KR20170053467A - Method for continuous preparing a butadiene rubber and apparatus for continuous preparing a butadiene rubber using the same - Google Patents

Method for continuous preparing a butadiene rubber and apparatus for continuous preparing a butadiene rubber using the same Download PDF

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KR20170053467A
KR20170053467A KR1020150156019A KR20150156019A KR20170053467A KR 20170053467 A KR20170053467 A KR 20170053467A KR 1020150156019 A KR1020150156019 A KR 1020150156019A KR 20150156019 A KR20150156019 A KR 20150156019A KR 20170053467 A KR20170053467 A KR 20170053467A
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polymerization
polymerization reactor
butadiene
reactor
butadiene rubber
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KR1020150156019A
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Korean (ko)
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고준석
정회인
황우성
이종구
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주식회사 엘지화학
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836—Heating and cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins

Abstract

Disclosed is a continuous production method of butadiene rubber and a continuous production apparatus of butadiene rubber by dispersing and removing polymerization heat generated in butadiene polymerization reaction to produce butadiene rubber at a high yield. The continuous production method of the butadiene rubber is characterized in that a butadiene, a catalyst and a solvent are supplied to a first polymerization reactor and then a polymerization reaction is performed to produce a first polymerization solution containing a butadiene polymer, The generated gas is condensed in a heat exchanger and refluxed into the first polymerization reactor; Wherein the first polymerization solution is supplied to a second polymerization reactor and then a polymerization reaction is performed to produce a second polymerization solution containing a butadiene polymer and the gas generated by the polymerization heat in the second polymerization reactor is condensed in a heat exchanger A second polymerization step of supplying the first polymerization reactor to the first polymerization reactor; And a third polymerization solution containing a butadiene polymer is prepared by supplying the second polymerization solution to a third polymerization reactor and performing a polymerization reaction, wherein the gas generated by the polymerization heat in the third polymerization reactor is supplied to the heat exchanger And a third polymerization step wherein the first polymerization reactor is condensed and supplied to the first polymerization reactor, wherein the conversion of butadiene in the first polymerization reactor is 60 to 85%, and the first polymerization reactor, the second polymerization reactor, It is a continuous polymerization reactor connected in series.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a continuous process for producing butadiene rubber and a continuous process for producing butadiene rubber using the same,

The present invention relates to a continuous process for producing butadiene rubber and a continuous apparatus for producing butadiene rubber using the same, and more particularly, to a process for producing butadiene rubber by dispersing and removing heat of polymerization occurring during butadiene polymerization And a continuous apparatus for producing butadiene rubber using the same.

The butadiene rubber is prepared by 1,3-butadiene polymerization. The butadiene rubber is produced by polymerization of 1,3-butadiene in the presence of a double bond structure in a butadiene molecule, that is, whether it is a cis or a trans, Greatly depends on the kind of the catalyst compound made of the transition metal. In such a synthetic butadiene rubber, the properties most similar to the natural rubber are the content of cis 1,4, and the characteristics of the butadiene rubber are changed most depending on the content of cis 1,4. As the catalyst used for the synthesis (production) of butadiene rubber, a transition metal compound is mainly used, and examples thereof include nickel (Ni), cobalt (Co), titanium (Ti) and neodymium (Nd) Alkyl lithium, such as n-butyllithium, may also be used.

The polymerization reaction for preparing the butadiene rubber is usually carried out by solution polymerization in the presence of a solvent using the above catalyst. As the solvent used for the production of the butadiene rubber, n-hexane, cyclohexane, Hexane, benzene, toluene, cyclopentane, and n-heptane. The rate of the polymerization reaction varies depending on the type of the solvent, and therefore, the method of removing the heat of polymerization generated during the polymerization reaction varies do. Generally, when the butadiene rubber is prepared, the amount of the solvent and the butadiene introduced into the polymerization reactor is in the range of 6: 4 to 8: 2. When the content of the solvent is higher, the polymerization heat generated by the polymerization reaction is easier to remove . In addition, the solvent serves to lower the viscosity of the polymer (polymer) solution produced by the polymerization reaction.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a process for continuously polymerizing butadiene rubber. That is, unlike the batch polymerization method, which is a non-continuous polymerization method, the polymerization reaction can be carried out by a continuous reaction, which is advantageous in productivity compared with the batch polymerization method. The continuous polymerization reaction, that is, the continuous solution polymerization, is a method in which the catalyst is continuously fed into the polymerization reactors 10 and 20 together with a monomer (butadiene) and a solvent as shown in FIG. 1 , The polymerization reaction temperature is usually about 60 to 120 DEG C, and the polymerization reaction pressure is 0.01 to 5.0 kg / cm < 2 & gt ;. On the other hand, the heat of polymerization generated by the polymerization reaction is approximately 340 Kcal / kg per kg of butadiene, partially removed by the raw material supplied at a low temperature, and partially removed by using butadiene (BD) and the boiling point of the solvent, And the solvent is vaporized and removed. At this time, the gas generated by the vaporization flows into the heat exchangers (12, 22) and is condensed (liquefied) and then re-introduced into the reactor.

