KR101888783B1 - Catalyst composition for producing polybutene, Polybutene produced by employing the same and Method of producing the same - Google Patents

Abstract

The present invention relates to a catalyst composition for manufacturing polybutene, polybutene manufactured from the catalyst composition, and a method for manufacturing the catalyst composition. The present invention relates to a catalyst composition for manufacturing polybutene containing aluminum chloride dispersed in a hydrocarbon solvent, wherein the aluminum chloride has a D90 of 60 μm or less. D90 is a size value at which a cumulative particle size distribution of the particle size corresponds to 90%.

Description

TECHNICAL FIELD The present invention relates to a catalyst composition for producing polybutene, a polybutene prepared from the catalyst composition, and a process for producing the catalyst composition,

The present invention relates to a catalyst composition for producing polybutene, polybutene prepared from the catalyst composition and a process for producing the catalyst composition.

Polybutene is an isobutene polymer produced by Cationic polymerization using a C4 residue produced by naphtha pyrolysis process or C4 oil produced by catalytic cracking of heavy oil during petroleum refining process as a raw material, It is a liquid or rubber liquid which is generally used in adhesives, lubricants, lubricant thickeners, plasticizers, asphalt modifiers, battery insulating oils, sealants, caulking agents and dispersants, etc., having odorless, non-toxic, viscous and adhesive properties. It is a polymer.

The method of injecting an aluminum chloride catalyst in the production of polybutenes using anhydrous aluminum chloride as a catalyst is divided into a homogenization method in which a liquid phase is injected and a heterogeneous method in which the catalyst is injected into a slurry or a complex phase.

Anhydrous aluminum chloride used as a catalyst is sold in bulk or in powder form. The size of the particles is about 1 mm in the powder phase and the mass is in the range of 2 to 10 mm. In the homogenization method, both bulk and powder phase are used, But it does not dissolve in hydrocarbon compounds at room temperature. Unsaturated hydrocarbon reacts partially at room temperature to form an aluminum chloride-hydrocarbon complex, which has good fluidity. However, the more aluminum chloride involved in forming such a complex, the more polymer And the total activity is lowered.

Aluminum chloride, a Friedel-Craft type catalyst, is a catalyst for preparing polybutene by cationic polymerization method of unsaturated hydrocarbon monomer, especially isobutene. In this case, physical properties of polybutene are determined according to the amount and activity of aluminum chloride.

In the homogenization method, aluminum chloride is dissolved in high-temperature and high-pressure butane to inject (US Pat. No. 3,501,551), or hydrochloric acid or a mixture of hydrocarbon and hydrocarbon is injected in a liquid state (US Pat. No. 3,985,822) , Butane separation purification is required for the production of a large amount of purified butane and catalyst and an increase in the vapor pressure of the high temperature increases the manufacturing cost of the catalyst manufacturing apparatus and the transferring apparatus, Cooling proceeds. At this time, dissolved aluminum chloride precipitates, which causes a problem of clogging of the cooler or the heat exchanger. In order to increase the solubility of hydrocarbons and aluminum chloride, hydrochloric acid or chlorinated hydrocarbons may be mixed. This is because the method of dissolving aluminum chloride by hydrochloric acid and hydrocarbons causes corrosion of the dissolver and the reactor part due to corrosive hydrochloric gas, A separate chlorine separation process must be added since unreacted C4 and the hydrogen chloride compound remain in the product due to the recovery and low molecular weight polybutene removal process.

In another method (Korean Patent No. 1995-032312) in which aluminum chloride is mixed with polybutene having a number average molecular weight in the range of 500 to 3,000 and the catalyst is injected by a metering pump in order to suppress the settling of the catalyst, the deactivation of the catalyst can be avoided, There is a possibility that the mixture of the charged catalyst and the polybutene may have an influence on the final product although it is a trace amount, and the higher the number average molecular weight, the disadvantage is that it is necessary to raise the temperature for smooth transport.

It is an object of the present invention to provide a catalyst composition for polybutene production which can increase the dispersibility of aluminum chloride and inject the catalyst at a uniform concentration smoothly and increase the activity of the catalyst and reduce the amount of catalyst used.

