WO2020080647A1 - Method for producing non-reactive polybutene, apparatus for producing non-reactive polybutene, and non-reactive polybutene produced thereby - Google Patents

Abstract

The present invention relates to a method for producing polybutene containing a low halogen element and, more particularly, to a method for producing a non-reactive polybutene (polybutene having a vinylidene content of 40 wt.% or less at the alpha position) having a low chlorine content in a halogen element by adjusting the composition ratio of an aluminum chloride cocatalyst which is a catalyst of non-reactive polybutene such as water.

Description

Method for manufacturing non-reactive polybutene, apparatus for manufacturing non-reactive polybutene, and non-reactive polybutene prepared thereby

The present invention relates to a method for producing a non-reactive polybutene having a low chlorine content by controlling a molar ratio of water (water) / catalyst, a manufacturing apparatus for a non-reactive polybutene, and a non-reactive polybutene produced thereby.

Polybutenes are isobutene polymers made from C4 residue oil produced during the naphtha pyrolysis process or C4 oil produced during catalytic cracking of heavy oil in the petroleum refining process, which are colorless, odorless, and non-toxic, and leave no residue when thermally decomposed. It is a liquid or rubber with viscosity that is widely used in adhesives, lubricants, lubricant thickeners, fuel additive raw materials, plasticizers, asphalt modifiers, battery insulation oils, sealing agents, caulking agents, dispersants, etc. Polymer. In the past, since polybutene was mainly used as an adhesive, adhesive, or insulating oil, low-reactivity products were preferred, and such low-reactivity polybutene was used as a non-reactive polybutene (Conventional PIB, Con-PIB, vinylidene content in alpha position) 40w%, hereinafter referred to as polybutene).

In general, it is a widely known method to use aluminum chloride as a catalyst for non-reactive polybutene. The catalyst, aluminum chloride, is reacted with water or hydrogen chloride to generate hydrogen ions, and the hydrogen ions cause cations in isobutylene, and are prepared by a cationic polymerization method in which polymerization is initiated. The non-reactive polybutene thus prepared may contain residual chlorine. As a non-reactive polybutene, it is used as a fuel additive for a two-stroke engine, or used as an additive for materials that come into contact with metal in various forms. In this case, if the chlorine content of polybutene is high, corrosion of the engine is prevented. Can promote. As described above, various methods are known to reduce the halogen content of polybutene, which greatly affects corrosion of metals.

U.S. Pat.No. 7,365,152 as a prior art discloses a method for removing fluorine from a halogen element of a highly reactive polybutene prepared using a Lewis acid-based catalyst. This is a method of preparing high-reactivity polybutene with low fluorine content by diluting the highly-reactive polybutene prepared in a detailed method in a solvent and then passing the alumina column impregnated with a compound for fluorine removal. There are disadvantages that require periodic replacement of the installation and adsorbent, and the process of removing the solvent from the removed polybutene solution has to be added. And the high-reactivity polybutene produced in this way has a disadvantage that the content of fluorine is lower than that of the initial product, but the content of vinylidene at the alpha position, which is an important factor of high-reactivity polybutene, is also lowered. And the patent does not disclose the content of chlorine removal of polybutene.

The present invention is proposed to solve the above problems,

As a method of controlling the composition of aluminum chloride used as a catalyst for non-reactive polybutene and moisture (water) that can be used as a co-catalyst, a method for preparing non-reactive polybutene having a low chlorine content by controlling the content of chlorine in the non-reactive polybutene It aims to provide.

In addition, an object of the present invention is to provide an apparatus for producing non-reactive polybutene and a non-reactive polybutene produced thereby.

Aspects of the present invention for solving the above problems,

Polymerizing non-reactive polybutene by supplying a reaction raw material containing isobutene and a solvent to a reactor under a catalyst for polymerization of non-reactive polybutene; And

Adjusting the total water content in the reactor to a molar ratio of water (water) / catalyst of 1.0 or less using a water supply device; It is to provide a method for producing a non-reactive polybutene comprising a.

