WO2016105037A1 - Hydrogenation method and apparatus for phthalate compound - Google Patents

Abstract

The present invention relates to a hydrogenation method and apparatus for a phthalate compound. The hydrogenation method and apparatus of the present invention can increase the entire catalyst lifespan through operation after dividing an area which has different catalyst activity, during a hydrogenation reaction process of a phthalate compound. Accordingly, it is possible to increase productivity since process maintenance and repair costs are reduced, and process stability is increased.

Description

 [Name of invention]

 Method and apparatus for hydrogenating phthalate compounds

 [Cross Citation with Related Application (s)]

 This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0186394 dated December 22, 2014, and all content disclosed in the literature of that Korean patent application is incorporated as part of this specification.

 Technical Field

 The present invention relates to a phthalate compound and a hydrogenation method and apparatus. More specifically, the present invention relates to a method and apparatus for hydrogenating a phthalate compound, which can improve the life of the entire catalyst by operating the reactor in multiple stages according to the degree of deterioration of the catalyst activity.

 [Technique to become background of invention]

 Phthalate compounds are widely used as plasticizers for plastics, especially polyvinyl chloride (PVC). For example, electrical and electronic products, pharmaceuticals, paint pigments, lubricants, binders, surfactants, adhesives, tiles, food containers, packaging materials, such as the use is very versatile.

However, as some phthalate-based compounds are known to cause environmental pollution and human endocrine disorders, efforts to reduce their use are being strengthened in advanced countries such as Europe and the United States. Some products, especially di ( ^2- ethylhexyl) phthalate (DEHP), butyl benzyl phthalate (BBP) and di-n-butyl phthalate (DBP), are among the phthalate plasticizers. It is suspected of being an environmental hormone as an endocrine disrupter, and there is a movement to regulate it. Thus, efforts have been made to develop environmentally friendly plasticizers free of environmental hormone debate while showing conventional performance, and one of these methods is to use a compound that hydrogenates a benzene ring included in a phthalate compound.

The hydrogenation reaction of aromatic compounds, such as a benzene ring, is known using the catalyst which contains the transition metal, such as ruthenium, in the support as an active component. However, since the activity of the catalyst of the transition metal rapidly decreases as the reaction proceeds, the yield is lowered. Therefore, maintenance of the catalyst activity is a very important problem from a commercial point of view. The decrease in catalytic activity is caused by various physical and chemical effects on the catalyst, for example, the blocking of the catalytically active site or the loss of the catalytically active site as a result of thermal, mechanical or chemical treatment. For example, catalyst deactivation or aging is generally caused by sintering of catalytically active sites, loss of metal as a result of deposits, or poisoning of active sites and various mechanisms exist. The replacement and regeneration process due to this reduced activity of the catalyst leads to product production costs.

 Therefore, in order to produce a material that can be used as an eco-friendly plasticizer on a commercial scale, there is a need for a method for increasing the life time of the catalyst by improving the performance and maintaining the activity of the catalyst used in the hydrogenation reaction. [Content of invention]

 Problem to be solved

 In order to solve the above problems, it is an object of the present invention to provide a hydrogenation method and a hydrogenation apparatus for improving the life of the catalyst in the hydrogenation process of the phthalate compound to reduce the cost and ensure the stability of the operation.

 [Measures of problem]

 Thus, according to one embodiment of the present invention,

 Dividing the reaction space filled with a hydrogenation catalyst into a plurality of independent reaction zones, and introducing a phthalate compound and hydrogen into the reaction zone of the first stage; And reacting the reaction product after the first step reaction zone by adding the reaction product in the previous reaction zone.

In addition, according to another embodiment of the present invention, a phthalate compound supply unit; Hydrogen supply; A first stage reactor connected to the phthalate compound supply unit and the hydrogen supply unit and layered with a hydrogenation catalyst; And at least one independent, connected to said first stage reactor, each filled with a hydrogenation catalyst. Provided is a hydrogenation apparatus for a phthalate compound containing a counterung group.

 【Effects of the Invention】

 According to the hydrogenation method and apparatus of the present invention, in the hydrogenation reaction process of the phthalate-based compound, it is possible to increase the overall catalyst life by operating the zones having different catalyst activities. Therefore, the maintenance and repair cost of a process can be reduced, and the stability of a process can be improved and productivity can be improved. [Brief Description of Drawings]

 1 is a graph showing the change in catalyst activity over time in Examples 1 to 3 and Comparative Example 1.

 2 is a flowchart of a hydrogenation method according to an embodiment of the present invention. 3 is a view showing a hydrogenation apparatus according to an embodiment of the present invention.

 4 is a view showing a hydrogenation apparatus according to another embodiment of the present invention.

