阅读说明：本技术 苯二甲酸酯化合物的氢化方法 (Method for hydrogenating phthalate compound ) 是由 李惠媛 金孝锡 丁基泽 朴圣慜 郑在钦 于 2018-11-01 设计创作，主要内容包括：本发明涉及一种苯二甲酸酯化合物的氢化方法。根据本发明,在氢化反应中抑制副产物的产生,因此,可以改善催化活性以及延长催化剂寿命,从而提高商业过程的效率和经济效率。此外,通过本发明制备的氢化反应产物由于其高纯度和低酸值而具有作为增塑剂的优异品质,因此可用于各种产品。(The invention relates to a hydrogenation method of phthalate compounds. According to the present invention, the production of by-products is suppressed in the hydrogenation reaction, and therefore, it is possible to improve the catalytic activity and to extend the catalyst life, thereby increasing the efficiency and economic efficiency of the commercial process. In addition, the hydrogenation reaction product prepared by the present invention has excellent quality as a plasticizer due to its high purity and low acid value, and thus can be used for various products.)

1. A process for hydrogenating a phthalate compound, which comprises the step of reacting the phthalate compound with hydrogen in the presence of a hydrogenation catalyst in a reactor,

Wherein the temperature deviation in the reactor during the reaction is from 0 ℃ to 30 ℃, and

The acid value of the hydrogenation product separated after the reaction was 0.3KOHmg/g or less.

2. The method for hydrogenating the phthalate compound according to claim 1, wherein the temperature change per unit length (m) of the reactor during the reaction is 10 ℃ or less.

3. The method for hydrogenating the phthalate compound of claim 1 wherein the amount of hydrogen gas introduced into the reactor is 3 to 300 moles per 1 mole of the phthalate compound.

4. The method for hydrogenating the phthalate compound according to claim 1, wherein the phthalate compound is one or more selected from the group consisting of phthalates, terephthalates, isophthalates and carboxylic acid compounds thereof.

5. The method for hydrogenating the phthalate compound according to claim 1, wherein a gas phase raw material is fed from an upper portion or a lower portion of said reactor, and a liquid raw material is fed from an upper portion of said reactor.

6. The method for hydrogenating the phthalate compound according to claim 1, wherein the hydrogenation catalyst is one or more selected from the group consisting of ruthenium (Ru), rhodium (Rh), palladium (Pd) and platinum (Pt).

7. The method for hydrogenating the phthalate compound according to claim 1, wherein the amount of the hydrogenation catalyst is 3% by weight or less based on 100% by weight of the carrier.

8. A hydrogenated phthalate or terephthalate compound prepared by the process of any one of claims 1 to 7.

9. A plasticizer comprising the hydrogenated phthalate or terephthalate compound of claim 8.

10. A resin composition comprising the plasticizer according to claim 9; and a resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polybutadiene, silicone, thermoplastic elastomers, or copolymers thereof.

Technical Field

Cross Reference to Related Applications

This application claims the benefit of korean patent application No. 10-2017-0161951, filed on 29/11/2017 with the korean intellectual property office, the entire contents of which are incorporated herein by reference.

The invention relates to a hydrogenation method of phthalate compounds. Specifically, the present invention relates to a process for hydrogenating a phthalate compound, which not only suppresses the production of by-products and extends the catalyst life, but also keeps the acid value of the hydrogenated product low, thereby improving the quality as a plasticizer.

Background

Phthalate-based compounds are materials widely used as plasticizers for plastics, especially polyvinyl chloride (PVC). For example, it is used in various applications such as electric and electronic products, medicines, paints, lubricants, adhesives, surfactants, adhesives, tiles, food containers, packaging materials, and the like.

However, several phthalate compounds are known to cause environmental pollution and endocrine destruction in humans, and regulations on use are also being strengthened in developed countries such as europe, the united states, and the like. In particular, among phthalate-based plasticizers, some products, such as di (2-ethylhexyl) phthalate (DEHP), butylbenzyl phthalate (BBP) or di-n-butyl phthalate (DBP), are considered as endocrine disruptors that interfere or disturb the action of human hormones, and therefore, it is necessary to manage them.

Accordingly, efforts are being made to develop an environmentally friendly plasticizer exhibiting the same properties as conventional plasticizers without environmental hormone problems, one of which is a method using a compound in which a benzene ring contained in a phthalate compound is hydrogenated.

As hydrogenation of aromatic compounds such as benzene rings, a method using a catalyst comprising a transition metal such as ruthenium on a support as an active ingredient is known. For example, korean registered patent No. 1556340 proposes a hydrogenation method of reacting a phthalate compound with hydrogen in the presence of a hydrogenation catalyst and an alcohol, and discloses that the performance and life of the catalyst are improved according to the method.