In addition, a catalyst supply device for polymerization; A device for supplying a reaction raw material containing isobutene and a solvent;

A reactor polymerized with non-reactive polybutene; And

A water supply device for supplying water (water) to the reactor front end or the reactor; In the apparatus for producing a non-reactive polybutene comprising:

The water supply device is to provide an apparatus for manufacturing a non-reactive polybutene that controls the total water content in the reactor so that the molar ratio of water (water) / catalyst is 1.0 or less.

According to the method and apparatus for manufacturing non-reactive polybutene according to the present invention, high-quality non-reactive polybutene can be produced by adjusting the chlorine (Cl) content and color (APHA) of the non-reactive polybutene.

1 is a schematic view showing a manufacturing process of non-reactive polybutene according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail. However, this is for the purpose of describing the present invention and should not be interpreted as a method of limiting the scope of the present invention.

The present invention adjusts the composition ratio of water and aluminum chloride in the process of producing polybutene using isobutylene as a raw material in the C4 fraction produced during the catalytic cracking of heavy oil in the process of petroleum refining or C4 residue generated in the process of naphtha pyrolysis. It relates to a method for producing a low-reactivity halogen, particularly a non-reactive polybutene having a low chlorine content in a halogen element (polybutene having an vinylidene content of 40% by weight or less at the alpha position).

In the present invention, the term 'polybutene' means polybutene excluding reactive polybutene (over 70% by weight of vinylidene content at alpha position) and heavy reactive polybutene (40 to 70% by weight vinylidene content at alpha position). .

That is, the method for preparing the non-reactive polybutene of the present invention can be used for the production of polybutene excluding reactive polybutene and heavy-reactive polybutene, preferably non-reactive polybutene (40% or less vinylidene content in the alpha position) It is a manufacturing method.

The method for preparing a non-reactive polybutene of the present invention comprises the steps of polymerizing a non-reactive polybutene by supplying a reaction raw material containing isobutene and a solvent to a reactor under a catalyst for polymerization of the non-reactive polybutene; And adjusting the total water content in the reactor so that the molar ratio of water (water) and catalyst is 1.0 or less using a water supply device. It may include.

In one embodiment of the present invention, the step of polymerizing the non-reactive polybutene may be performed under a catalyst for polymerization of the non-reactive polybutene.

The catalyst for polymerization of the non-reactive polybutene is preferably aluminum chloride dispersed in a hydrocarbon solvent, and the aluminum chloride may be included in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the isobutene.

If the content of the aluminum chloride is less than 0.01 parts by weight, a problem occurs in that the yield of the polybutene to be produced is lowered, and if it exceeds 0.5 parts by weight, a problem of difficulty in controlling polymerization heat and removing catalyst residues may occur.

In addition, the reaction raw material containing isobutene may be an olefin component (C4 fraction) having 4 carbon atoms (C4) derived from the decomposition process of naphtha, and the solvent may be LPG having 4 carbon atoms (C4).

The reaction raw material and the solvent are preferably supplied to the reactor in a state in which moisture is removed to 1 ppm or less through the water purification column formed at the front end of the reactor, that is, almost no moisture.

In the method for preparing non-reactive polybutene of the present invention, the total moisture content of raw materials, solvents, and catalyst compositions inputted to the reactor during the production of non-reactive polybutene is adjusted to be 1.0 or less in a molar ratio of water (water) / catalyst to lower It is possible to prepare non-reactive polybutenes having a low content of halogen elements, especially chlorine among halogen elements.

More specifically, it is preferable to adjust the total water content in the reactor to a molar ratio of water (water) / catalyst (aluminum chloride) of 0.01 to 1.0 using a water supply device, and to adjust the molar ratio of 0.01 to 0.3. It is more preferable.

When the molar ratio of the water (water) / catalyst (aluminum chloride) is less than 0.01, the polymerization activity may drop and the yield may be lowered. If it exceeds 1.0, the formation of a complex of aluminum chloride / water may be promoted by reacting with aluminum chloride.