 [Specific contents to carry out invention]

 As the present invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, equivalent, component, component, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof. Hereinafter, a method and apparatus for hydrogenating a phthalate compound of the present invention will be described in detail with reference to the accompanying drawings. Hydrogenation method according to an embodiment of the present invention, comprising the step of separating a plurality of independent reaction zone filled with a hydrogenation catalyst, the phthalate compound and hydrogen in the first step reaction zone to react; And reacting the reaction product after the reaction in the previous reaction region by inputting the reaction product in the previous reaction region.

 The reaction target of the hydrogenation method of the present invention is a phthalate compound, which is a reaction in which hydrogen is added to the benzene ring of the phthalate compound by hydrogenation to be converted to a tetrachlorohexane polycarboxylate compound.

 The phthalate compound may be at least one selected from phthalate, terephthalate, isophthalate, and carboxylic acid. Specific examples of the phthalate compound include dibutyl phthalate (DBP), dinuxyl phthalate (DHP; dihexyl phthalate), dioctyl phthalate (DOP), di-n-octyl phthalate (DnOP; di-n- phthalate compounds such as octyl phthalate, diisononyl phthalate, or diisodecyl phthalate (DIDP; diisodecyl phthalate) (di-Rl phthalate, R1 is a straight or branched chain alkyl group having 1 to 20 carbon atoms); Terephthalates such as dibutyl terephthalate (DBTP), dioctyl terephthalate (DOTP; dioctyl terephthalate), diisononyl terephthalate (DINTP), or diisodecyl terephthalate (DIDTP). Di-R2 terephthalate, R2 is a straight or branched chain alkyl group having 1 to 20 carbon atoms; dibutyl isophthalate (DB IP; dibutyl isophthalalate), dioctyl isophthalate (DOIP), diisononyl isophthalate ( Isophthalate compounds such as DINIP; diisononyl isophthalate), or diisodecyl isophthalate (di-R3 isophthalate, R3 is a straight or branched chain alkyl group having 1 to 20 carbon atoms); These compounds can be used alone or in combination.

Preferably, it may be dioctyl terephthalate (DOTP) have.

 The hydrogenation catalyst may include a transition metal of Group 8 as an active ingredient, preferably one selected from ruthenium (Ru), nickel (Ni), palladium (Pd), rhodium (Rh), platinum (Pt), and the like. It may contain the above.

 By this hydrogenation reaction, the aromatic ring of the phthalate compound is hydrogenated and converted into a cyclonucleic acid dicarboxylate compound. _

 Throughout the specification of the present invention, "reaction zone" means a region having a physically independent zone and satisfying a condition in which hydrogenation reaction of a phthalate compound can occur, and in terms of apparatus, the condition In addition, it means that the reaction zone can be separately separated and the reactor is separated. In addition, the reaction zone is divided into the first stage, the second stage, the third stage, and the like (n is an integer of 1 or more). The term refers to the reaction steps which are connected in sequence according to the flow of the hydrogenation reaction of the phthalate compound, which can be divided in series. For example, the crab two stage reaction zone is a reaction zone connected in series with the previous first stage reaction zone, and the third stage reaction zone is a reaction zone connected in series with the previous second stage reaction zone.

The reactor used in the conventional hydrogenation method is a tube type reaction vessel in which a solid hydrogenation catalyst is layered inside the tube type reactor. The reaction raw material containing the phthalate compound and hydrogen is introduced into the upper part of the reactor to form a flow stream, and the reaction of hydrogenation takes place under the hydrogenation catalyst charged inside the reactor, and the reaction product is discharged to the bottom of the reactor. However, as the reaction proceeds as described above, the activity of the catalyst is reduced by impurities present in the reaction material. The decrease in catalytic activity is due to various physical and chemical effects on the catalyst, for example caused by the blocking of the catalytically active site or the loss of the catalytically active site as a result of thermal, mechanical or chemical treatment. In addition, in the early stage of reaction, the reaction proceeds rapidly due to the high concentration of reaction raw materials, and the reaction reaction partially accumulates to generate a hot spot. As sintering occurs due to such hot spots, the deactivation of the catalyst is further accelerated. This decrease in catalytic activity It causes a reduction in overall reaction and causes a decrease in conversion and purity of the reaction product.

However, according to the hydrogenation method of the present invention, the reaction reaction is divided into a plurality of independent reaction zones each layered with a hydrogenation catalyst, and the hydrogenation reaction is carried out in multiple stages. That's my _. In the first stage reaction zone, the phthalate compound. Hydrogen was added to react, and in the crab two-step reaction zone, the reaction product was added and reacted in the first stage reaction zone. In the next third stage reaction zone, the reaction product in the second stage reaction zone is added and reacted, and the reaction product in the previous reaction zone is added to perform the hydrogenation reaction in multiple stages. The reaction zone may be filled with a hydrogenation catalyst separately, and may be filled with the same kind of hydrogenation catalyst.