The product prepared by hydrogenation is obtained as a mixture of cis and trans isomers. Here, since the cis-isomer content is high, excellent plasticization efficiency for PVC resin, a fast absorption speed and high transparency of the product after curing are exhibited, and leaching is rarely generated on the surface of the product even though it is used for a long time, thus exhibiting excellent properties as a plasticizer.

Therefore, in order to obtain a plasticizer having excellent quality, a hydrogenation method of a phthalate compound having improved stereoselectivity so that the content of cis-isomer is high is required.

[ Prior art documents ]

Patent document 1: korean registered patent No. 1556340, "method for hydrogenating phthalate ester"

Disclosure of Invention

Technical problem

In order to solve the above problems, it is an object of the present invention to provide a novel method for hydrogenating a phthalate compound, which not only suppresses side reactions and controls the acid value of the product, but also improves the purity of the product, and improves the hydrogenation properties of the phthalate-based compound, thereby improving the reaction yield.

Technical scheme

To achieve the object, there is provided a method for hydrogenating a phthalate compound, which comprises the step of reacting the phthalate compound with hydrogen in the presence of a hydrogenation catalyst in a reactor,

Wherein the temperature deviation in the reactor during the reaction is from 0 ℃ to 30 ℃, and

The acid value of the hydrogenation product separated after the reaction was 0.3KOHmg/g or less.

Preferably, the temperature change per unit length (m) of the reactor during the reaction may be 10 ℃ or less.

The amount of hydrogen introduced into the reactor may be 3 to 300 moles per 1 mole of the phthalate compound.

The phthalate compound may be one or more selected from the group consisting of phthalates, terephthalates, isophthalates, and carboxylic acid compounds thereof.

The gas phase raw material may be fed from the upper or lower part of the reactor, and the liquid raw material may be fed from the upper part of the reactor.

The hydrogenation catalyst may be one or more selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), and platinum (Pt).

The amount of the hydrogenation catalyst may be 3 wt% or less based on 100 wt% of the support.

Also provided are hydrogenated phthalate or terephthalate compounds prepared by the above process.

Hydrogenated phthalate or terephthalate compounds may be used as plasticizers.

Also provided is a resin composition comprising the plasticizer, and a resin selected from ethylene-vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polybutadiene, silicone, thermoplastic elastomers, or copolymers thereof.

Effects of the invention

According to the hydrogenation method for phthalate compounds, the production of by-products can be suppressed during the hydrogenation reaction, and thus, the catalytic activity can be improved and the catalyst life can be extended, thereby improving the efficiency and economic feasibility of commercial processes. Also, since the hydrogenated product produced by the method has high purity and a low acid value, it has excellent quality as a plasticizer and thus can be used for various products.

Drawings

Figure 1 schematically shows a hydrogenation apparatus for use in the hydrogenation process of the present invention.

Detailed Description

While the present invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that these are not intended to limit the invention to the particular disclosure, but rather, the invention includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

As used herein, the inclusion of ordinal terms such as "first", "second", etc., is used to explain various structural elements, but the structural elements are not limited by the terms. The term is used only to distinguish one structural element from another. For example, a first structural element may be referred to as a second structural element, and similarly, a second structural element may be referred to as a first structural element.

The singular encompasses the plural unless it is explicitly stated or is obvious from the context. As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" and the like are intended to specify the presence of stated features, quantities, steps, elements, or combinations thereof, and they are not intended to preclude the presence or addition of one or more other features, quantities, steps, elements, or combinations thereof.

Hereinafter, the hydrogenation method of phthalate compounds according to the present invention will be explained in detail with reference to the accompanying drawings.

According to a preferred embodiment of the present invention, there is provided a method for hydrogenating a phthalate compound, which comprises the step of reacting the phthalate compound with hydrogen in the presence of a hydrogenation catalyst in a reactor,

Wherein the temperature deviation in the reactor during the reaction is from 0 ℃ to 30 ℃, and

The acid value of the hydrogenation product separated after the reaction was 0.3KOHmg/g or less.

By minimizing the temperature deviation of the reactor during the reaction and preventing the generation of hot spots, the reaction efficiency can be improved and the generation of byproducts can be suppressed. Therefore, the life of the hydrogenation catalyst in the reactor can be prolonged, and the effects of productivity improvement, yield improvement, and economic efficiency improvement can be ensured. Further, according to the hydrogenation process of the present invention, a product having an acid value below a certain level can be prepared, thereby improving the quality as a plasticizer.

The object of hydrogenation is a phthalate compound, and by hydrogenation, hydrogen is added to the benzene ring of the phthalate compound and the phthalate compound is converted into the corresponding cyclohexanedicarboxylate ester.

The phthalate compound may be one or more selected from the group consisting of phthalates, terephthalates, isophthalates, and corresponding carboxylic acids.

First, the phthalate compound may be represented by the following chemical formula 1.

[ chemical formula 1]

In chemical formula 1, R1 and R1' are the same as or different from each other, and are each independently hydrogen, or a C1 to 20, preferably C4 to 20, more preferably C5 to 20, even more preferably C5 to 10 linear or branched alkyl group.