Therefore, if the removal of the aluminum chloride catalyst residue after polymerization is not easy, it remains in the final product, polybutene, increasing the chlorine content of the polybutene, and the color (APHA) may be increased.

In one embodiment of the present invention, the non-reactive polybutene is a low chlorine polybutene, and the content of chlorine contained in the polybutene may be 30 ppm or less, and preferably 10 ppm or less.

When the content of chlorine contained in the polybutene exceeds 30 ppm, the chromaticity may increase, and high-quality non-reactive polybutene cannot be obtained due to the catalyst residue.

In one embodiment of the present invention, the number average molecular weight (Mn) of the non-reactive polybutene may be 300 to 1,000,000 g / mol, and preferably 300 to 5,000 g / mol.

In one embodiment of the present invention, the non-reactive polybutene can be performed under normal reaction conditions, and considering the molecular weight, polymerization is preferably performed at a temperature of 0 to 40 ° C., and the raw material maintains a liquid state. A pressure of 7 kgf / cm ² or higher is preferred. When considering the vapor pressure of C4-R and C4-LPG depending on the polymerization pressure, the reaction temperature can be determined, so it is usually set to 7 kgf / cm ² or more, and the conversion rate is 95% or more and the reaction time is 5 to It is economical to react for a residence time of 60 minutes, preferably 10 to 30 minutes. Thereafter, the polymerized product is produced as a final product through processes such as neutralization, washing, recovery, LMPIB removal, and packaging.

Depending on the polymerization pressure, considering the vapor pressures of C4-R and C4-LPG, the reaction temperature can be determined, and a pressure of 7 kgf / cm ² or higher is usually preferred.

The present invention can provide an apparatus for producing non-reactive polybutene.

The manufacturing apparatus includes a catalyst supply device for polymerization; A device for supplying a reaction raw material containing isobutene and a solvent; A reactor polymerized with non-reactive polybutene; And a water supply device for supplying water (water) to the front end of the reactor or the reactor. It may include.

More specifically, the apparatus for manufacturing the non-reactive polybutene of the present invention will be described with reference to FIG. 1, but is not all inclusive of the present invention.

In the present invention, the manufacturing apparatus of the non-reactive polybutene is a slurry (a state in which aluminum chloride is dispersed in a hydrocarbon solvent) catalyst supply device (a), a solvent supply device as a line for pressure control and solvent control of the reactor (b) , Reaction raw material supply device (c), a water supply device (d) and a reactor (e) for supplying raw materials, the solvent supply device and the reaction material supply device include a water purification column, and a polymerization product discharge line (f) ), Neutralization and water washing process (g) to remove the catalyst residues of the polymer, separated into organics ((h), a mixture of polybutene and C4-LPG) and washings (catalytic residues, water, etc.), separated organics In the silver product and process (i), the solvent C4-LPG is recovered, and the low-molecular polybutene (LMPIB) that affects the physical properties is removed and the final polybutene polymer produced is sent to the packaging process (j) for packaging and shipping. In addition, the residual washing (k) is characterized by being sent to a wastewater treatment process (l) for treatment.

At this time, the water supply device should be injected into the C4-Raffinate or C4-LPG line where the moisture except for the catalyst supply line is removed or directly into the reactor to prevent the catalyst from deteriorating.

In one embodiment of the present invention, the water supply device controls the total moisture content of the raw material, solvent, and catalyst composition to be introduced into the reactor during the production of non-reactive polybutene to be 1.0 or less in a molar ratio of water (water) / catalyst. It may contain a low halogen element, and particularly, a non-reactive polybutene having a low chlorine content in the halogen element can be produced.

More specifically, it is preferable to adjust the total water content in the reactor to a molar ratio of water (water) / catalyst to be 0.01 to 1.0 using a water supply device, and more preferably to a molar ratio of 0.01 to 0.3.