If the polymerization reaction heat (polymerization heat) of the first reactor is high, then the polymer is entrained and flows into the heat exchanger (condenser), which interferes with the heat transfer. As a result, the performance of the heat exchanger is lowered, , It becomes a situation requiring washing. Therefore, in order to produce a butadiene rubber having a high solid content, it is important to effectively disperse the heat of polymerization of the first reactor. Also, if the conversion of the butadiene monomer in the first reactor is maintained at a certain level or less, It is possible to prevent the polymer contained in the produced gas from being entrained in the heat exchanger. Also, the gas produced by the heat of polymerization in the reactor disposed after the first reactor is condensed and used to effectively remove the heat of polymerization after being fed to the first reactor, thereby reducing the inflow of the entrained polymer and reducing the conversion of the butadiene monomer .

As shown in FIG. 1, the polymerization reactor in the continuous reaction mainly uses two reactors 10 and 20 connected in series, and the volume of the reactor is such that the final conversion of butadiene in the polymerization reactor is 90% or more . When the butadiene rubber is produced by using two series reactors 10 and 20 so as to have the same residence time, the first polymerization reactor 10 generally has a final conversion of about 95% in the second polymerization reactor 20. [ Conversion rate is about 85% or more.

Korea Patent Registration No. 10-0031529 Korean Patent Publication No. 10-2015-0085655

As described above, since the heat of polymerization generated by the polymerization reaction in the first polymerization reactor 10 is much higher than the heat of polymerization produced by the polymerization reaction in the second polymerization reactor 20, In addition, there is a need for a method capable of preventing the plugging phenomenon due to the polymer which is entrained with the gas generated by the heat of polymerization . In addition, since the polymerization solution is transferred to the subsequent polymerization reactor connected to the first polymerization reactor 10, or the conversion to the butadiene polymer decreases with time, and the amount of unreacted butadiene monomer is increased, and the concentration of the butadiene polymer So that the energy consumption is increased.

It is therefore an object of the present invention to provide a butadiene rubber which can be produced in a high yield by dispersing and eliminating the heat of polymerization occurring during the butadiene polymerization reaction to prevent the plugging phenomenon by the polymer entrained with the gas generated by the heat of polymerization A continuous process for producing butadiene rubber, and an apparatus for continuous production of butadiene rubber using the same.

In order to achieve the above object, the present invention provides a process for producing a polymerized product, comprising the steps of: feeding a first polymerization reactor with butadiene, a catalyst and a solvent and then carrying out a polymerization reaction to produce a first polymerization solution containing a butadiene polymer, Wherein the gas generated by heat is condensed in a heat exchanger and refluxed into the first polymerization reactor; Wherein the first polymerization solution is supplied to a second polymerization reactor and then a polymerization reaction is performed to produce a second polymerization solution containing a butadiene polymer and the gas generated by the polymerization heat in the second polymerization reactor is condensed in a heat exchanger A second polymerization step of supplying the first polymerization reactor to the first polymerization reactor; And a third polymerization solution containing a butadiene polymer is prepared by supplying the second polymerization solution to a third polymerization reactor and performing a polymerization reaction, wherein the gas generated by the polymerization heat in the third polymerization reactor is supplied to the heat exchanger And a third polymerization step wherein the first polymerization reactor is condensed and supplied to the first polymerization reactor, wherein the conversion of butadiene in the first polymerization reactor is 60 to 85%, and the first polymerization reactor, the second polymerization reactor, Wherein the butadiene rubber is a continuous polymerization reactor connected in series.

The present invention also provides an apparatus for continuous production of butadiene rubber using the continuous production method of butadiene rubber.