 As described above, in the early stage of the hydrogenation reaction, as the reaction proceeds in a state where the reaction raw material is in a high concentration, the reaction is rapidly progressed and a hot spot, which is a phenomenon in which reaction heat accumulates partially, is likely to occur. This hot spot accelerates the deactivation of the catalyst. This reduction in catalytic activity causes a reduction in overall reactivity and causes a decrease in the conversion rate and purity of the reaction product. Therefore, a process of replacing or regenerating the deteriorated catalyst is indispensable to maintain the catalyst activity at a constant level as the hydrogenation reaction proceeds.

 However, since the reaction raw material forms a flow stream from the upper or raw material inlet to the lower or the reaction product outlet inside the reaction vessel, and the hydrogenation reaction proceeds, the catalyst at the front side of the reaction vessel is rapidly aging even in one reactor, but the catalyst at the rear side The catalytic activity still remains. In spite of such a difference in the rate of aging of the catalyst, the catalyst layered in one reaction vessel remains in an integrated state, so that the entire replacement or regeneration of the catalyst must proceed, which leads to an increase in replacement cost and a decrease in productivity.

However, according to the hydrogenation method of the present invention, by dividing the reaction zone into a plurality of steps, and proceeding the hydrogenation reaction in multiple stages, it is possible to increase the efficiency by varying the replacement cycle of the catalyst according to the degree of catalyst activity decrease. In the reaction zone, the initial hydrogenation reaction is carried out by adding phthalate compound and hydrogen. The reaction may be divided into a first step reaction zone, in which the reaction is performed, and a reaction zone after the second step in which the hydrogenation reaction is performed by inputting the reaction product in the previous reaction chamber.

 As described above, when the hydrogenation reaction is performed by dividing the first stage reaction zone independently from the lower reaction zone, the catalyst may be independently replaced according to the degree of deterioration of the catalytic activity in the reaction zone of each stage. Since the lower activity of the catalyst in the first stage reaction zone where the high concentration of the reaction raw material is introduced to form a flow downward and the reaction proceeds faster than the lower activity of the catalyst in the subsequent reaction zone, Even if it is reduced, the catalyst in the reaction zone after the second step is fully available. Therefore, since only the catalyst of the first stage reaction zone having reduced activity needs to be replaced, the inefficiency of replacing the catalyst after the second stage reaction region with sufficient activity can be improved.

 Therefore, according to the production method of the present invention, it is possible to evenly use the catalyst layered in each reaction zone evenly, thereby improving the overall catalyst life.

 The number of the reaction zones is not particularly limited to two or more, and according to one embodiment of the present invention, it may be divided into two. That is, the hydrogenation reaction may be performed in two steps in which the phthalate compound and hydrogen are added and reacted in the first stage reaction zone, and then the reaction product in the first stage reaction zone is added and reacted in the second stage reaction zone. .

In addition, according to an embodiment of the present invention, the reaction zones belonging to the same step may also be divided into a plurality of parallel reactions, and each reaction may be independently performed. It can also be operated selectively by switching. As described above, when each stage reaction zone is divided into a plurality, there is an advantage that the operation can be continuously performed in other reaction zones belonging to the same reaction stage zone even when the catalyst replacement is required in any one stage reaction zone. 2 is a flowchart illustrating a hydrogenation method according to an embodiment of the present invention. . Referring to FIG. 2, first, a phthalate compound and hydrogen as raw materials are introduced into a first step reaction zone (step S10).

 According to one embodiment of the present invention, the phthalate compound may be added to the first step reaction zone by increasing the pressure and temperature.

 More specifically, the step of boosting and raising the phthalate compound may be performed simultaneously or in sequence, and the desired pressure and temperature may be reached by boosting and raising the temperature at once or in several steps. For example, first, the pressure of the phthalate compound may be increased, and the elevated phthalate compound may be heated to flow into the first stage reaction region in a liquid state having an appropriate viscosity. According to one embodiment of the present invention, the viscosity of the phthalate compound may be about 0.5 to about 20.0 cps in the pressure and temperature conditions range when entering the first stage reaction zone. When the viscosity of the phthalate compound is within the above range, it may exhibit appropriate flowability and reactivity in the reaction zone. In addition, the phthalate compound may be added in a state dissolved in a suitable organic solvent, if necessary.

 The target pressure boosted to be introduced into the first stage reaction zone may be about 50 to about 500 bar, preferably about 100 to about 300 bar. If the pressure is less than 50 bar, the reactivity becomes low, and it is difficult to obtain a desired level of conversion. If the pressure is too high above 500 bar, it may be difficult to manufacture the semi-ungwoong, or the manufacturing cost may be greatly increased.