When the molar ratio of the water (water) / catalyst is less than 0.01, the polymerization activity may drop and the yield may be lowered. If it exceeds 1.0, the formation of a complex of aluminum chloride / water may be promoted by reacting with aluminum chloride.

Therefore, if the removal of the aluminum chloride catalyst residue after polymerization is not easy, it remains in the final product, polybutene, increasing the chlorine content of the polybutene, and the color (APHA) may be increased.

In the non-reactive polybutene production apparatus of the present invention, the apparatus for supplying the reaction raw material and the solvent may further include a water purification column.

According to an embodiment of the present invention, the input raw material and the solvent are characterized in that they are introduced into the reactor in a state in which water is almost removed through a water purification column in front of the reactor. In particular, the water injection pump is characterized in that it is placed in the front of the reactor or directly injected into the reactor after passing through a moisture removal column to the C4-LPG as a solvent or the C4-raffinate line as a raw material. This is because when the water injection pump is located in the catalyst slurry injection line, the activity of the catalyst is reduced by forming an aluminum chloride / water complex before the reaction.

In one embodiment of the present invention, the polymerization catalyst is preferably aluminum chloride dispersed in a hydrocarbon solvent, and the aluminum chloride may be included in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the isobutene.

In one embodiment of the present invention, the non-reactive polybutene is a low chlorine polybutene, and the content of chlorine contained in the polybutene may be 30 ppm or less, and preferably 10 ppm or less.

The present invention can provide a non-reactive polybutene produced by the method for producing the non-reactive polybutene or produced by the apparatus for manufacturing the non-reactive polybutene.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are intended to illustrate the invention, and the invention is not limited by the following examples.

C4 oil composition component

ingredient	mol (%)
Methane	0.01
Propane	0.07
Cyclo-propane	0.06
Propylene	0.30
Isobutane	5.24
n-Butane	9.66
n-Butane	0.04
2-Butene (Trans)	1.27
1-Butene	0.95
Isobutene	81.53
2-Butene (Cis)	0.83
1,2-B.D	0.05

Example 1

Using a pilot facility including a 30L CSTR-type polybutene reactor, C4 fractions of 16 kg / hr and 32 kg / hr of C4-LPG and 32 kg / hr of C4-LPG of the components shown in Table 1 were removed to a reactor maintained at 20 ° C. Injection was continuously. Aluminum chloride, a catalyst for polymerization of non-reactive polybutene, was injected so that the amount of isobutene in the C4 fraction was 0.05 wt% / hr, and polymerization was performed at 20 ° C at a pressure of 7 kgf / cm ² for 20 minutes.

At this time, water was injected into the front end of the reactor with a C4-LPG line so that the total water content in the raw material, solvent, and catalyst was 0.03 using a water supply device, and the pressure in the reactor was maintained to maintain the liquid phase of the raw material. It was maintained at 7 kgf / cm ² or more.

Subsequently, the polymer was transferred to a neutralization tank to neutralize and wash with an aqueous sodium hydroxide solution, and only the upper organic matter was recovered from the settler to the recovered purification tower to recover the solvent C4-LPG, and the remaining polybutene was transferred to the reduced pressure polybutene purified tower. By removing the low molecular polybutene (LMPIB) at 210 ℃, 20 mbar conditions to prepare a non-reactive polybutene.

At this time, the total moisture content contained in the raw material, solvent, and catalyst was analyzed by a moisture meter (Karl Fischer titration method), and the yield was analyzed by GC (Gas chromatography) analyzing the difference in the composition of isobutene between the injected C4 fraction and the recovered C4 fraction. It was measured.

Using GPC (Gel permeation chromatography), the number average molecular weight (Mn) and molecular weight distribution (MWD) of the prepared non-reactive polybutene were measured, and the chlorine content in polybutene was measured by C-IC (Combustion Ion Chromatography). , Chromaticity (APHA) was measured using a chromaticity analyzer. The results are shown in Table 2 below.