According to the continuous production method of butadiene rubber according to the present invention and the apparatus for continuous production of butadiene rubber using the same, it is possible to disperse and remove polymerization heat generated during butadiene polymerization reaction, By preventing the plugging phenomenon, the butadiene rubber can be produced with a high yield.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a process for continuously polymerizing butadiene rubber.
2 is a process diagram for explaining the continuous polymerization reaction of butadiene rubber according to an embodiment of the present invention.
3 is a process diagram for explaining the continuous polymerization reaction of butadiene rubber according to another embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

FIG. 2 is a process diagram for explaining a continuous polymerization reaction of a butadiene rubber according to an embodiment of the present invention. FIG. 3 is a process diagram for explaining a continuous polymerization reaction of a butadiene rubber according to another embodiment of the present invention. The butadiene rubber according to the present invention can be produced by supplying butadiene, a catalyst and a solvent (through a raw material supply pipe (not shown)) to the first polymerization reactor 100 as shown in Figs. 2 and 3, And the gas generated by the polymerization heat in the first polymerization reactor 100 is condensed in the heat exchanger 120 and is supplied to the first polymerization reactor 100 A second polymerization solution containing the butadiene polymer is prepared by carrying out a polymerization reaction after supplying the first polymerization solution to the second polymerization reactor (200), and the second polymerization solution The gas generated by the polymerization heat in the inert gas 200 is condensed in a heat exchanger (120 in FIG. 2 or 220 in FIG. 3) to be supplied to the first polymerization reactor (100) Is supplied to the third polymerization reactor (300), and a polymerization reaction is performed to produce a third polymerization solution containing a butadiene polymer. The gas generated by the polymerization heat in the third polymerization reactor (300) (120 in FIG. 2 or 320 in FIG. 3) and supplied to the first polymerization reactor (100)

The first polymerization reactor 100, the second polymerization reactor 200, and the third polymerization reactor 300 are continuously connected in series with each other in a continuous polymerization reactor 100 connected in series, and the butadiene conversion rate in the first polymerization reactor 100 is 60 to 85% to be.

In the continuous production of butadiene rubber using the above three polymerization reactors, that is, the first polymerization reactor 100, the second polymerization reactor 200, and the third polymerization reactor 300, A polymerization reaction in which the heat becomes larger to accelerate the plugging phenomenon of the heat exchanger, that is, to increase the content of butadiene with respect to the content of the solvent supplied to the polymerization reactor in order to increase the production amount), the first polymerization reactor The heat of polymerization occurring in the first polymerization reactor 100 is effectively dispersed to thereby prevent the plugging of the heat exchanger 120 or reduce the frequency of occurrence of the plugging phenomenon, In addition, not only the butadiene rubber can be produced at a high production yield, but also the number of washing cycles of the butadiene rubber production apparatus is increased It is possible.

Accordingly, the present invention provides a method of controlling the retention time of raw materials in the first polymerization reactor (100) so that the butadiene conversion of the first polymerization reactor (100) is 60 to 85% And the polymerization heat is effectively dispersed in the second polymerization reactor (200) and the third polymerization reactor (300). When the polymerization heat of the first polymerization reactor (100) is dispersed in order to remove the heat of polymerization of the first polymerization reactor (100) generated by the polymerization reaction as described above, And the plugging of the heat exchanger by the polymer that entrainment together with the gas can be prevented.

2 and 3, the gas generated in the second polymerization reactor 200 and the third polymerization reactor 300 is condensed through a heat exchanger, and then the condensed gas is condensed in the first polymerization reactor 100, , The amount of gas generated in the first polymerization reactor (100) can be reduced, and the butadiene polymerization conversion rate can also be improved. That is, when the gases generated in the second polymerization reactor 200 and the third polymerization reactor 300 are condensed and supplied to the first polymerization reactor 100, the gases produced in the respective reactors are condensed, (For example, after condensation of the gas produced in the first, second and third polymerization reactors 100, 200 and 300), the condensate is subjected to first, second and third polymerization The final conversion ratio of butadiene in the third polymerization reactor 300 is higher than in the case of refluxing the raw materials to the reactors 100, 200, and 300, respectively.

In addition, as in the present invention, when three polymerization reactors are connected in series to continuously polymerize, even if a high content of butadiene monomer is fed into the reactor, the polymerization heat is effectively dispersed to prevent plugging of the heat exchanger The butadiene rubber having a high solid content can be produced by stably carrying out the polymerization reaction without stopping and the energy used when recovering the solvent and the unreacted butadiene monomer from the polymerization solution can be reduced.