It is still another object of the present invention to provide polybutene which is low in impurities and can provide excellent quality to the final product.

It is still another object of the present invention to provide a method for producing a catalyst composition for polybutene production which can increase the dispersibility of aluminum chloride and smoothly inject the catalyst at a uniform concentration, .

In order to achieve the object of the present invention, the present invention provides a catalyst composition for the production of polybutene containing aluminum chloride dispersed in a hydrocarbon solvent, wherein the aluminum chloride has a D ₉₀ of not more than 60 탆.

Here, D ₉₀ is a size value at which the cumulative particle size distribution of the particle size corresponds to 90%.

In order to accomplish still another object of the present invention, there is provided a process for preparing a catalyst composition, comprising: adding aluminum chloride to a hydrocarbon solvent and pulverizing the same with a pulverizer to prepare a catalyst composition; And pulverizing and homogenizing the pre-treated catalyst composition with a high-pressure homogenizer so that the D ₉₀ of the aluminum chloride is 60 탆 or less. The present invention also provides a method for producing a catalyst composition for polybutene production.

Since the catalyst composition according to the present invention is uniformly dispersed in the hydrocarbon solvent, it is possible to inject the catalyst at a uniform concentration. Particularly, since the size of the catalyst particles is reduced, the activity of the catalyst is increased, The stability can be maintained.

In addition, the method for producing a catalyst composition according to the present invention makes it possible to produce a catalyst composition containing uniformly small particles of aluminum chloride only by using a special high-pressure homogenizer without any special solvent or specific conditions or complicated processes, The manufacturing cost can be lowered and the post-treatment cost can also be reduced.

Hereinafter, the present invention will be described in more detail. However, this is for the purpose of illustration only and should not be construed as limiting the scope of the invention.

According to one embodiment of the present invention, the catalyst composition for the production of polybutene according to the present invention is a catalyst composition for the production of polybutene containing aluminum chloride dispersed in a hydrocarbon solvent, wherein the aluminum chloride has a D ₉₀ of not more than 60 μm .

The polybutene is generally obtained by polymerizing an olefin component having 4 carbon atoms (C4) derived from the decomposition of naphtha using a Friedel-Craft type catalyst, and has a number average molecular weight (Mn) of about 300 To 1,000,000 g / mol, preferably 300 to 5,000 g / mol. C4 raffinate-1 is obtained by extracting 1,3-butadiene from the C4 raw material, and isobutane, normalbutane paraffins and 1-butene (1- butene, 2-butene, isobutene, and the like. The C4 residue-1 is mainly used for the production of methyl t-butylether (MTBE) or polybutene, which is an octane value improver, and isobutene among the olefin components of the C4 residue-1 The produced polybutene is mainly composed of isobutene units.

In the present invention, "polybutene" means polybutene recovered from reactive polybutene (vinylidene content of 70 wt% or more). That is, the catalyst composition according to the present invention can be used for producing polybutene excluding reactive polybutene, and preferably non-reactive polybutene (content of vinylidene is 20% or less).

Here, D ₉₀ is a size value corresponding to 90% of the cumulative particle size distribution of the particle size, and is a concept distinct from the average particle size of aluminum chloride particles. That is, even if the average particle diameter of the aluminum chloride particles is 60 탆 or less, D90 may exceed 60 탆, and in such a case, a desired effect can not be obtained.

According to one embodiment of the present invention, D90 of preferably zinc chloride, more preferably aluminum chloride (aluminum trichloride) is 0.1 탆 or more, more preferably 8 탆 or less.

If the D90 of aluminum chloride is smaller than 0.1 mu m, the catalyst activity becomes too high to become unstable and may explode depending on the surrounding environment.

According to an embodiment of the present invention, it is preferable that D ₉₀ -D ₁₀ of aluminum chloride is 20 탆 or less.

Here, D ₉₀ and D ₁₀ mean the particle size at which the cumulative particle size distribution (cumulative curve) of the particle size becomes 90% and 10% when the cumulative curve of the particle size distribution is obtained with the total weight being 100%. When D ₉₀ -D ₁₀ of aluminum chloride is larger than 20 탆, the sedimentation rate becomes high and the lifetime of the catalyst composition is shortened, or the quality of the polybutene produced when used in the production of polybutene may be deteriorated.