Example 2

Non-reactive in the same manner as in Example 1, except that water was injected into the front end of the reactor through the C4-LPG line so that the total water content in the raw materials, solvent, and catalyst was 0.1 by using a water supply device, in a molar ratio of water / catalyst. Polybutene was prepared.

Example 3

Non-reactive in the same manner as in Example 1, except that water was injected into the front end of the reactor through the C4-LPG line so that the total water content in the raw materials, solvent, and catalyst was 0.3 by using a water supply device. Polybutene was prepared.

Example 4

Non-reactive in the same manner as in Example 1, except that water was injected into the front end of the reactor through the C4-LPG line so that the total water content in the raw materials, solvent, and catalyst was 0.5 by using a water supply device, such that the molar ratio of water / catalyst was 0.5. Polybutene was prepared.

Example 5

Non-reactive in the same manner as in Example 1, except that water was injected into the front end of the reactor through a C4-LPG line so that the total water content in the raw materials, solvent, and catalyst was 1.0 by using a water supply device. Polybutene was prepared.

Example 6

The polymerization temperature was maintained at 35 ° C., except that water was injected into the front end of the reactor with a C4-LPG line so that the total water content in the raw materials, solvent, and catalyst was 1.0 at a molar ratio of water / catalyst using a water supply device. Non-reactive polybutene was prepared in the same manner as in Example 1.

Example 7

The polymerization temperature was maintained at 15 ° C, and water was injected into the reactor front end with a C4-LPG line so that the total water content in the raw materials, solvent, and catalyst was 1.0 at a molar ratio of water / catalyst using a water injection pump. A non-reactive polybutene was prepared in the same manner as in Example 1, except that.

Example 8

The polymerization temperature was maintained at 5 ° C., except that water was injected into the front end of the reactor with a C4-LPG line so that the total water content in the raw materials, solvent, and catalyst was 1.0 at a molar ratio of water / catalyst using a water supply device. Non-reactive polybutene was prepared in the same manner as in Example 1.

Comparative Example 1

Using a pilot facility including a 30 L CSTR-type polybutene reactor, C4 fractions of 16 kg / hr and 32 kg / hr of C4-LPG and 32 kg / hr of C4-LPG of the components shown in Table 1 were continuously removed into a reactor maintained at a temperature of 20 ° C. Was injected. Aluminum chloride, a catalyst for polymerization of non-reactive polybutene, was injected so that the amount of isobutene in the C4 fraction was 0.05 wt% / hr, and polymerization was performed at 20 ° C at a pressure of 7 kgf / cm ² for 20 minutes.

At this time, water was injected into the front end of the reactor through the C4-LPG line so that the total water content in the raw materials, solvent, and catalyst became 1.2 by the molar ratio of water / catalyst using a water supply device, and the pressure in the reactor was maintained to maintain the liquid phase of the raw materials. It was maintained at 7 kgf / cm ² or more.

Subsequently, the polymerized polymer was transferred to a neutralization tank to be neutralized and washed with an aqueous sodium hydroxide solution, and only the upper organic matter was recovered from the settler to the recovery purification tower to recover the solvent C4-LPG, and the remaining polybutene was a reduced pressure polybutene purification tower. Moving to and removing the low molecular polybutene (LMPIB) under the conditions of 210 ℃, 20 mbar to prepare a non-reactive polybutene.

Comparative Example 2

Non-reactive in the same manner as in Comparative Example 1, except that water was injected into the front end of the reactor through the C4-LPG line so that the total water content in the raw materials, solvent, and catalyst was 1.5 by using a water supply device, in a molar ratio of water / catalyst. Polybutene was prepared.

Comparative Example 3

Non-reactive in the same manner as in Comparative Example 1, except that water was injected into the front end of the reactor through the C4-LPG line so that the total water content in the raw material, solvent, and catalyst was 2.0 by using a water supply device to a molar ratio of water / catalyst. Polybutene was prepared.

