KR101871071B1 - Device of preparing polybutene, Method of preparing polybutene, Polybutene prepared by the same and Device of preparing polybutent prepared by the same - Google Patents

Abstract

The present invention relates to a process for producing polybutenes continuously by polymerizing isobutene, wherein a polymerization reactor connected in parallel is subjected to a grade change in a process for producing non-reactive polybutene and reactive polybutene (intermediate reactive and highly reactive) The present invention relates to a new polybutene manufacturing apparatus and a manufacturing method thereof, which increase the production efficiency by continuously operating the process by selectively cleaning only the reactor in place of the entire process.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polybutene, a polybutene, and a polybutene produced by the method.

The present invention relates to a process for continuously producing polybutenes by polymerizing isobutene, wherein a polymerization reactor connected in parallel is used in a process for producing non-reactive polybutene and reactive polybutene (intermediate reactive and highly reactive) in one plant The present invention relates to a new polybutene manufacturing apparatus and a manufacturing method thereof, in which production efficiency is improved by continuously operating a process in which only the reactor is selectively cleaned in place of the entire process.

Polybutene is an isobutene polymer produced from C4 oil produced during naphtha pyrolysis process or C4 oil produced by catalytic cracking of heavy oil during petroleum refining process. It is a colorless, odorless, non-toxic, viscous and adhesive property And is generally a viscous liquid or rubber-like polymer widely used for adhesives, lubricants, lubricant thickeners, plasticizers, asphalt modifiers, battery insulating oils, sealants, caulking agents and dispersants.

 In the past, polybutene was mainly used as a pressure-sensitive adhesive, an adhesive, or an insulating oil. Therefore, a product having low reactivity was preferred. Polybutene having such low reactivity is referred to as a non-reactive polybutene (Con-PIB). In recent years, polar groups have been introduced into polybutene to be used as an anti-scuff agent and viscosity index improver for engine oil, or used as a detergent or the like by mixing with fuel of internal combustion engines such as automobiles The high reactivity polyisobutylene (HR-PIB) is a highly reactive polybutene. In addition, middle-reactive polybutene located between non-reactive polybutene and highly reactive polybutene is also produced and sold.

 Aluminum chloride is used commercially in the production of non-reactive polybutene (Con-PIB) (Con-PIB), and boron trifluoride complex is used as a catalyst in the production of highly reactive polybutene. Reactive polybutene is prepared at higher temperature (above 0 ° C) than high reactivity using the same catalyst as highly reactive polybutene. Generally, in producing polybutene, non-reactivity and reactivity are separated and produced because aluminum chloride and boron trifluoride complex react with each other to lower the activity of the catalyst. Therefore, in the same production line, The manufacturing process of the reactor and other equipment should be preceded by a cleaning process.

The production of non-reactive polybutene in commercially produced polybutene uses aluminum chloride as a catalyst, and a highly reactive, highly reactive polybutene catalyst is mostly used as a boron trifluoride complex. Both catalysts are used as a Friedel-Craft type catalyst to selectively react isobutene in C4 fraction by cationic polymerization to produce polybutene.

Korean Patent No. 10-0055713 discloses an apparatus and a method for selectively producing highly reactive polybutene, heavy reactive polybutene, and non-reactive polybutene in one plant. This is a method in which a catalyst tank is divided into reactive and non-reactive ones in order to selectively produce reactive and non-reactive polybutenes in one plant. Thus, all of the highly reactive, reactive and non-reactive polybutenes can be produced in the same plant . However, since the polymerization reactor is operated as a single product, when the grade of the product is changed, the cleaning process of the reactor must be preceded, and the production efficiency is lowered.

It is an object of the present invention to provide a process for continuously producing polybutenes by continuously polymerizing C4 isobutene produced by naphtha pyrolysis process or C4 oil produced by catalytic cracking of heavy oil during petroleum refining process, In the process of producing polybutene and reactive polybutene (reactive and highly reactive) at the same time, it is possible to change the grade and to selectively clean the reactor only in place of the entire process. And to provide a manufacturing apparatus and a manufacturing method of polybutene.

In order to achieve the object of the present invention, the present invention provides an apparatus for producing polybutene selectively producing reactive polybutene and non-reactive polybutene in the same production line, wherein the apparatus for producing polybutene comprises a reaction comprising isobutene And a reactor in which a raw material is supplied and polymerized into polybutene, wherein the reactor has at least two reactors connected in parallel.

According to the apparatus and the method for producing polybutene according to the present invention, in the process of simultaneously producing reactive and non-reactive polybutene in one plant, grade change can be freely performed only by washing only the reactor without changing the entire process, And the production efficiency can be increased.