The fact that the polymerization reactors 100, 200 and 300 are connected in series means that the first polymerization solution discharged from the first polymerization reactor 100 is supplied to the second polymerization reactor 200, And the second polymerization solution discharged from the reactor 200 is supplied to the third polymerization reactor 300. On the other hand, on the upper part of the polymerization reactors 100, 200 and 300, gas generated by polymerization heat is transferred to a heat exchanger (or a condenser, 120 of FIG. 2 or 120, 220 and 320 of FIG. 3) (1 to 3 in FIGS. 2 and 3) are connected to the polymerization reactors 100, 200, and 300, and a polymerization solution containing butadiene polymer is discharged or transferred to the next polymerization reactor The piping is connected. The structure of the polymerization reactor (100, 200, 300) is not particularly limited, but preferably has a structure of a stirring tank reactor or a loop reactor.

In the present invention, the heat exchanger for condensing the gas generated by the heat of polymerization may use only one heat exchanger 120 as shown in FIG. 2, but as shown in FIG. 3, It is also possible to provide the same number of polymerization reactors so as to be connected to the gas discharge pipes 1 to 3 of the polymerization reactor respectively. That is, the heat exchanger may be formed as a single unit to condense the gases generated in the respective polymerization reactors or may be connected to the polymerization reactors and use different heat exchangers for each polymerization reactor.

As shown in FIGS. 2 and 3, the polymerization solution discharged from the third polymerization reactor 300 located at the last position is transferred to a flash vessel 400, and some unreacted butadiene and solvent in the polymerization solution The remaining polymer solution is removed as a gas, and the concentrated polymer solution is transferred to a stripper (500). In the stripper 500, hydrocarbons such as unreacted butadiene except for the polymer and the solvent are removed by gas using water and steam, and the polymer is removed from the crumb tank crumb tank 600, and is supplied to the dewatering device 700 together with water to produce a bale-shaped product from which water is removed. Unreacted butadiene and the solvent removed from the flashing device 400 and the stripper 500 are removed from the decanter (not shown) and transferred to the distillation column 800, (Not shown) in which C4-based substances such as cis-2-butene and trans-2-butene, which are raw material-derived impurities, are partially removed and a molecular sieve for removing moisture is filled, After passing, the C4-based materials and solvent are refluxed and recycled to the reactor.

The polymerization reaction is carried out at a temperature of 70 to 110 DEG C, preferably 80 to 100 DEG C and a pressure of 0.1 to 5 kgf / cm 2 , preferably 1 to 5 kgf / cm 2 , It is preferably carried out in an atmosphere, for example, a nitrogen atmosphere. The polymerization reactor may be heated to adjust the temperature in the polymerization reaction. However, since the internal temperature of the polymerization reactor can be raised by the heat of polymerization occurring during the polymerization reaction, the step of separately heating the polymerization reactor is performed only as needed . On the other hand, when the solvent and the unreacted butadiene monomer are discharged to the gas discharge pipe under the above-mentioned temperature and pressure, a trace amount of polymer can be discharged together with the gas discharge pipe (i.e., can be entrained) As the heat of polymerization and the gas generation amount of the first polymerization reactor 100 are increased, plugging of the gas discharge pipe and gas flow inside the heat exchanger when the polymer is discharged to the gas discharge pipe, The occurrence rate of the phenomenon is increased, and the production yield of butadiene rubber is reduced.

On the other hand, in the present invention, the number of reactors used in the butadiene polymerization reaction is defined as three, but this is an optimal number that can most effectively disperse the heat of polymerization generated by the polymerization reaction. As a result, a polymerization reactor can be added (that is, the total number of the reactors can be increased) according to the conversion rate of the polymerization solution discharged from the last polymerization reactor and the amount of the butadiene rubber produced. Therefore, the total number of polymerization reactors is 3 or more, preferably 3 to 4, and more preferably 3. That is, if the number of reactors is set to 3, it is advantageous in terms of investment cost because of sufficient heat removal and dispersion, and it is possible to set it to 5 or more, but in this case, the investment cost is rather inefficient.

Of the raw materials used for the present invention, precisely the raw materials supplied to the first polymerization reactor 100, the catalyst used in the polymerization reaction is a Ziegler-Natta catalyst, which is a transition metal compound such as an organic nickel compound, Lanthanum compounds, organoaluminum compounds, fluorinated compounds, and mixtures thereof. In addition, conventional catalysts used in the production of butadiene rubber can be used without limitation.

