WO2020262774A1 - Polybutene producing method, polybutene producing apparatus, and polybutene produced thereby - Google Patents

Abstract

The present invention relates to a producing method for high-functional polybutene with a halogen component removed therefrom, a producing apparatus therefor, and polybutene produced thereby.

Description

Polybutene manufacturing method, polybutene manufacturing apparatus, and polybutene manufactured thereby

The present invention relates to a method for producing high-performance polybutene from which a halogen component is removed, a production apparatus, and a polybutene produced thereby.

Polybutene is a polymerization of an olefin component having 4 carbon atoms, which is generally derived from the decomposition process of naphtha, and uses high purity isobutene, C4 raffinate-1, and butane-butene fraction (BB fraction). It is manufactured using as. In the case of polybutene and low-molecular polymer prepared by using the high-purity isobutene diluted with a solvent of butanes as a raw material, the content of halogen is not high, whereas the content of 1,3-butadiene from the C4 raw material is extracted and the remaining above When C4 residues-1 and the butane-butene fraction, which is a C4 mixture derived from the crude oil refining process, are used as raw materials, a high content of halogen is present in the polybutene and low molecular weight polymers produced. Due to the high content of organic halogen, it is difficult to directly use it as a fuel additive using a low molecular weight polymer, a friction reducing agent, a non-romantic organic solvent, and a cosmetic additive, and a low molecular weight polymer containing a halogen component (Light Polymer) Are sold only as waste or low-cost fuel oil.

U.S. Patent No. 7,365,152 discloses a method of removing fluorine contained in highly reactive polybutene prepared using a Lewis acid-based catalyst. Disclosed is a method of preparing a highly reactive polybutene with a low fluorine content by diluting the highly reactive polybutene prepared by the above method in a solvent and passing through an alumina column impregnated with a compound for removing fluorine, but an additional process after polybutene production As a result, there is a disadvantage that the installation of an adsorption column and periodic replacement of the adsorbent are required, and a process of removing the solvent from the removed polybutene solution has to be added.Therefore, a method capable of producing polybutene with reduced halogen content more economically and The demand for the device continues.

The present invention provides a method for producing a high-performance polybutene from which a halogen component has been removed, a production apparatus, and a polybutene produced thereby.

The present invention comprises the steps of: (a) polymerizing polybutene by supplying a reaction raw material to a polybutene reactor;

(b) removing low molecular weight polybutene (LMPIB) from the polybutene of step (a);

(c) removing a halogen component from the polybutene of step (b) in a fixed tubular reactor including a hydrogen supply device and a catalyst for hydrogenation;

In the polybutene production method comprising the step of (d) removing an acidic gas component from the polybutene of step (c),

The fixed tubular reactor in step (c) has a weight hourly space velocity (WHSV) of 50 to 200, and a hydrogen pressure of 1 to 10 kgf/cm ² .

In addition, the present invention is a polybutene production apparatus in which a fixed-bed reactor including a low molecular weight removal device, a hydrogen supply device, and a catalyst for hydrogenation are sequentially connected to the rear end of the polybutene reactor,

A scrubber for treating acidic gas is connected to the fixed tubular reactor,

The fixed tubular reactor has a weight hourly space velocity (WHSV) of 50 to 200, and a hydrogen pressure of 1 to 10 kgf/cm ² .

In addition, the present invention provides a polybutene manufactured by the above manufacturing method or manufactured by the above manufacturing apparatus.

The method and apparatus for producing polybutene of the present invention provides high-performance polybutene from which halogen components are removed. In addition, the method and apparatus for producing polybutene according to the present invention can increase production efficiency by providing polybutene having a halogen component content of close to 0 ppm and a high olefin content without a separate additional process.