FIG. 1 is a schematic view showing an apparatus for selectively producing non-reactive polybutene and reactive polybutene capable of efficiently changing grade using two reactors connected in parallel according to an embodiment of the present invention.
Fig. 2 is a schematic view showing an apparatus for producing polybutene using one reactor according to Comparative Examples 1 and 2. Fig.

Hereinafter, the present invention will be described in more detail.

A manufacturing apparatus according to the present invention for increasing the efficiency of selectively producing reactive polybutene and non-reactive polybutene in one plant according to the present invention will be described. FIG. 1, which will be referred to in the detailed production method, is one of various methods for selectively improving the production efficiency of non-reactive and reactive polybutene, but does not include all of the present invention.

According to one embodiment of the present invention, the production apparatus according to the present invention is an apparatus for producing polybutene selectively producing reactive polybutene and non-reactive polybutene in the same production line, The reactor is characterized in that at least two or more reactors are connected in parallel.

The apparatus for producing polybutene according to the present invention may further comprise a catalyst storage tank for a non-reactive polybutene for polymerizing the non-reactive polybutene, and a reactive polybutene catalyst storage tank for polymerizing the reactive polybutene.

According to an embodiment of the present invention, the reactive polybutene may include a reactive polybutene having a vinylidene content of 40% by weight to 70% by weight and a highly reactive polybutene having a vinylidene content of 70% And the non-reactive polybutene is a non-reactive polybutene having a vinylidene content at the molecular end of less than 40 mol%.

Specifically, according to an embodiment of the present invention, as shown in Fig. 1, there are provided a polymerization catalyst supply device (a) for non-reactive polybutene, a catalyst supply device (b) for reactive polybutene polymerization, (f), a polymer discharge line (g), a storage tank (h) capable of storing polymeric water, and a reactor (c) and a reactor (d, e) (I) for the commercialization process which can be commercialized as required, for example, a neutralization and washing device, a separation device, a C4 distillation column, and an LP distillation column, and if necessary, A washing water storage device (j) of the reactor and, if necessary, a neutralization, recovery, wastewater treatment device (k).

According to an embodiment of the present invention, the raw material supply line may be directly connected to the reactors to feed the raw material, or the raw material supply line may be connected to the polybutene polymerization catalyst supply line to mix the catalyst and the feedstock, Can be supplied.

According to an embodiment of the present invention, as shown in FIG. 1, the polybutene polymerization catalyst feeding device is composed of two or more, at least one of which is a polymerization catalyst feeding device of reactive polybutene, and the other is a non- Butene polymerization catalyst feeder.

Further, the two polybutene polymerization catalyst feeders of different types may be connected in parallel.

The polymerization catalyst is supplied from the non-reactive polybutene polymerization catalyst feeder (a) or the highly reactive polybutene polymerization catalyst feeder (b) to the reactor 1 (d) or the reactor 2 (e) c) is supplied to the reactor 1 (d) or the reactor 2 (e) to which the catalyst has been supplied. At this time, the temperature and pressure of the reaction process are controlled according to the kind of the supplied catalyst, and the molecular weight, yield and vinylidene content of the product are controlled by adjusting the catalyst amount.

According to an embodiment of the present invention, the reactive polybutene polymerization catalyst is firstly supplied to prepare the reactive polybutene first, then the supply of the reactive polybutene polymerization catalyst is stopped, and at the same time, the non-reactive polybutene polymerization catalyst is supplied, The polybutene can be polymerized.

According to one embodiment, the reactive polybutene polymerization catalyst supply apparatus (b) is supplied with the catalyst first to polymerize the reactive polybutene in the reactor 1 (d) (or the reactor 2 is also possible), and if necessary, The aluminum chloride catalyst dispersed in the solvent according to the composition of the C4 oil and the solvent is introduced into the reactor (e) (or the reactor 1 is also possible) to initiate the reaction. At the same time, the reactor (d) , The introduction of the boron trifluoride complex catalyst is stopped. In addition, the washing and drying processes for the reactor (d) may be carried out directly in accordance with necessity.

According to an embodiment of the present invention, the discharge line through which the polybutene polymer is discharged from the reactors may be connected to one or more storage tanks h. This results in a range that is mixed with the previous grade in the product family change, which causes deterioration of the properties of the final product. At this time, if an extra storage tank is connected to the reactor, it is preferable that the mixing section can be efficiently managed.