In addition, a target temperature for raising the temperature to be introduced into the first stage reaction zone may be in the range of about 50 to about 500 ^° C, preferably about 100 to about 300 ^° C. If the temperature is lower than 50 ^° C, the catalyst is deactivated due to the low temperature, the viscosity of the mixture is high, the flow in the reactor is poor, and the permeation of hydrogen to the phthalate compound in the liquid phase is lowered so that the reaction does not occur properly. , If the temperature is too high exceeding 50CTC, the decomposition of the reactants occurs a lot, there is a difficulty in the production of the reactor, the rapid reaction may be difficult to remove the heat.

The phthalate compound, which has been boosted and elevated by the above-described process, is introduced into the first stage reaction zone in which the hydrogenation catalyst is layered. In addition, a hydrogen (H ₂ ) in the gaseous state is introduced into the reaction zone through a separate supply line to perform a hydrogenation reaction. At this time, the pressure and temperature conditions of the hydrogen is the same as the temperature and pressure conditions of the phthalate compound, the pressure of about 50 to about 500 bar, preferably about 100 to about 300 bar and about 50 to about 500 ^° C, preferably Can be adjusted to be in the range of about 100 to about 300 ^° C.

 Next, the hydrogenation reaction of the phthalate compound is carried out in the presence of a hydrogenation catalyst in the first stage reaction region into which the phthalate compound and hydrogen are charged (step S20).

 Temperature and pressure conditions in the first stage reaction zone are about 50 to about

It can be adjusted to a pressure of 500 bar, preferably about 100 to about 300 bar and a temperature range of about 50 to about 500 ^° C., preferably about 100 to about 300 ^° C.

 According to an embodiment of the present invention, the first step reaction zone is divided into a plurality of parallel reactions, such as a 1-1 step reaction zone and a step 1-2 reaction zone, and a phthalate compound and hydrogen are independently added and Can react. The plurality of first stage reaction regions may be selectively operated in such a manner that all of them operate simultaneously or alternately. As such, when the first stage reaction zone is divided into a plurality of reactors, the catalyst replacement in the first stage reaction zone—if necessary, may be continuously operated in another preliminary first stage reaction zone.

 The hydrogenation process of the present invention can be carried out in liquid phase or gas phase. According to an embodiment of the present invention, the phthalate compound may be subjected to hydrogenation reaction in a liquid state and hydrogen in a gaseous state.

 The phthalate compound is converted into the corresponding cyclonucleic acid dicarboxylate compound in the presence of a hydrogenation catalyst.

According to one embodiment of the invention, in the first stage reaction zone, hydrogenation until the reaction conversion rate of the initially added phthalate compound reaches about 40% to about 95%, preferably about 60% to about 90% You can perform a reaction. As described above, the reaction rate in the first stage reaction zone By adjusting, the efficiency of final hydrogenation conversion and catalyst activity can be made higher.

 Throughout the specification of the present invention, "banung conversion rate" means the ratio (percentage) of the number of moles of the phthalate hydrogenated compound produced by the hydrogenation reaction with respect to the number of moles of the phthalate compound introduced into the reactor or the reaction zone, as shown in Equation 1 below. do.

 [Equation 1]

¾ formed ≤ t¾o | ^£ hydrogen ¾ ¾S water ^

Ioa spg- group (: * S region Pitu ¾ is ϊί¾ί ¾g * ^' , followed by the reaction products in the first stage reaction zone are continuously introduced into the second stage reaction zone ( Step S30).

 The reaction product in the first stage reaction zone includes not only the hydrogenated compound of the phthalate compound, but also the phthalate compound and hydrogen in the raw reaction state.

 In the second stage reaction region into which the reaction product in the first stage reaction region is introduced, hydrogenation reaction proceeds to the unbanung raw materials included in the reaction product in the presence of a hydrogenation catalyst (step S40).

 The unreacted phthalate compound included in the reaction product is converted to the corresponding cyclonucleic acid dicarboxylate compound by reaction in the second stage reaction zone. Since the second stage reaction zone is filled with a hydrogenation catalyst separately from the first stage reaction zone, the hydrogenation reaction may proceed at a still high conversion rate to the uncoated phthalate compound.

The temperature and pressure conditions in the second stage reaction zone are about 50 to about 500 bar, preferably about 100 to about 300 bar and about 50 to about 500 ^° C., as in the first stage reaction zone. Preferably it can be adjusted to a temperature range of about 100 to about 300 ^° C.

Although only the second stage reaction zone is shown in the flowchart of FIG. 2, a third stage reaction zone, a fourth stage reaction zone, and the like may be continuously provided after the second stage reaction zone as necessary. In the subsequent reaction area added Each hydrogenation catalyst is charged separately, and the reaction product of the previous step is delivered so that the hydrogenation reaction proceeds to the unbanung phthalate compound.

 After all the hydrogenation reactions are completed, the liquid phase hydrogenation reaction product and the unreacted gas phase raw material are separated and purified from the reaction product (step S50). The separated gaseous raw material may be recycled to a hydrogenation process. The recovered hydrogenation reaction product can be finally separated through a reduced pressure and cooling process.