Hereinafter, the present invention will be described in detail. However, it is not limited only by the following contents, and each component may be variously modified or selectively used as necessary. Therefore, it is to be understood as including all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

The present invention comprises the steps of: (a) polymerizing polybutene by supplying a reaction raw material to a polybutene reactor;

(b) removing low molecular weight polybutene (LMPIB) from the polybutene of step (a);

(c) removing a halogen component from the polybutene of step (b) in a fixed tubular reactor including a hydrogen supply device and a catalyst for hydrogenation;

In the polybutene production method comprising the step of (d) removing an acidic gas component from the polybutene of step (c),

The fixed tubular reactor in step (c) has a weight hourly space velocity (WHSV) of 50 to 200, and a hydrogen pressure of 1 to 10 kgf/cm ² .

According to one embodiment, the low molecular weight polybutene refers to polybutene of C ₂₀ or less.

In addition, the present invention is a polybutene production apparatus in which a fixed-bed reactor including a low molecular weight removal device, a hydrogen supply device, and a catalyst for hydrogenation are sequentially connected to the rear end of the polybutene reactor,

A scrubber for treating acidic gas is connected to the fixed tubular reactor,

The fixed tubular reactor has a weight hourly space velocity (WHSV) of 50 to 200, and a hydrogen pressure of 1 to 10 kgf/cm ² .

Hereinafter, steps and devices included in the manufacturing method and manufacturing apparatus will be described in detail.

According to an embodiment of the present invention, a raw material supply line is directly connected to the polybutene reactor to supply the reaction raw material. The kind of the reaction raw material is not particularly limited as long as it is an olefin compound having 4 carbon atoms, but may be, for example, a fraction of 4 carbon atoms, a 4 carbon number LPG (liquefied petroleum gases), and mixtures thereof.

For example, the polybutene reactor may be a polymerization of polybutene by adding a polybutene polymerization catalyst together with the above-described reaction raw material. The catalyst may be used without particular limitation as long as it is a conventional catalyst used for polybutene polymerization. For example, the catalyst may include at least one selected from an aluminum chloride catalyst and a boron trifluoride complex catalyst.

The type of the polybutene reactor is not particularly limited, and may be one selected from a continuous stirring tank reactor (CSTR), a batch reactor, and a tubular reactor. For example, the polybutene reactor may be a continuous stirring tank reactor (CSTR), and two or more continuous stirring tank reactors (CSTR) may be connected in parallel.

The polymerization of polybutene in the polybutene reactor may be carried out under normal reaction conditions, and in consideration of molecular weight, the reaction is preferably carried out at a temperature of -25 to 50 °C, and 7 kgf so that the raw material can maintain a liquid state. It may be economical to set the pressure at a pressure of /cm ² or more, and to react for a residence time of 90% or more and a reaction time of 5 to 60 minutes, preferably 10 to 30 minutes. After the reaction of the polybutene, neutralization, washing, and solvent recovery may be additionally performed.

According to an embodiment of the present invention, the prepared polybutene may remove low molecular weight polybutene (LMPIB) by passing through a low molecular weight removal device. When the low molecular weight polybutene (LMPIB) remains, there may be a problem in that the flash point is lowered. For example, as the low molecular weight removal device, a vacuum purification tower may be used.

The process conditions of the low molecular weight removal device are not particularly limited, and for example, may be performed under conditions of 180 to 230° C. and 5 to 50 mbar. When the process conditions of the low molecular weight removal device satisfy the above-described range, low molecular weight polybutene (LMPIB) can be efficiently removed.

According to an embodiment of the present invention, the polybutene includes the step of passing through a fixed tubular reactor including a hydrogen supply device and a catalyst for hydrogenation. The polybutene may remove the halogen component contained in the polybutene by passing through a fixed tubular reactor including a hydrogen supply device and a catalyst for hydrogenation.

The process conditions of the hydrogen supply device are not particularly limited, and for example, may be performed under conditions of 120 to 200° C. and 2 to 5 kgf/cm ² .