The polymerization of the reactive polybutene may be carried out under the usual reaction conditions and is preferably carried out at a temperature of -35 to 10 ° C in consideration of the content of vinylidene, kgf / cm ² Or higher, and it is economical to conduct the reaction for a retention time of 90% or more and a reaction time of 5 to 60 minutes, preferably 10 to 30 minutes. Afterwards, the polymerized products are neutralized, washed, recovered, and removed by low polymer (LP).

The production of the non-reactive polybutene may also be carried out under ordinary reaction conditions. The polymerization is preferably carried out at a temperature of -10 to 50 ° C in consideration of the molecular weight, and is usually 8 kgf / cm It is economical to conduct the reaction for a residence time of at least ² , a conversion of 90% or more, and a reaction time of 5 to 60 minutes, preferably 10 to 30 minutes. Subsequently, the polymer product is produced as a final product through processes such as neutralization, washing, recovery, and LP removal.

According to an embodiment of the present invention, the polymerization catalyst of the reactive polybutene is a boron trifluoride complex, and the polymerization catalyst of the non-reactive polybutene is aluminum chloride.

According to one embodiment of the present invention, the reactive polybutene polymerization catalyst is preferably a boron trifluoride complex and a catalyst comprising water, an alcohol having 1 to 4 carbon atoms, and a dialkyl ether complex catalyst having 2 to 8 carbon atoms.

According to an embodiment of the present invention, the reactor is selected from a batch reactor, a continuous stirred tank reactor (CSTR), and a tubular reactor, and the two or more reactors may be the same type or different types of reactors . Preferably, a tubular reactor is used because it is advantageous to the reactor heat.

According to one embodiment of the present invention, the tubular reactor includes a plug flow reactor (PFR), a fixed bed (packed bed) reactor.

According to an embodiment of the present invention, the polybutene has a number average molecular weight of 300 to 1,000,000 g / mol, and preferably 300 to 100,000 g / mol.

The process for producing polybutene according to the present invention includes the steps of supplying a reactive or non-reactive catalyst and a raw material, changing the feed of raw materials and catalyst into a redundant reactor at the time of grade change, and washing and drying the previously operated reactor .

According to the manufacturing method of the present invention, it is possible to continuously produce the catalyst without deteriorating the activity among different kinds of catalysts when the catalyst is changed according to the grade change by simply changing the polymerization reactor without cleaning operation of the entire process line, It is possible to quickly respond to grade changes later, and it is also possible to produce reactive and non-reactive polybutene simultaneously in one manufacturing process line.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention.

[ Reference Example  One]

C4 feedstock of component composition of Table 1 at 420 g / min and LPG at 300 g / min were continuously injected into reactor 1 (d) maintained at 0 ° C using a polybutene continuous pilot plant in which CSTR type reactors were connected in parallel. Respectively. In order to maintain the raw material liquid phase, the internal pressure of the reactor was maintained at 3 kgf / cm ² or more, and the residence time in the reactor was adjusted to 10 minutes. Reactor 1 (d) was charged with aluminum chloride from the non-reactive polymerization catalyst feeder (a) at a concentration of 0.05 wt% / min relative to the isobutene content in the C4 fraction. After 10 minutes, the sample was neutralized and washed with caustic soda and water, and the unreacted C4 fraction and residual solvent were removed using a rotary distillation apparatus. The conversion was then calculated, and the conversion was then calculated using a fractional distillation apparatus at 160, 5 torr Lt; / RTI > The number average molecular weight (Mn) and the polydispersity of the produced non-reactive polybutene were measured using GPC (Gel Permeation Chromatography), and the content of vinylidene in polybutene was analyzed by ¹ H-NMR . The results are shown in Table 2.

C4 oil composition component ingredient mol (%) methane 0.01 Propane 0.07 Cyclopropane 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

[ Reference Example 2 ]

C4 feed oil of the composition shown in Table 1 at 420 g / min and LPG at 300 g / min were continuously injected into the reactor 2 (e) maintained at -20 DEG C using a polybutene continuous pilot plant in which CSTR type reactors were connected in parallel. Respectively. In order to maintain the raw material liquid phase, the internal pressure of the reactor was maintained at 3 kgf / cm ² or more, and the residence time in the reactor was adjusted to 10 minutes. A boron trifluoride complex (boron trifluoride and ethanol were prepared at the same molar ratio of -30) was fed into the reactor 2 (e) from the reactive polymerization catalyst feeder (b) so as to be 0.2 wt% / min with respect to the isobutene amount in the C4 fraction A sample was prepared and analyzed in the same manner as in Reference Example 1, except that. The results are shown in Table 2.