According to an embodiment of the present invention, (D ₉₀ -D ₁₀ ) / D ₅₀ of the aluminum chloride is preferably 0.5 to 3.

Here, D ₉₀ and D ₁₀ mean the particle size at which the cumulative particle size distribution cumulative curves (cumulative curves) of 90% and 10%, respectively, are obtained when the cumulative curve of the particle size distribution is 100% ₅₀ is the average particle size.

According to an embodiment of the present invention, the hydrocarbon solvent may be a paraffinic hydrocarbon having 3 to 100 carbon atoms, a hydrocarbon including a reducing structure, or a hydrocarbon including an aromatic group. N-hexane, heptane, C4 LPG and the like can be used.

According to one embodiment of the present invention, the aluminum chloride is contained in the catalyst composition in an amount of 5 to 60 g / ml% (g of the solid catalyst is added to 100 ml of solvent). Outside of this range, the dispersibility may be poor or the catalytic activity may be lowered.

According to another embodiment of the present invention, there is provided a method for preparing a catalyst composition, comprising: adding aluminum chloride to a hydrocarbon solvent, pulverizing the mixture with a pulverizer to prepare a catalyst composition; And crushing and homogenizing the pretreated catalyst composition with a high pressure homogenizer so that the D ₉₀ of aluminum chloride is 60 탆 or less.

The step of using the high pressure homogenizer is preferably performed under a pressure of 200 to 500 bar, preferably 10 to 30 minutes.

The pulverizer may be at least one selected from a spike mill, a hammer mill, a rod mill, a ball mill, a Raymond mill, a VETICAL ROLL mill, a PIN mill, a jet mill, a conical ball mill and a vibratory mill.

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

 ≪ Preparation of polybutene using catalyst composition >

Example  1 to Example  9, and Comparative Example  One

The C4 oil fraction (200 g) having the composition shown in Table 1 was used, and the catalyst composition was prepared by dispersing 600 g of hexane as a solvent in hexane according to Table 2, and the content of isobutene in the C4 oil fraction at 20 < And the aluminum content was adjusted to 0.02 wt% to prepare polybutene.

The average particle size of the aluminum chloride catalyst dispersed in the used hexane was confirmed by using an optical microscope from Olympus, and the uniformity was 10% and 90% of the maximum value in the particle size cumulative distribution measured by the particle size analyzer And D90, respectively.

Comparative Example  2

Polybutene was prepared in the same manner as in Example 1, except that 5 g of a massive aluminum chloride particle having a particle size of 2 to 5 mm was dispersed in 100 ml of hexane.

C4 oil composition component ingredient mol (%) methane 0.01 Propane 0.07 Cyclopropane 0.06 Propylene 0.30 Isobutane 5.24 n-butane 9.70 2-butene (trans) 1.27 1-butene 0.95 Isobutene 81.53 2-butene (cis) 0.83 1,2-butadiene 0.05

Example Catalyst concentration
(g / ml%) Catalyst average
Particle size
(탆) Particle size
D ₉₀
(탆) Uniformity
(D ₉₀ -D ₁₀ )
(탆) Span
(D ₉₀ -D ₁₀ ) / D ₅₀ One 5 15 50 49 3.27 2 5 12 30 28 2.33 3 5 9 16 14 1.56 4 5 6 10 9 1.50 5 10 7 12 12 1.71 6 15 9 16 15 1.67 7 20 13 29 28 2.15 8 30 16 38 36 2.25 9 5 14 50 48 3.43 Comparative Example 1 5 21 95 91 4.33

Experimental Example  1: catalytic activity

The yields of polybutene prepared according to Examples and Comparative Examples were as follows: the yields of isobutene to polyisobutene in the C4 oil fraction after 10 minutes from the introduction of both the C4 oil fraction and the catalyst composition according to Examples and Comparative Examples Were measured. The results are shown in Table 3 below.