Examples of the transition metal compound include transition metal halide complexes combined with a halogen compound such as lithium, cobalt, nickel and titanium compounds, preferably chlorine and bromine, and compounds containing a ligand excellent in solubility in a non-polar solvent More specifically, examples of the compound containing nickel in the transition metal include nickel benzoate, nickel acetate, nickel naphthenate, nickel octanoate, nickel neodecanoate, nickel 2-ethylhexanoate , Bis (-A-allyl nickel), bis (n-cycloocta-1,5-diene), bis (n-allylnitrifluoroacetate) Nickel stearate, nickel acetylacetonate, nickel salicylaldehyde, bis (salicylaldehyde) ethylenediamine nickel, bis (cyclopentadiene) nickel, cyclopentadienyl nickel It may be used rosil and nickel tetra carbonyl.

In addition, among the transition metals, the lanthanum-based metal compound may be an element from lanthanum of atomic number 57 to rutethium of atomic number 71, and may be lanthanum, cerium, gadolinium, and neodinium compound, A halogenated complex of a lanthanum series metal combined with a halogen compound such as bromine, and a carboxylate alcoholate, an acetylacetonate and an allyl derivative compound of a lanthanum series metal containing a ligand having a good solubility in a nonpolar solvent, Neodymium complex formed with neodymium naphthaleneate, neodymium octanoate, neodymium octoate, neodymium trichloride, neodymium trichloride complex formed with tetrahydrofuran (THF) (for example, NdCl 3 (THF) 2 ) (e.g., NdCl 3 (EtOH) 3) , neodymium 2,2-diethyl-HEX Maleate, neodymium 2-ethylhexoate, neodymium 2-ethyl octoate, neodymium 2,2-diethyl heptanoate dano benzoate, allyl neodymium dichloride, bis-allyl neodymium or the like may be used-allyl neodymium chloride, and tris.

Examples of the organoaluminum compounds include alkyl aluminum, alkyl aluminum halides and aluminoxanes. More specific examples include trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, triisobutyl aluminum, tri Hexyl aluminum, diisobutyl aluminum hydride, diethyl aluminum chloride, and the like.

Examples of the solvent used in the polymerization include aliphatic, alicyclic, aromatic hydrocarbons having 4 to 6 carbon atoms and mixtures thereof. Examples of the aliphatic hydrocarbons include butane, pentane, hexane, isopentane, heptane, Cyclohexane, methylcyclohexane, and ethylcyclohexane. Examples of the aromatic hydrocarbon include benzene, toluene, ethylbenzene, and xylene, and the like. Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, Among them, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene and toluene are preferably used. In addition, it is preferable that the solvent is distilled and dried to be used in a state in which water and oxygen are removed. Meanwhile, in the continuous production method of the butadiene rubber according to the present invention, the raw material used in the polymerization reaction (or in the first polymerization reactor 100) may be used in addition to the butadiene, the catalyst and the solvent, Of a polymerization modifier, a quencher, and a mixture thereof may be further included (or supplied).

In the present invention, the conversion of butadiene during the polymerization reaction can be controlled by the residence time of the polymerization solution in the reactor. That is, in order to increase the conversion to the butadiene polymer, the conversion of the feedstock in the first polymerization reactor (100) The residence time should be longer. The residence time is determined by the volume of the polymerization solution in the reactor (the volume occupied by the polymerization solution in the polymerization reactor) and the flow rate of the reaction raw material supplied to the reactor, and can be expressed by the following relational expression.

[Equation 1]

Retention time (hr) = {volume by volume (m 3) / raw material feed flow rate (kg / hr)} × density of the polymer solution (kg / m 3)

The present invention is characterized in that the first polymerization reactor (100) has a butadiene conversion of 60 to 85%, preferably 70 to 85%, and more preferably 75 to 85% Is intended to effectively disperse the polymerization heat of the first polymerization reactor (100) into the second polymerization reactor (200) and the third polymerization reactor (300) by adjusting the retention time of the first polymerization reactor It is important to control the residence time of the raw material in the raw material 100.

In order to increase the residence time, it is necessary to increase the volume of the reactor in the reactor or reduce the flow rate of the raw material supplied to the reactor. However, since the heat of polymerization also increases when the volume of the reactor is increased, And the plugging phenomenon is accelerated. Therefore, it is preferable and stable to increase the residence time by reducing the flow rate of the raw material supplied to the reactor. In contrast, in order to reduce the residence time, it is necessary to reduce the volume volume in the reactor or increase the flow rate of the raw material supplied to the reactor.