The type of the catalyst for the hydrogenation reaction is not particularly limited, but, for example, a Group 10 metal compound such as Ni, Pd, and Pt may be used.

According to an embodiment of the present invention, the polybutene includes the step of removing an acidic gas component through a scrubber. The scrubber can remove acid gases generated as by-products in the process step, and can efficiently treat various waste gases containing acidic gas components such as hydrogen chloride, hydrogen fluoride, sulfur oxide, nitrogen oxide, hydrogen sulfide, and sulfurous acid gas. . For example, the scrubber may be connected to the fixed tubular reactor.

The scrubber may employ a commonly known structure, and for example, a compressed air supply conduit, a scrubber storage tank, a waste gas supply conduit, a return pipe, and the like may be used.

The present invention provides polybutene, characterized in that it is manufactured by the above manufacturing method and manufacturing apparatus. Polybutene produced by the above manufacturing method and manufacturing apparatus has a halogen content close to 0 ppm, so it can be used as a fuel additive, a friction reducing agent, an organic solvent, and a cosmetic additive without any additional process after manufacturing, and has excellent olefin content. There is an advantage.

The polybutene manufactured by the above manufacturing method and manufacturing apparatus may be a non-reactive polybutene. The non-reactive polybutene may have a vinylidene content of less than 20% by weight at a molecular end and a number average molecular weight of 200 to 5,000 g/mol, preferably 300 to 2,500 g/mol.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to aid understanding of the present invention, and the scope of the present invention is not limited to the examples in any sense.

[Example 1-3]

Using a pilot facility including a 30L CSTR type polybutene reactor, 20 kg/hr of C4 fraction and 40 kg/hr of C4-LPG were continuously injected into a reactor maintained at a temperature of 20°C. In order to keep the raw material liquid, the pressure in the reactor was maintained at 7 kgf/cm ² or higher. Aluminum chloride, which is a catalyst for polymerization of non-reactive polybutene, was injected so as to be 0.05 wt%/hr based on the amount of isobutene in the C4 fraction. The polymerized polymer was transferred to a neutralization tank, neutralized and washed with an aqueous sodium hydroxide solution, and only the organic matter in the upper layer was recovered from a settler, and C4-LPG, a solvent, was recovered and the remaining polybutene was transferred to a reduced pressure polybutene purification tower. Moving and removing the C ₂₀ or less low molecular weight polybutene (LMPIB) under the condition of 210 ℃, 20 mbar to prepare a non-reactive polybutene. The prepared polybutene at about 150℃ supplies hydrogen to the rear end of the polybutene refining tower at a pressure of 3 kgf/cm ² , and is placed in a fixed-bed reactor containing nickel-supported alumina, a catalyst for hydrogenation. WHSV (weight hourly space velocity) was adjusted to be 108 (Example 1), 80 (Example 2), and 50 (Example 3), respectively, and passed through to prepare non-reactive polybutene. The gas generated during the hydrogenation reaction was treated by passing through an aqueous sodium hydroxide solution.

The pressure of the hydrogen supply device, the WHSV of the fixed tubular reactor, the chlorine content and olefin content of the prepared polybutene are shown in Table 1 below.

[Comparative Example 1-3]

Polybutene according to Comparative Example 1-3 was prepared in the same manner as in Example 1-3, except that the weight hourly space velocity (WHSV) was adjusted not to exceed 10.

The pressure of the hydrogen supply device, the WHSV of the fixed tubular reactor, the chlorine content and olefin content of the prepared polybutene are shown in Table 1 below.