	Water / catalyst molar ratio	Polymerization temperature (℃)	yield(%)	Mn (g / mol)	MWD	Chlorine content in polybutene (ppm)	Chromaticity (APHA)
Example 1	0.03	20	94	1020	1.74	<1	5
Example 2	0.1	20	96	980	1.72	2	6
Example 3	0.3	20	99	950	1.70	5	6
Example 4	0.5	20	97	960	1.73	18	8
Example 5	1.0	20	95	980	1.75	25	10
Example 6	1.0	35	92	580	1.64	22	10
Example 7	1.0	15	96	1320	1.86	29	10
Example 8	1.0	5	90	2380	2.39	24	10
Comparative Example 1	1.2	20	87	1010	1.91	33	16
Comparative Example 2	1.5	20	86	1140	2.21	38	17
Comparative Example 3	2.0	20	83	1380	2.49	54	33

As shown in Table 2, when the molar ratio of the water / catalyst of Examples 1 to 8 is 1.0 or less, the chlorine content contained in the polybutene can be confirmed to be 30 ppm or less. However, in Comparative Examples 1 to 3, when the molar ratio of water / catalyst exceeds 1.0, it was confirmed that the chlorine content exceeds 30 ppm, and thus the yield showing the activity of the catalyst decreases and the color also increases.

Claims (13)

1. Polymerizing non-reactive polybutene by supplying a reaction raw material containing isobutene and a solvent to a reactor under a catalyst for polymerization of non-reactive polybutene; And

   Adjusting the total water content in the reactor to a molar ratio of water (water) / catalyst of 1.0 or less using a water supply device; Method for producing a non-reactive polybutene, characterized in that it comprises a.
2. According to claim 1,

   The polymerization catalyst is a method for producing a non-reactive polybutene, characterized in that the aluminum chloride.
3. According to claim 2,

   The aluminum chloride is a method for producing a non-reactive polybutene, characterized in that contained in 0.01 to 0.5 parts by weight based on 100 parts by weight of isobutene.
4. According to claim 1,

   The reaction raw material is a method for producing a non-reactive polybutene, characterized in that the olefin-based oil having 4 (C4) carbon atoms, and the solvent is LPG having 4 (C4) carbon atoms.
5. According to claim 1,

   The reaction raw material and solvent is a method for producing non-reactive polybutene, characterized in that water is supplied to 1 ppm or less through a water purification column formed at the front end of the reactor.
6. According to claim 1,

   The non-reactive polybutene is a low-chlorine polybutene, wherein the chlorine content is 30 ppm or less.
7. According to claim 1,

   The non-reactive polybutene has a number-average molecular weight (Mn) of 300 to 1,000,000 g / mol.
8. According to claim 1,

   The polymerization method of the non-reactive polybutene is a pressure of 7kgf / cm ² or higher at a temperature of 0 to 40 ° C., and the reaction time is performed for 5 to 60 minutes.
9. Catalyst supply device for polymerization;

   A device for supplying a reaction raw material containing isobutene and a solvent;

   A reactor polymerized with non-reactive polybutene; And

   A water supply device for supplying water (water) to the reactor front end or the reactor; In the apparatus for producing a non-reactive polybutene comprising:

   The water supply device is a non-reactive polybutene production apparatus characterized in that the total water content in the reactor is adjusted so that the molar ratio of water (water) / catalyst is 1.0 or less.
10. The method of claim 9,

    The apparatus for supplying the reaction raw material and the solvent is a manufacturing apparatus for non-reactive polybutene, further comprising a water purification column.
11. The method of claim 9,

    The polymerization catalyst is a non-reactive polybutene production apparatus, characterized in that the aluminum chloride.
12. The method of claim 9,

    The non-reactive polybutene is a low-chlorine polybutene, wherein the chlorine content is 30 ppm or less.
13. It is produced by the method for producing the non-reactive polybutene of any one of claims 1 to 8, or

    A non-reactive polybutene, characterized in that it is produced by the apparatus for manufacturing the non-reactive polybutene according to any one of claims 9 to 12.

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