[ Example 1 ]

C4 feed oil of the composition shown in Table 1 at 420 g / min and LPG at 300 g / min were continuously injected into the first reactor (d) maintained at 0 캜 using a polybutene continuous pilot plant in which CSTR type reactors were connected in parallel . From the unreacted polybutene polymerization catalyst feeding apparatus (a), aluminum chloride was injected into the reactor 1 (d) so that the amount of aluminum chloride was 0.05 wt% / min relative to the isobutene content in the C4 fraction. In order to maintain the raw material liquid phase, the internal pressure of the reactor was maintained at 8 kgf / cm ² or more, and the residence time in the reactor was adjusted to 10 minutes.

Thereafter, the supply of the catalyst and the feedstock to the reactor 1 (d) was stopped, and the boron trifluoride complex (0.2 wt% based on the isobutene content in C4) and the C4 fraction were fed from the catalyst feeder (b) Except that the sample was injected into the reactor 2 (e) maintained at a constant temperature for 10 minutes. A sample was prepared and analyzed in the same manner as in Reference Example 1. The results are shown in Table 2.

[ Example 2 ]

C4 feed oil of the composition shown in Table 1 at 420 g / min and LPG at 300 g / min were continuously injected into the reactor 2 (e) maintained at -25 DEG C using a polybutene continuous pilot plant in which CSTR type reactors were connected in parallel. Respectively. In order to maintain the raw material liquid phase, the internal pressure of the reactor was maintained at 3 kgf / cm ² or more, and the residence time in the reactor was adjusted to 10 minutes. The boron trifluoride complex was injected from the reactive polybutene polymerization catalyst feeder (b) so that the amount of the boron trifluoride complex was 0.2 wt% / min relative to the isobutene content in the C4 fraction, and the reaction was continued without changing the injection amount. ) Was sampled after 10 minutes except that the aluminum chloride catalyst (0.05 wt% relative to the amount of isobutene in C4) and the C4 fraction were fed into reactor 1 (d) maintained at -25 캜. Samples were prepared and analyzed in the same manner. The results are shown in Table 2.

[ Comparative Example 1 ]

C4 feed oil fraction of the composition shown in Table 1 of 420 g / min and LPG of 300 g / min were continuously injected into the reactor 3 maintained at 0 캜 at a temperature of 0 캜 using a polybutene continuous pilot plant equipped with one CSTR type reactor . The pressure in the reactor was maintained above ³ kgf / cm ² to maintain the liquid phase in the reactor, and the residence time in the reactor was adjusted to 10 minutes. The reaction was carried out by injecting aluminum chloride catalyst so that the amount of isobutane in C4 oil was 0.05 wt% / min. After the reaction for 10 minutes, the catalyst was changed except that the catalyst was changed to the boron trifluoride complex (0.2 wt% based on the amount of isobutene in C4) without changing the amount of the catalyst, and after 10 minutes, the sample was sampled Samples were prepared and analyzed. The results are shown in Table 2.

[ Comparative Example 2 ]

C4 feed oil fraction of the composition shown in Table 1 of 420 g / min and LPG of 300 g / min were continuously injected into the reactor 3 maintained at 0 캜 at a temperature of 0 캜 using a polybutene continuous pilot plant equipped with one CSTR type reactor . In order to maintain the raw material liquid phase, the internal pressure of the reactor was maintained at 3 kg / cm ² or more, and the residence time in the reactor was adjusted to 10 minutes. The boron trifluoride complex used as the catalyst was injected at a rate of 0.2 wt% / min with respect to the isobutene content in the C4 fraction, and the catalyst was changed to aluminum chloride (0.05 wt% with respect to the amount of isobutene in the C4) without changing the injection amount The catalyst was changed except for the injection, and after 10 minutes, the sample was sampled and analyzed in the same manner as in Reference Example 1. The results are shown in Table 2.

Catalyst changes Acting catalyst yield
(%) Mn
(g / mol) MWD Vinylidene
(wt%) Reference Example 1 X AlCl ₃ 96 3540 2.4 14 Reference Example 2 X BF ₃ / EtOH 92 1960 1.9 89 Example 1 O AlCl ₃ 96 3540 2.4 14 BF ₃ / EtOH 93 1910 1.8 88 Example 2 O BF ₃ / EtOH 92 1960 1.9 89 AlCl ₃ 95 3600 2.3 13 Comparative Example 1 O AlCl ₃ 96 3540 2.4 14 BF ₃ / EtOH 84 2230 2.7 71 Comparative Example 2 O BF ₃ / EtOH 92 1960 1.9 89 AlCl ₃ 48 5570 3.7 34