Experimental Example  2: APHA (Chromaticity)

APHA of the polybutene prepared according to Examples and Comparative Examples was measured by ASTM D1209 using a PFX? -195 Series equipment manufactured by Lovibond. The results are shown in Table 3 below. A low APHA value means high transparency. The higher the transparency of the PIB used as a lubricant additive is, the better the property is, and preferably 20 or less.

As can be seen from the above Table 2, according to the present invention, when D90 was 60 탆 or less, excellent catalytic activity was exhibited, and it was found that the crushed aluminum chloride catalyst exhibited a low APHA value to improve the final PIB property . However, when Comparative Example 1 and Example 8 are compared, it is found that the average particle size of the catalyst particles is 60 탆 or less, but D90 is out of the scope of the present invention.

Experimental Example  3: Number average  Molecular weight measurement

The molecular weights of the polybutenes prepared according to Examples and Comparative Examples were measured by using a polystyrene standard sample (molecular weight: 5000 g / mol) in the polymer and two solvents in a 5-μm polystyrene mixed-C column of PLgel . The detector uses a refractive index detector (RI). The results are shown in Table 3 below. The number average molecular weight can be suitably adjusted according to the PIB application. According to one embodiment of the present invention, the number average molecular weight of the PIB polymer may be adjusted to 300 to 5,000 g / mol.

Physical properties of polybutene Example Catalyst activity (%) APHA Mn (g / mol) One 71 10 1,880 2 89 10 1,390 3 95 10 1,260 4 97 10 1,170 5 95 10 1,220 6 94 10 1,240 7 91 10 1,280 8 89 12 1,360 9 83 15 1,440 Comparative Example 1 56 28 2,520

≪ Preparation of catalyst composition >

Example  10

One) Catalyst pretreatment step

7 liters of hexane and 0.35 kg of aluminum chloride were added to a 10 liter round reactor in a nitrogen atmosphere and the mixture was refluxed for 2 minutes with a stirrer. To the bridge half by means of a pump milled for 30 minutes mill repeatedly to the average particle size and particle size distribution D ₁₀ is 300㎛ 150㎛, D ₉₀ was prepared by pre-treatment so that the 450㎛.

2) With high pressure homogenizer  Catalyst crushing and Homogenization

The pretreated slurry was homogenized repeatedly at 200 bar pressure for 10 minutes using a high pressure homogenizer to prepare a catalyst in which aluminum chloride having a particle size D ₉₀ of 60 μm or less was dispersed in hexane.

Example  11 - Example  16

A catalyst composition in which aluminum chloride was dispersed in hexane was prepared in the same manner as in Example 10, except that the pressure of the high-pressure homogenizer was changed as shown in Table 4.

Comparative Example  3

Massive aluminum chloride particles having a particle size of 2 to 5 mm were pulverized in a nitrogen atmosphere using a ball mill, and then 5 g of aluminum chloride was dispersed in 100 ml of hexane to prepare a catalyst composition.

Comparative Example  4

A 500 cc capacity mixer equipped with a ribbon or spiral impeller was placed in the mixer several times with nitrogen gas. The temperature in the mixer was kept constant at 20 캜, 100 cc of polybutene having a number average molecular weight of 1,000, 30 g of aluminum chloride powder having a mesh size was added and stirred at 50 rpm for 30 minutes to prepare a catalyst composition.

Comparative Example  5

Massive aluminum chloride particles having a particle size of 2 to 5 mm were crushed in a nitrogen atmosphere using a laboratory mixer (Waring 4 Liter Laboratory Blender), and 5 g of aluminum chloride pulverized in 100 ml of hexane was dispersed to prepare a catalyst composition.

Experimental Example  4: Measurement of sedimentation velocity

In the catalyst compositions prepared according to Examples 10 to 16 and Comparative Examples 3 to 5, the settling rate of the catalyst particles was confirmed by using a tableting machine of Formulation Co., Ltd., without any change in the aluminum chloride layer. The particle size distribution of the catalyst composition was carried out in the same manner as in the measurement of the catalyst in Example 1. The results are shown in Table 4.