 According to another embodiment of the present invention, a phthalate compound supply unit; Hydrogen supply; A first stage semi-unggi device connected to the phthalate compound supply unit and the hydrogen supply unit and filled with a hydrogenation catalyst; And a hydrogenation apparatus for the phthalate compound connected to the first stage reaction reactor, each containing at least one independent reaction vessel filled with a hydrogenation catalyst.

 The reactor used in the hydrogenation apparatus of the present invention is a tubular reactor in which a solid hydrogenation catalyst is layered inside a tube-type reactor.

 In the hydrogenation apparatus of the present invention, a plurality of independent reactors each filled with a hydrogenation catalyst are divided into a plurality of reactors to proceed with hydrogenation reaction in each stage. That is, in the first step reaction step, the phthalate compound and hydrogen are introduced into the reaction from the phthalate compound supply part and the hydrogen supply part. The second stage reactor is connected to the first stage reactor, and the reaction product discharged from the first stage reactor is introduced and reacted. The next third stage reactor is connected to the second stage reaction reactor, and the reaction product in the second stage reaction reactor is introduced to react, and the reaction product in the previous reactor is introduced to proceed the hydrogenation reaction in multiple stages. do. Hydrogenation catalysts are layered separately in the reaction vessels, and the same kind of hydrogenation catalysts may be layered.

 The hydrogenation catalyst may include a transition metal of Group 8 as an active ingredient, preferably one selected from ruthenium (Ru), nickel (Ni), palladium (Pd), rhodium (R), platinum (Pt), and the like. It may include the following

As described above, according to the hydrogenation apparatus of the present invention, the reaction activity is reduced by providing a reaction reactor in multiple stages and proceeding the hydrogenation reaction in stages. Depending on the degree, the replacement cycle of the catalyst can be varied to increase efficiency. For example, by separating the upper zone where the deterioration of the catalyst activity is concentrated, the first stage reactor is then distinguished from the lower half-ungker, allowing the catalyst to be replaced independently at each stage of the reaction. In a first stage reactor in which a high concentration of reaction raw material is introduced to form a flow in a downward direction and reaction is progressed, since the lowering of catalytic activity is faster than the lowering of catalytic activity in subsequent reactions, Even if it is reduced, the semi-unggi catalyst after the second step is fully available. Therefore, since only the catalyst of the first stage half-unggi having lowered activity needs to be replaced, the inefficiency of replacing the catalyst after the second stage reactor, which is still highly active, is improved. ^'

 Through the present invention it is possible to use evenly enough catalyst filled in the reactor through which it is possible to enhance the overall catalyst life.

 According to an embodiment of the present invention, the hydrogenation apparatus is connected to the phthalate compound supply unit and the hydrogen supply unit, and is connected to the first stage reactor in which the hydrogenation catalyst is layered, and the first stage reactor, and the hydrogenation catalyst is charged. It may comprise a two stage reactor comprising a second stage reaction.

 As described in the hydrogenation method of the phthalate compound, the reaction rate of the phthalate compound in the first stage reactor may have a conversion rate of about 40% to about 95%, preferably about 60% to about 90%. By adjusting the reaction rate in the first stage reactor to the above range, it is possible to exhibit the effect of improving the life of the entire catalyst catalyst.

 In addition, a plurality of first stage reactors may also be provided in parallel so that each of the first stage reactors separated in parallel may be independently connected to a phthalate compound supply unit and a hydrogen supply unit. The plurality of first stage reactors separated in parallel may be selectively operated in such a manner that all of them operate simultaneously or alternately switch. As such, when the first stage reactor is divided into a plurality of reactors, the first stage reactor may be continuously operated in another first stage reactor even when a catalyst replacement is required.

3 illustrates a hydrogenation apparatus according to an embodiment of the present invention. Drawing.

 Referring to FIG. 3, the hydrogenation apparatus 100 of the present invention comprises a phthalate compound supply section 10; Hydrogen supply 20; A first stage reaction vessel 30 connected to the phthalate compound supply portion 10 and the hydrogen supply portion 20 and filled with a hydrogenation catalyst; A second stage reactor 40 is connected to the first stage reaction reactor 30 and filled with a hydrogenation catalyst.

 The phthalate compound, which is a raw material, is supplied to the first stage reactor 30 through the phthalate compound supply unit 10. The phthalate compound may be elevated and elevated to be fed to the first stage semiaerator 30 at an appropriate temperature and pressure.

 Separately, hydrogen from the hydrogen supply unit 20 is also heated up and boosted and supplied to the first stage semiaerator 30. According to an embodiment of the present invention, the phthalate compound may be supplied in a liquid state and the hydrogen may be supplied in a gaseous state.

