case of Examples 1 to 7 in which BF ₃ was supplied to the loop reactor through the circulation pipe after the circulation pump according to the production method of the present invention, the residence time of the BF ₃ gas in the reactor was By increasing, the total molar ratio of BuOH/BF ₃ could be adjusted to less than 1.

On the other hand, in the case of Comparative Example 1, as the catalyst was injected in the form of BF ₃ -BuOH, the total molar ratio of BuOH/BF ₃ was 1.0, and in Comparative Examples 2 to 4, most of the BF was injected even if an excessive amount of BF ₃ gas was injected. ₃ gas was separated from the reactant (liquid phase) and existed as a gas phase, and as a result, the reaction proceeded in a 2-phase (liquid-vapor phase) form, so there was little effect of injecting an excessive amount of BF ₃ gas, and BuOH involved in the reaction The total molar ratio of /BF ₃ is judged to be 1.0.

In this way, in Examples 1 to 7, in which BF ₃ gas was separately injected through the loop reactor and the total molar ratio of BuOH / BF ₃ in the catalyst and cocatalyst was adjusted to be less than 1, the hydrogenated decene dimer compared to Comparative Examples 1 to 5 The proportion of the decene dimer (C20) was significantly low, and even though the simple distillation separation process was not performed, the content of the decene dimer (C20) was low at less than 7.3% by weight, and the ratio of the trimer, tetramer, and pentamer useful for lubricating oil. It was higher than this, confirming its usefulness as a lubricant.

10: continuous reactor 20: loop reactor
21: circulation pump 22: heat exchanger
30: gas separator 31: gas vent
40: Separator (coalesce)

Claims (18)

continuous reactor; And a loop reactor that receives reactants from the bottom discharge of the continuous reactor and re-supplies the reactants to the continuous reactor through a circulation pump and circulation pipe. In the method for producing polyalphaolefin using a reaction device comprising a,
Injecting raw materials containing alpha-olefin into the continuous reactor;
Injecting a catalyst containing BF ₃ gas into the loop reactor; and
BF ₃ - Injecting a complex of a complexing agent or a cocatalyst containing a complexing agent into the continuous reactor,
A method for producing polyalphaolefin, characterized in that the molar ratio of complexing agent / BF ₃ in the catalyst and cocatalyst is less than 1. According to paragraph 1,
A method for producing polyalphaolefin, wherein the BF ₃ gas is injected into a loop reactor after a circulation pump. According to paragraph 1,
A method for producing polyalphaolefin, wherein the BF ₃ gas is added in an amount of 0.01 to 10 mol based on 100 mol of the raw material. According to paragraph 1,
A method for producing polyalphaolefin, wherein the complexing agent includes an alcohol compound. According to paragraph 4,
A method for producing polyalphaolefin, wherein the complexing agent includes an alcohol compound having 1 to 10 carbon atoms. According to clause 5,
A method for producing polyalphaolefin, wherein the complexing agent is butanol. According to paragraph 1,
A method for producing polyalphaolefin, wherein the alpha olefin includes an alpha olefin having 6 to 14 carbon atoms. In clause 7,
The alpha olefin is 1-decene, a method for producing polyalpha olefin. According to paragraph 1,
A method for producing polyalphaolefin, wherein the polyalphaolefin is an oligomer mixture of alphaolefins. According to clause 9,
The method for producing polyalphaolefin, wherein the oligomer mixture has a dimer content of alphaolefin of less than 11% by weight. According to clause 9,
A method for producing polyalphaolefin, wherein the oligomer mixture has a pentamer content of alphaolefin of 5% by weight or more. According to clause 9,
The method for producing polyalphaolefin, wherein the oligomer mixture has a dimer/pentamer weight ratio of alphaolefin of 3 or less. According to clause 9,
The method for producing polyalphaolefin, wherein the oligomer mixture has a trimer/tetramer weight ratio of alphaolefin of 2 or less. Polyalphaolefin produced by the method for producing polyalphaolefin according to any one of claims 1 to 13,
The polyalphaolefin is an oligomeric mixture of alphaolefins,
The oligomer mixture is a polyalphaolefin having a dimer content of alphaolefin of less than 11% by weight. According to clause 14,
The oligomer mixture is a polyalphaolefin having a pentamer content of 5% by weight or more. According to clause 14,
The oligomer mixture is a polyalphaolefin in which the dimer/pentamer weight ratio of alphaolefin is 3 or less. According to clause 14,
The oligomer mixture is a polyalphaolefin having a trimer/tetramer weight ratio of alphaolefin of 2 or less. continuous reactor; And a loop reactor that receives reactants from the bottom discharge of the continuous reactor and re-supplies the reactants to the continuous reactor through a circulation pump and circulation pipe. A reaction device for producing polyalphaolefin, comprising:
A raw material containing alpha-olefin and a complex of BF ₃ -complexing agent or a cocatalyst containing a complexing agent are directly injected into the continuous reactor,
A reaction device for producing polyalphaolefin, characterized in that the catalyst containing BF ₃ gas is injected into the loop reactor through the circulation pipe after the circulation pump.