Example High pressure homogenizer
Operating pressure
(bar) Catalyst concentration
(g / ml%) Settling time
(min) D ₉₀
(탆) Uniformity
(D ₉₀ -D ₁₀ )
(탆) 10 200 5 One 50 49 11 300 5 1.5 30 28 12 400 5 3 16 14 13 500 5 7.5 10 9 14 500 10 7 12 12 15 500 15 7 16 15 16 500 30 7 38 36 Comparative Example 3 Using a ball mill 5 <0.2 340 325 4 200 mesh catalyst dispersion in PB 30 > 7 * 70 55 5 Experimental Mixer 5 0.5 240 170

*: The catalyst was dispersed in a PB having a viscosity, and the settling velocity was much larger than that in Hx. (Not subject to comparison)

From Table 4, only when the high-pressure homogenizer according to the present invention was used, D90 of the catalyst particles was 60 mu m or less, and by the same method as Comparative Examples 3 to 5, It can be seen that the composition can not be obtained.

Claims (16)

A catalyst composition for producing polybutene, comprising aluminum chloride dispersed in a hydrocarbon solvent,
The D ₉₀ of the aluminum chloride is 60 탆 or less,
Here, D ₉₀ means the particle size at which the cumulative curve of the particle size becomes 90% when calculating the cumulative curve of the particle size distribution with the total weight being 100%
Wherein the catalyst composition for producing polybutene does not contain polybutene. The method according to claim 1,
Wherein the hydrocarbon solvent is a paraffinic hydrocarbon having a carbon number of 3 to 100 or a hydrocarbon containing a reducing structure or a hydrocarbon containing an aromatic group. The method according to claim 1,
Wherein the aluminum chloride has a D ₉₀ of 8 μm or less. The method according to claim 1,
Catalyst compositions, characterized in that not less than D ₉₀ of the aluminum chloride 0.1㎛. The method according to claim 1,
Wherein the aluminum chloride has a D ₉₀ -D ₁₀ of 20 μm or less.
(Where D ₉₀ and D ₁₀ are size values corresponding to cumulative particle size distributions of 90% and 10%, respectively) The method according to claim 1,
Of the aluminum chloride _{(D 90 -D 10) / D} 50 of the catalyst composition, characterized in that 0.5 to 3.
(Where D _90, D ₅₀ and D ₁₀ are size values corresponding to cumulative particle size distributions of 90%, 50% and 10%, respectively) The method according to claim 1,
Wherein the content of aluminum chloride is 5 to 60 g / ml%. A polybutene prepared from the catalyst composition according to any one of claims 1 to 7. The polybutene according to claim 8, wherein the polybutene has a number average molecular weight of 300 to 1,000,000 g / mol. Adding aluminum chloride to the hydrocarbon solvent and pulverizing the mixture with a pulverizer while stirring to pre-treat the catalyst composition; And
Crushing and homogenizing the pretreated catalyst composition with a high-pressure homogenizer so that the D ₉₀ of aluminum chloride is 60 탆 or less, the method comprising the steps of:
Wherein the catalyst composition for producing polybutene does not contain polybutene. 11. The method of claim 10,
Wherein the step of using the high pressure homogenizer is performed under a pressure of 200 to 500 bar. 11. The method of claim 10,
Process for producing a catalyst composition, characterized in that the D ₉₀ of the aluminum chloride 8㎛ or less. 11. The method of claim 10,
Process for producing a catalyst composition, characterized in that not less than D ₉₀ of the aluminum chloride 0.1㎛. 11. The method of claim 10,
Wherein the aluminum chloride has a D ₉₀ -D ₁₀ of 20 μm or less.
(Where D ₉₀ and D ₁₀ are size values corresponding to cumulative particle size distributions of 90% and 10%, respectively) 11. The method of claim 10,
Wherein the aluminum chloride (D ₉₀ -D ₁₀ ) / D ₅₀ is 0.5 to 3.
(Where D _90, D ₅₀ and D ₁₀ are size values corresponding to cumulative particle size distributions of 90%, 50% and 10%, respectively) 11. The method of claim 10,
Wherein the pulverizer is at least one selected from the group consisting of a spike mill, a hammer mill, a rod mill, a ball mill, a Raymond mill, a VETICAL ROLL mill, a PIN mill, a jet mill, a conical ball mill and a vibratory mill.