In the first stage reactor 30, in the presence of a hydrogenation catalyst packed therein, a hydrogenation reaction proceeds in which the phthalate compound and hydrogen react and are converted to the corresponding cyclonucleic acid dicarboxylate compound. The hydrogenation catalyst may include a transition metal of Group 8 as an active ingredient, preferably one selected from ruthenium (Ru), nickel (Ni), palladium (Pd), rhodium (Rh), platinum (Pt), and the like. It may contain the above. The first stage reactor 30 may be adjusted to a pressure of about -50 to about 500 bar and a temperature of about 50 to about 500 ^° C.

 By the way, in the first stage half-unggi (30), the reaction proceeds abruptly due to the high concentration of the reaction material, resulting in a rapid decrease in activity of the catalyst due to the accumulation of reaction heat. This lowering of the catalytic activity leads to a decrease in the overall reaction and leads to a decrease in conversion and purity of the reaction product. Therefore, the replacement cycle of the catalyst in the first stage reaction reactor 30 is faster than in the reactor after the second stage, and the catalyst can be replaced or regenerated independently of such a different catalyst replacement cycle so that the overall catalyst Can improve lifespan.

The length of the first stage half-reactor 30 is determined by the first _. Step and second step reaction It can have a ratio of about 10 to about 50%, preferably about 20 to about 35%, of the total combined reactor length. By adjusting the length of the first stage reactor 30 to the above range, after both the first and second stage reactions are finished, the non-banung phthalate-based compound may not remain substantially.

The reaction product discharged from the first stage reactor 30 is transferred to the second stage reaction vessel 40, and the hydrogenation reaction takes place in the second stage reactor 40 in which the hydrogenation catalyst is layered independently. The reaction product contains not only the hydrogenation reaction product of the phthalate compound, but also the phthalate compound and hydrogen, which are unreacted raw materials, such that the unreacted raw material is subjected to the hydrogenation reaction again in the second stage reaction reactor 40. The second stage reactor 40 is also filled with a hydrogenation catalyst, which is a group 8 transition metal, preferably ruthenium (Ru), nickel (Ni), palladium (Pd) and rhodium (Rh) as active ingredients. , platinum may include ^'at least one member selected etc. (Pt).

 The final reaction product from the second stage reactor 40 is separated and purified through the separation device 50 into a liquid reaction product and a gaseous unreacted product, and the resulting impurities are removed as a final reaction product. Can be.

 4 is a view showing a hydrogenation apparatus according to another embodiment of the present invention.

 Referring to FIG. 4, the hydrogenation apparatus 200 of the present invention includes a phthalate compound supply unit 110; Hydrogen supply (? 0); A first stage reaction vessel (130, 140) connected to the phthalate compound supply unit (110) and the hydrogen supply unit (120) and having a hydrogenation catalyst layered thereon; It is connected to the first stage reaction reactors 130 and 140 and includes a second stage reaction reactor 150 in which a hydrogenation catalyst is layered.

 The phthalate compound, which is a raw material, is supplied to the first stage semi-aerators 130 and 140 through the phthalate compound supply unit 110. The phthalate compound may be elevated and elevated to feed first stage reactors 130 and 140 at appropriate temperature and pressure conditions.

Separately, hydrogen from the hydrogen supply 120 is also warmed up and boosted and supplied to the first stage semi-aerators 130, 140. According to an embodiment of the present invention, the The phthalate compound may be supplied in a liquid state and the hydrogen may be supplied in a gaseous state. The first stage reaction vessels 130 and 140 can be adjusted to a pressure of about 50 to about 500 bar and a lightness of about 50 to about 500 ^° C.

 In the first stage reactors 130 and 140, in the presence of a hydrogenation catalyst layered therein, a hydrogenation reaction proceeds in which the phthalate compound and hydrogen react and are converted to the corresponding cyclonucleic acid dicarboxylate compound. The hydrogenation apparatus 200 shown in FIG. 4 is provided with two first stage half-aerators 130 and 140, and the phthalate compound supply part 1 10 and hydrogen are supplied to each crab first stage half-aerator 130 and 140, respectively. The supply parts 120 are each independently connected. The two first stage reactors 130 and 140 may all operate at the same time, or may be selectively operated in a manner of switching by operating one of the two but not the other. Although only two first stage reactors 130 and 140 are illustrated in the drawing, three or more reactors may be provided as necessary.

 As such, when a plurality of first-stage reactors are provided, it is possible to operate in the other first-stage reactor even when the catalyst replacement of the first-stage reactor is necessary, so that there is an additional advantage that the operation can be continuously performed when the catalyst is replaced. ,

 The reaction product discharged from the first stage reaction vessels 130 and 140 is transferred to the second stage reaction reactor 150, where the hydrogenation reaction proceeds independently of the second stage reaction reactor 150 filled with the hydrogenation catalyst. The reaction product includes not only the hydrogenation reaction product of the phthalate compound, but also the phthalate compound and hydrogen, which are the reaction agent, and the reaction agent proceeds to the hydrogenation reaction in the second stage reaction reactor 150 again.