In the present invention, by controlling the residence time in such a manner that the conversion rate to the butadiene polymer in the first polymerization step is 60 to 85%, the heat of polymerization generated in the first polymerization reactor (100) is reduced, The amount of gas generated in the reactor 100 is reduced and the heat of polymerization in the second polymerization reactor 200 and the third polymerization reactor 300 is increased and the second polymerization reactor 200 and the third polymerization reactor 300 ) Can be increased. Accordingly, it is possible to reduce the amount of gas in the first polymerization reactor 100 in which the amount of gas is most generated among the reactors, and disperse the polymerization heat in the second polymerization reactor 200 and the third polymerization reactor 300 .

Also, since the heat of polymerization generated in the first polymerization reactor 100 is effectively dispersed, the phenomenon that the polymer is entrained together with the gas generated by the polymerization heat also does not occur or occurs at a minimum, Can prevent the plugging phenomenon of the butadiene rubber from being produced at a high yield with a high yield of the butadiene rubber (i.e., high solid content).

In addition, by efficiently dispersing and removing the heat of polymerization generated in the first polymerization reactor 100, the conversion ratios in the second polymerization reactor 200 and the third polymerization reactor 300 are sequentially increased, The final conversion of butadiene is 95% or more, preferably 97% or more, and more preferably 98 to 99.9%, from which the loss of the butadiene raw material can be minimized. However, by controlling the retention time of the raw materials in the first polymerization reactor 100, the conversion of butadiene in the first polymerization reactor 100 may be lower than that of a conventional butadiene rubber, The conversion of butadiene in the final polymerization reactor to be discharged is improved as compared with the conventional method (described in more detail in the following examples).

In addition, the problems such as the lowering of the conversion rate and the plugging phenomenon of the heat exchanger which are caused when the solid content is increased, and the amount of the consumed energy is decreased because of the high concentration of the butadiene polymer (solid content) Due to the reduction, it is possible to operate the reactor with low pressure. In addition, since the gas generated in the polymerization reactors disposed after the first polymerization reactor 100 is condensed and sent to the first reactor 100, the phenomenon of polymer droplets in the first reactor 100 Can be suppressed and the final conversion rate can be increased.

The conversion of butadiene in the first polymerization reactor 100 is preferably 60 to 85%, and when the conversion of butadiene in the first polymerization reactor 100 is less than 60%, the uniformity of the polymer structure in the first polymerization stage is lowered In addition, the conversion rate in the second polymerization stage is increased, and the amount of gas emission in the second polymerization reactor 200 is rapidly increased. On the contrary, the plugging phenomenon due to the second polymerization reactor 300 Lt; / RTI > If the conversion of butadiene in the first polymerization reactor (100) exceeds 85%, the amount of gas discharged from the first polymerization reactor (100) is increased and the plugging phenomenon due to the first polymerization reactor (100) Lt; / RTI >

The present invention also provides an apparatus for continuous production of butadiene rubber using the continuous production method of butadiene rubber, wherein the butadiene rubber continuous production apparatus will be briefly described with reference to FIGS. 2 and 3. The butadiene rubber The continuous production apparatus of the present invention is characterized in that butadiene, a catalyst and a solvent are supplied (through a raw material supply pipe (not shown)), as shown in Figs. 2 and 3, A second polymerization reactor (200) in which a second polymerization solution containing a butadiene polymer is prepared by performing a polymerization reaction after the first polymerization solution is supplied, a second polymerization reactor A third polymerization reactor 300 in which a polymerization solution is supplied and then a polymerization reaction is performed to produce a third polymerization solution containing a butadiene polymer and a third polymerization reactor 300 in which the first polymerization reactor 100, A condenser 200 for condensing the gas generated by the polymerization heat in the third polymerization reactor 300 and a condenser for condensing the gas generated by the condensation heat in the condenser 200 and the third condenser 300 to be connected to the gas discharge pipes of the respective polymerization reactors 120 of FIG. 3, or 120, 220, 320 of FIG. 3)

The condensed condensate in the heat exchanger (120 in FIG. 2 or 120, 220 and 320 in FIG. 3) is supplied to the first polymerization reactor 100 and the butadiene conversion in the first polymerization reactor 100 Is 60 to 85%, and the first polymerization reactor (100), the second polymerization reactor (200), and the third polymerization reactor (300) are continuous polymerization reactors connected in series. Meanwhile, another description of the apparatus for continuous production of butadiene rubber is the same as that described in the above-mentioned continuous production method of butadiene rubber.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as set forth in the appended claims. Such changes and modifications are intended to be within the scope of the appended claims.