[Comparative Example 4]

Using a pilot facility including a 30L CSTR type polybutene reactor, 20 kg/hr of C4 fraction and 40 kg/hr of C4-LPG were continuously injected into a reactor maintained at a temperature of 20°C. In order to keep the raw material liquid, the pressure in the reactor was maintained at 7 kgf/cm ² or higher. Aluminum chloride, which is a catalyst for polymerization of non-reactive polybutene, was injected so as to be 0.05 wt%/hr based on the amount of isobutene in the C4 fraction. The polymerized polymer was transferred to a neutralization tank, neutralized and washed with an aqueous sodium hydroxide solution, and only the organic matter in the upper layer was recovered from a settler, and C4-LPG, a solvent, was recovered and the remaining polybutene was transferred to a reduced pressure polybutene purification tower. Moving and removing low-molecular polybutene (LMPIB) under conditions of 210° C. and 20 mbar to prepare non-reactive polybutene.

The pressure of the hydrogen supply device, the chlorine content and the olefin content of the prepared polybutene are shown in Table 1 below.

	Pressure (kgf/cm 2 )	WHSV	Chlorine content (ppm)	Olefin content (%)
Example 1	3	108	<0.1	100
Example 2	3	80	<0.1	98
Example 3	3	50	<0.1	80
Comparative Example 1	3	3	<0.1	50
Comparative Example 2	60	3	<0.1	3.4
Comparative Example 3	30	3	<0.1	7.7
Comparative Example 4	3	0	10	100

As can be seen from Table 1, in the case of polybutene prepared according to Example 1-3 in which the weight space velocity (WHSV) and pressure of the fixed tubular reactor were set within the ranges limited by the present invention, the chlorine content was 0 It was confirmed that it was close to ppm and the olefin content was high. On the other hand, in the case of polybutene prepared according to Comparative Example 1-3 whose weight and space velocity (WHSV) and/or pressure were out of the range defined in the present invention, compared with the polybutene prepared according to Example 1-3. As a result, it was confirmed that the chlorine content was the same, but the olefin content was low, resulting in deterioration of physical properties of the product. In addition, in the case of the polybutene prepared according to Comparative Example 4 without a fixed tubular reactor, it was confirmed that the chlorine content was very high.

Claims (9)

1. (a) polymerizing polybutene by supplying a reaction raw material to a polybutene reactor;

   (b) removing the low molecular weight polybutene (LMPIB) from the pullybutene of the step (a);

   (c) removing a halogen component from the pullybutene of step (b) in a fixed tubular reactor including a hydrogen supply device and a catalyst for hydrogenation;

   In the polybutene production method comprising the step of (d) removing an acidic gas component from the polybutene of step (c),

   The weight hourly space velocity (WHSV) of the fixed tubular reactor in step (c) is 50 to 200, and the hydrogen pressure is 1 to 10 kgf/cm ² .
2. The method of claim 1, wherein the polybutene reactor comprises at least one selected from an aluminum chloride catalyst and a boron trifluoride complex catalyst.
3. The method of claim 1, wherein the polybutene reactor is at least one selected from a continuous stirring tank reactor (CSTR), a batch reactor, and a tubular reactor.
4. The method of claim 1, wherein the hydrogenation catalyst is at least one selected from Ni, Pd, and Pt.
5. In the polybutene production apparatus in which a fixed-bed reactor including a low molecular weight removal device, a hydrogen supply device, and a catalyst for hydrogenation are sequentially connected to a rear end of the polybutene reactor,

   A scrubber for treating acid gas is connected to the fixed tubular reactor,

   The fixed tubular reactor has a weight hourly space velocity (WHSV) of 50 to 200, and a hydrogen pressure of 1 to 10 kgf/cm ² .
6. The apparatus of claim 5, wherein the polybutene reactor comprises at least one selected from an aluminum chloride catalyst and a boron trifluoride complex catalyst.
7. The apparatus of claim 5, wherein the polybutene reactor is one selected from a continuous stirring tank reactor (CSTR), a batch reactor, and a tubular reactor.
8. The method of claim 5, wherein the hydrogenation catalyst is at least one selected from Ni, Pd, and Pt.
9. It is manufactured by the manufacturing method of any one of claims 1 to 4, or

   Polybutene, characterized in that produced by the production apparatus of any one of claims 5 to 8.