 The final reaction product from the second stage reactor 150 can be separated and purified through the separation device 160 into a liquid reaction product and a gaseous unreacted material, and can be obtained as a final reaction product by removing impurities. have.

According to the hydrogenation method and apparatus of the phthalate compound according to the present invention, the catalyst life is increased by a multi-step reaction and a switch reaction, Stable operation is possible, which reduces the cost of maintaining and repairing the process.

 Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific examples of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

<Example>

 Example 1

 In order to carry out the hydrogenation reaction, as shown in FIG. 3, a reaction vessel having a first and a second stage reactor was configured. Each of the first and second stage reactors was in the form of a single tube, the length of the reaction zone of the first stage reactor was 5 m, and the length of the reaction chamber of the second stage reactor was 10 m. In the outer jacket, the hydrogenation reaction was performed while maintaining the temperature by removing heat generated in the reaction vessel through hot oil. The catalyst used in the first and second stage reactors was ruthenium (Ru), and a size of 3 mm in diameter and 3 mm in height was used as a pellet type.

Dioctyl terephthalate was preheated to a pressure of 150 bar and a temperature of 120 ^° C. and injected into the first stage reactor in a liquid state via a pump. Hydrogen (¾) was also preheated to the same pressure and temperature and then fed in the gaseous phase to the top of the first stage semi-aerator separately from dioctyl terephthalate. The reaction conversion rate of the first stage half-ungki of the dioctyl terephthalate-l hydrogenation reaction proceeds to the initial reaction (the initial time of the reaction and the product exit from the reaction, i.e., the total catalytic activity is 1). After proceeding up to%, the reaction product of the first stage reactor was transferred to the second stage reactor to proceed with the second stage hydrogenation reaction to obtain a final reaction conversion rate of 99.9%.

As the reaction proceeded, the activity of the catalyst began to decrease at 1, and when the activity of the entire catalyst reached 0.95, the catalyst of the first stage reactor was replaced by one. Example 2

 In Example 1, the hydrogenation reaction was carried out in the same manner as in Example 1, except that the reaction zone of the first stage reaction reactor was 7 m and the length of the reaction zone of the second stage reactor was 8 m.

 Hydrogenation reaction of dioctyl terephthalate proceeded, resulting in a reaction rate of 81.3% of the first stage reaction reaction of the initial reaction (the initial point of reaction and when the product emerges from the reactor, i.e. when the total catalytic activity is 1). After proceeding to, the reaction product of the first stage reactor was transferred to the second stage reactor to proceed with the second stage hydrogenation reaction, and the final reaction reaction yield was 99.9%.

 As the reaction proceeded, the activity of the catalyst began to decrease at 1, and when the activity of the entire catalyst reached 0.95, the catalyst of the first stage of the reaction was replaced once. Example 3

 In Example 1, the hydrogenation reaction was performed in the same manner as in Example 1 except that the reaction region of the first stage half-unggi was 10 m and the length of the reaction region of the second stage half-unggi was 5 m.

Hydrogen reaction of dioctyl terephthalate proceeds and the reaction rate of the reaction of the first stage of the reaction in the first stage of the initial reaction (when the reaction begins and the product emerges from the reaction, i.e., the total catalytic activity is 1) ^. After proceeding to 89.1%, the reaction product of the first and the first stages of the reaction product was transferred to the second stage of the reactor to undergo the second stage of the hydrogenation reaction to obtain a final reaction reaction rate of 99.9%.

 As the reaction proceeded, the activity of the catalyst began to decrease at 1, and when the activity of the entire catalyst reached 0.95, the catalyst of the first stage reactor was replaced once. Comparative Example 1

One-stage half-foot machine in the form of a single tube (15m length of reaction zone, 2 Other conditions were carried out in the same manner as in Example 1 except that no step reaction area was used.

 As the reaction of hydrogenation reaction of dioctyl terephthalate proceeded, reaction of paracatalyst began to decrease at 1, and the reaction proceeded without replacing the catalyst until the activity of the entire catalyst reached 0.95.

 In Examples 1 to 3 and Comparative Example 1, the catalyst operating time, total catalyst usage, initial reaction conversion rate, final reaction conversion rate, final product purity, and operating time per unit catalyst were measured and shown in Table 1 below.

 In addition, changes in catalyst activity with time of Examples 1 to 3 and Comparative Example 1 are shown in FIG. 1.

Table 1

* 운전 가능 기간 : 전체 촉매의 활성 (activity)을 1이라 할 때, 연속적으로 수소화 반웅을 진행하면서 1차로 전체 촉매의 활성이 0.95 에 이르렀을 때 제 1 단계 반웅 영역 (반웅기)의 촉매를 교체한 후， 2차로 다시 전체 촉매의 활성이 0.95에 이를 때까지 걸리는 운전 시간을 의미한다.