[Example 1] Production of butadiene rubber using three polymerization reactors

A discharge pipe for a polymerization solution containing a butadiene polymer produced by a polymerization reaction at the bottom, a raw material containing a butadiene, a catalyst and a solvent at the side wall of 50 m 3 capacity, having a liquid supply pipe the first polymerization reactor, the first is but equal to the polymerization reactor the polymerization solution discharge pipe of the first polymerization reactor is connected to a raw material liquid supply pipe of the walls of the second polymerization reactor, and wherein in And a third polymerization reactor in which the polymerization solution discharge pipe of the second polymerization reactor is connected to the raw-material solution supply pipe of the side wall, the same as that of the first and second polymerization reactors, and the third polymerization reactor of the first, second and third polymerization reactors One end of the condenser is connected to the gas discharge pipe, and the other end of the condenser is connected to a temporary storage tank in which the butadiene monomer-containing solvent cooled through the heat exchange in the condenser is stored. Butadiene monomer containing solvent connected and, stored in the temporary storage tank as is connected to the first polymerization reactor, the raw liquid mixing tank was used as a continuous polymerization reactor that is connected to the raw material liquid supply pipe of the first polymerization reactor.

Using the three continuous polymerization reactors as described above, the butadiene monomer was continuously introduced into the first polymerization reactor at a flow rate of 13.5 T / h, the catalyst composition and hexane as a solvent at a flow rate of 31.5 T / h, At a temperature of 90 DEG C and a pressure of 2.7 kgf / cm < 2 & gt ;, the gas produced by the heat of polymerization is condensed by a heat exchanger and refluxed into the first polymerization reactor, and the first polymerization solution is transferred to the second polymerization reactor The gas produced by the heat of polymerization in the second polymerization reactor is further condensed by a heat exchanger to be supplied to the first polymerization reactor and the second polymerization solution is further transferred to the third polymerization reactor for further polymerization reaction, The gas produced by the polymerization heat in the polymerization reactor is condensed by a heat exchanger and supplied to the first polymerization reactor, and the third polymerization solution is transferred to a flash vessel The solvent and unreacted butadiene were partially removed and the remainder containing the polymerization solution was transferred to a stripper using water and steam. Then, most of the solvent and unreacted butadiene were removed to form a crumb Next, water was removed to prepare 13.05 t / h of butadiene rubber. At this time, the ratio of the polymerization solution in the total volume of the first polymerization reactor was operated at 45%, the ratio of the polymerization solution in the total volume of the second polymerization reactor was 20%, and the polymerization solution in the total volume of the third polymerization reactor And 50% of the total.

[Comparative Example 1] Production of butadiene rubber using two polymerization reactors

Using only two continuous reactors, i.e., the first and second polymerization reactors of Example 1, the butadiene monomer was fed at a flow rate of 12.5 T / h, the catalyst composition and the solvent hexane at a flow rate of 32.1 T / h, 11.9 t / h of butadiene rubber was prepared. The proportion of the polymerization solution in the total volume of the first polymerization reactor was 50%, the ratio of the polymerization solution in the total volume of the second polymerization reactor was 50 %, Respectively, in the same manner as in Example 1.

[Example 1, Comparative Example 1] Evaluation of the production process of butadiene rubber

In Example 1 and Comparative Example 1, the butadiene conversion and the solid content (TSC) of the butadiene rubber in each of the polymerization reactors were derived, and the results are shown in Table 1 below.

The first reactor
Conversion Rate (%) The second reactor
Conversion Rate (%) The third reactor
Conversion Rate (%) After polymerization
Solid content (%) Remarks Example 1 81.0 91.2 96.7 28 Stable operation
Comparative Example 1
89.5
95.1
-
26.7 After 15 days, stopping the reaction by heat exchanger plugging

As shown in Table 1, in Example 1, the plugging of the heat exchanger did not occur until 6 months after the start of operation, and the butadiene rubber could be stably produced at a high yield. On the other hand, in Comparative Example 1, the heat exchange efficiency of the heat exchanger was lowered due to the plugging phenomenon of the heat exchanger from the point in time when only 15 days passed after the operation, and the polymerization reaction was stopped. That is, the same results as in Example 1 can be obtained by the continuous production method of the butadiene rubber according to the present invention, that is, by using a method of sequentially dispersing the polymerization heat in three polymerization reactors, As a result, the conversion of butadiene in the final polymerization reactor in which the butadiene polymer was discharged to the outside of the reactor was improved as compared with Comparative Example 1, although the conversion of butadiene in the first polymerization reactor to which the initial raw material was supplied was lower than Comparative Example 1 (95.1% to 96.7%).