As can be seen from Table 2, when the grade is changed by changing the catalyst, the feed of the raw material and the catalyst is changed to the reactor connected in parallel to produce a product having the same properties as those of the polybutene prepared by a separate process It can be seen that

That is, comparing Example 1 with Comparative Example 1, according to Example 1, unreacted polybutene was prepared, and the raw material and the catalyst were fed to a reactor connected directly in parallel while simply changing the catalyst with a highly reactive polybutene polymerization catalyst , Polybutene can be selectively produced at a level substantially equivalent to that of Reference Examples 1 and 2 in which only one kind of polybutene is polymerized without changing the catalyst in the non-reactive polybutene and the highly reactive polybutene. On the other hand, in the case of Comparative Example 1, it was found that the yield and vinylidene content of the polymer of the highly reactive polybutene produced by changing the catalyst for producing the non-reactive polybutene were all lower.

Comparing Example 2 and Comparative Example 2, the non-reactive polybutene was prepared in the same manner as in Example 2 except that the raw material was supplied to the reactor connected in parallel with the change of the catalyst, The polymerization reaction can proceed in the washed reactor, and the polymerization reaction proceeds without being affected by the previous catalyst. As a result, it was confirmed that the yield, the molecular weight and the vinylidene content are superior to those of Comparative Example 2.

Therefore, the manufacturing apparatus and the manufacturing method according to the present invention can produce the polybutene products of the same physical properties without stopping the process for the washing process of the reactor, thereby increasing the production efficiency compared to the existing processes.

Claims (14)

In a method for producing polybutene selectively producing reactive polybutene and non-reactive polybutene in the same production line,
Supplying a reaction raw material containing isobutene under a polymerization catalyst of the polybutene to a first reactor which is one of reactors connected in parallel with at least two reactors to polymerize the polybutene;
Stopping the supply of the polymerization catalyst and the reaction raw material to the first reactor; And
And polymerizing the polybutene by feeding the polybutene polymerization catalyst and the reaction raw material to a second reactor other than the first reactor among the reactors connected in parallel. The method according to claim 1,
Reactive polybutene is polymerized in the first reactor, non-reactive polybutene is polymerized in the second reactor, or
Wherein the nonreactive polybutene is polymerized in the first reactor and the reactive polybutene is polymerized in the second reactor. The method according to claim 1,
Wherein the reactive polybutene polymerization catalyst is a boron trifluoride complex, and the non-reactive polybutene polymerization catalyst is aluminum chloride. The method of claim 3,
The polymerization reaction of the reactive polybutene is at a temperature of -35 to 10 ℃, and set to more than 3 kgf / cm ² pressure, and the reaction time is performed for 5 to 60 minutes,
Wherein the polymerization of the non-reactive polybutene is carried out at a temperature of -10 to 50 캜 at a pressure of not less than 8 kgf / cm ² and a reaction time of 5 to 60 minutes. A polybutene which is produced by the production method of any one of claims 1 to 4. An apparatus for producing polybutene produced by the production method according to any one of claims 1 to 4,
The present invention relates to an apparatus for producing polybutene selectively producing reactive polybutene and non-reactive polybutene in the same production line,
The reactors are connected to a raw material supply line,
Two or more polybutene polymerization catalyst feed units are connected to the raw material feed line or the reactor,
Wherein at least one of the polybutene polymerization catalyst feeders is a polymerization catalyst feed device for reactive polybutene,
Wherein the other one of the polybutene polymerization catalyst feeding devices is a polymerization catalyst feeding device for non-reactive polybutene. The method according to claim 6,
Wherein the discharge line through which the polybutene polymer is discharged from the reactors is connected to one or more storage tanks. The method according to claim 6,
The polymerization catalyst of the reactive polybutene is a boron trifluoride complex,
Wherein the polymerization catalyst of the non-reactive polybutene is aluminum chloride. The method according to claim 6,
Wherein the reactive polybutene polymerization catalyst is a catalyst comprising boron trifluoride and water, an alcohol having 1 to 4 carbon atoms, and an alkyl ether complex catalyst having 2 to 8 carbon atoms. The method according to claim 6,
The reactor is selected from a batch reactor, a continuous stirred tank reactor (CSTR), and a tubular reactor,
Wherein the two or more reactors are of the same type or different types. The method according to claim 6,
Wherein the tubular reactor comprises a plug flow reactor (PFR), a fixed bed (packed bed) reactor. The method according to claim 6,
Wherein the polybutene has a number average molecular weight of 300 to 1,000,000 g / mol. delete delete

Images