* Operation period: When the activity of the entire catalyst is 1, the hydrogenation reaction is continuously performed, and when the activity of the total catalyst reaches 0.95, the catalyst of the first stage reaction zone (the reaction vessel) is replaced. And then again It means the operation time until the activity of the total catalyst reaches 0.95.

 ** Initial Reaction Conversion Rate: The conversion rate of the one-step reaction zone at the initial point of reaction when the product emerges from the reactor.

 *** Final Reaction Conversion Rate: The final reaction conversion rate at the time when the reaction was finally completed. Referring to Table 1 and the contents of FIG. 1, as in Examples 1 to 3, when the reaction zone is divided into a first stage and a second stage, only the catalyst of the first stage reaction zone in which reaction is concentrated is replaced and operated. Compared to 1, the operating period and the total amount of catalyst used increased. Comparing this in terms of the operating period per unit catalyst it can be seen that in the case of Examples 1 to 3, at least 17%, up to 30% or more increased than Comparative Example 1.

 From these results, it was confirmed that the reaction zone was divided into multiple stages as in the present invention, and as the reaction was progressed, the catalyst was replaced only for the aged reaction zone, thereby improving the overall catalyst life and allowing stable operation in the long term.

 [Explanation of code]

 10, 110: phthalate compound supply unit

 20, 120: hydrogen supply unit

 30, 130, 140: first stage reactor

 40, 150: second stage reactor

 50, 160: separation device

 100, 200: hydrogenation device

Claims

 [Claim]  [Claim 1]  Dividing the independent reaction zone filled with the hydrogenation catalyst into a plurality of reactions, and introducing a phthalate compound and hydrogen into the first reaction zone; And (2) A hydrogenation method of a phthalate compound comprising the step of reacting the reaction product in the previous reaction zone in the reaction zone after the first step reaction zone. 【Claim ² 】  According to claim 1,  Dividing the reaction zone into two and reacting the phthalate compound with hydrogen in a first stage reaction zone; And injecting the reaction product in the first step reaction zone into the second step reaction zone for reaction. [Claim 3]  The method of claim 1,  A hydrogenation method of a phthalate compound is carried out until the reaction conversion of the phthalate compound introduced in the first step reaction region calculated by the following formula 1 reaches 40% to 95%:  [Equation 1]  ᅵ Production g is ≤ a | Number of times. Digestion ¾ 營 ¾ Full water ¾ »ι = ^{^} ᅳ ~- ^" ᅳ "― ― ~ X ΐδδ m ^~ m ^to ¾3 is the number of trips [claim 4]  The method of claim 1, A hydrogenation method of a phthalate compound in which the first step reaction zone is divided into a plurality of phthalate compounds and hydrogen are added and reacted independently. [Claim 5]  In U,  The hydrogenation catalyst is a hydrogenation method of a phthalate compound comprising at least one selected from the group consisting of ruthenium (Ru), palladium (Pd), rhodium (Rh), platinum (Pt) and nickel (Ni). [Claim 6]  The method of claim 1, Wherein each of the plurality of reaction zones is independently adjusted to a pressure of 50 to 500 bar and a silver of 50 to 500 ^° C. [Claim 7]  According to claim 11,  The phthalate compound is a liquid phase (liquid phase), the hydrogen is introduced into the gas phase (gas phase) hydrogenation method of the phthalate compound. [Claim 8]  The method of claim 1,  The reaction product is a hydrogenation compound of the phthalate compound, and a hydrogenation method of the phthalate compound comprising hydrogen and unreacted phthalate compound in the previous reaction step. [Claim 9]  Phthalate compound supply unit;  Hydrogen supply;  A first stage reaction reactor connected to the phthalate compound supply unit and the hydrogen supply unit and layered with a hydrogenation catalyst; And An apparatus for hydrogenating phthalate compounds connected to the first stage reactor and including one or more independent semi-ungers, each filled with a hydrogenation catalyst. [Claim 10]  The method of claim 9,  Connected to the first stage reactor, the hydrogenation apparatus of a phthalate compound comprising a second stage reactor layered hydrogenation catalyst. [Claim 1 11]  The method of claim 9,  The first stage reactor is provided with a plurality, the phthalate compound supply unit and the hydrogen supply unit is connected to each of the plurality of first stage reactors, phthalate compound hydrogenation device. . [Claim 12]  The method of claim 1,  The plurality of first stage reaction device is a hydrogenation apparatus of the phthalate compound to be operated by switching each independently. [Claim 13]  The method of claim 9,  The plurality of reactors are each independently a pressure of 50 to 500 bar and Device for hydrogenation of phthalate compounds controlled to a temperature of 50 to 500 ^° C.