In addition, as can be seen from the solid content after polymerization in Example 1, it can be seen that the phenomenon that the butadiene polymer is entrained with the gas by the heat exchanger is reduced or eliminated by dispersing and eliminating the heat of polymerization, and the solid content , The energy consumed in the manufacturing process is decreased. From this, it can be seen that by using the continuous production method of the butadiene rubber according to the present invention, the heat of polymerization generated from the first polymerization reactor is effectively dispersed and removed, and the plugging phenomenon is reduced or eliminated, Butadiene rubber can be produced at a high yield.

Claims (14)

A first polymerization solution containing a butadiene polymer is prepared by supplying a butadiene, a catalyst and a solvent to a first polymerization reactor and then performing a polymerization reaction. The gas generated by polymerization heat in the first polymerization reactor is condensed in a heat exchanger A first polymerization step of refluxing into the first polymerization reactor;
Wherein the first polymerization solution is supplied to a second polymerization reactor and then a polymerization reaction is performed to produce a second polymerization solution containing a butadiene polymer and the gas generated by the polymerization heat in the second polymerization reactor is condensed in a heat exchanger A second polymerization step of supplying the first polymerization reactor to the first polymerization reactor; And
A third polymerization solution containing the butadiene polymer is prepared by supplying the second polymerization solution to the third polymerization reactor and performing a polymerization reaction, and the gas generated by the polymerization heat in the third polymerization reactor is condensed in the heat exchanger And a third polymerization step of supplying the first polymerization reactor to the first polymerization reactor,
Wherein the butadiene conversion ratio in the first polymerization reactor is 60 to 85%, and the first polymerization reactor, the second polymerization reactor, and the third polymerization reactor are continuous polymerization reactors connected in series. The continuous process for producing butadiene rubber according to claim 1, wherein the conversion of butadiene in the third polymerization reactor is 95% or more. The continuous process for producing butadiene rubber according to claim 1, wherein the butadiene conversion in the first polymerization reactor is controlled by the residence time of the butadiene raw material in the first polymerization reactor. The method according to claim 1 or 3, wherein the retention time of the starting material in the first polymerization reactor is controlled so that the conversion of butadiene in the first polymerization reactor is 60 to 85% And a third polymerization reactor, wherein the first polymerization reactor and the second polymerization reactor are maintained at a constant temperature. [2] The continuous production method of butadiene rubber according to claim 1, wherein the heat exchangers are formed as one unit, and the gases produced in the respective polymerization reactors are condensed or connected to the polymerization reactors, respectively, and different heat exchangers are used for the respective polymerization reactors. The continuous process for preparing butadiene rubber according to claim 1, wherein the polymerization reaction is carried out at a temperature of 70 to 110 ° C and a pressure of 0.1 to 5 kgf / cm 2 . The method according to claim 1, wherein the total number of polymerization reactors is increased depending on the conversion rate of the polymerization solution discharged from the polymerization reactor disposed last in the polymerization reactor used in the continuous production method of the butadiene rubber or the butadiene rubber production amount Wherein the butadiene rubber is continuously produced. The catalyst according to claim 1, wherein the catalyst is a Ziegler-Natta catalyst selected from the group consisting of a transition metal compound, a lanthanum compound, an organoaluminum compound, a fluoride compound and a mixture thereof. . The continuous process for producing a butadiene rubber according to claim 1, wherein the solvent is selected from the group consisting of aliphatic hydrocarbons having 4 to 6 carbon atoms, alicyclic hydrocarbons, aromatic hydrocarbons, and mixtures thereof. The process of claim 9 wherein the aliphatic hydrocarbon is selected from the group consisting of butane, pentane, hexane, isopentane, heptane, octane, and isooctane, and the alicyclic hydrocarbon is selected from the group consisting of cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethyl Cyclohexane, and said aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, and xylene. The continuous process for producing butadiene rubber according to claim 1, wherein the first polymerization reactor is further fed with a polymerization regulator, a reaction terminator, and a mixture thereof. [3] The method according to claim 1, wherein a gas discharge pipe for transferring the gas generated by the polymerization heat to the heat exchanger is connected to the upper part of the first polymerization reactor, the second polymerization reactor and the third polymerization reactor, and a butadiene polymer Wherein a polymerization solution discharge pipe for discharging a polymerization solution or transferring the polymerization solution to a next polymerization reactor is connected. The continuous process for producing butadiene rubber according to claim 1, wherein the butadiene, the catalyst and the solvent are supplied to the first polymerization reactor through a raw material supply pipe. An apparatus for continuous production of butadiene rubber using the continuous production method of butadiene rubber according to any one of claims 1 to 13.
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