Specific examples of the phthalate compound may include dibutyl phthalate (DBP), dihexyl phthalate (DHP), dioctyl phthalate (DOP), di-n-octyl phthalate (dnap), diisononyl phthalate or diisodecyl phthalate (DIDP), but are not limited thereto. These compounds may be used alone or in combination.

The terephthalate compound may be represented by the following chemical formula 2.

[ chemical formula 2]

In chemical formula 2, R2 and R2' are the same as or different from each other, and are each independently hydrogen, or a C1 to 20, preferably C4 to 20, more preferably C5 to 20, even more preferably C5 to 10 linear or branched alkyl group.

Specific examples of the terephthalate compound may include dibutyl terephthalate (DBTP), dioctyl terephthalate (DOTP), diisononyl terephthalate (DINTP), or diisodecyl terephthalate (DIDTP), but are not limited thereto. These compounds may be used alone or in combination.

The isophthalate compound can be represented by the following chemical formula 3.

[ chemical formula 3]

In chemical formula 3, R3 and R3' are the same as or different from each other, and each independently hydrogen, or a C1 to 20, preferably C4 to 20, more preferably C5 to 20, even more preferably C5 to 10 linear or branched alkyl group.

Specific examples of the isophthalate compound may include dibutyl isophthalate (DBIP), dioctyl isophthalate (DOIP), diisononyl isophthalate (DINIP), or diisodecyl isophthalate (DIDIP), but are not limited thereto. These compounds may be used alone or in combination.

Preferably, as the phthalate compound, dioctyl terephthalate (DOTP) may be used.

The phthalate compound may have a purity of about 99% or more, preferably about 99.5% or more, more preferably about 98% or more, but is not limited thereto, and a commercially available phthalate compound of any quality and purity may be used.

The hydrogenation of the phthalate compound may be carried out in the liquid or gas phase. According to one embodiment of the present invention, the hydrogenation process may be carried out with a liquid phthalate compound and gaseous hydrogen.

Per unit area (m) ²) The mass flux of the phthalate compound introduced into the reactor, i.e., the volume per unit area (m) of the reactor packed with the catalyst ²) The mass flux of (a) may preferably be from 10,000 to 100,000kg hr ^-1*m^-2More preferably 17,000 to 50,000kg hr ^-1*m^-2。

If per unit area (m) ²) The phthalate compound(s) have a mass flux of less than 10,000kg hr ^-1*m^-2The input amount of raw materials may be insufficient, resulting in a decrease in productivity, and if it is more than 100,000kg hr ^-1*m^-2Then, the amount of the liquid raw material introduced into the reactor at one time may excessively increase, the thickness of the raw material film on the surface of the catalyst may increase, and thus hydrogen may be difficult to permeate, hydrogenation reaction may be difficult to occur, and thus, side reaction may increase and local heating may occur, thereby increasing the temperature deviation of the reactor.

Meanwhile, in order to minimize side reactions and control the acid value of the hydrogenated product below a certain level, and to optimize the ratio between reaction materials to increase productivity, the amount of hydrogen introduced into the reactor may be 3 moles or more, or 4 moles or more, or 7 moles or more, and 300 moles or less, or 100 moles or less, or 50 moles or less, or 30 moles or less, based on 1 mole of the phthalate compound.

If the amount of hydrogen is less than 3 moles per 1 mole of the phthalate compound, the reaction conversion rate decreases and a conversion rate of 95% or more cannot be obtained, while if it exceeds 300 moles, the residence time of the liquid raw material droplets is shortened by hydrogen, and therefore, the conversion rate may decrease or by-products may increase, or the catalyst life may be rapidly shortened. In this regard, the amount of hydrogen is preferably within the above range.

The temperature and pressure conditions of the gas-phase raw material and the liquid-phase raw material introduced into the reactor are not particularly limited, but the gas-phase raw material may be controlled to a pressure of about 100 bar to about 200 bar, preferably about 130 bar to about 160 bar, and a temperature of about 100 ℃ to about 200 ℃, preferably about 130 ℃ to about 180 ℃, and the liquid-phase raw material may be controlled to a pressure of about 100 bar to about 200 bar, preferably about 130 bar to about 160 bar, and a temperature of about 100 ℃ to about 200 ℃, preferably about 130 ℃ to about 180 ℃.

The hydrogenation catalyst may include a transition metal as an active ingredient, and preferably, may include one or more selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), and platinum (Pt).

Such a hydrogenation catalyst may be supported on a carrier, wherein any carrier known in the art may be used without limitation. Specifically, a material such as zirconium oxide (ZrO) may be used ₂) Titanium dioxide (TiO) ₂) Alumina (Al) ₂O₃) Silicon oxide (SiO) ₂) And the like.

In the case where the hydrogenation catalyst is supported on a carrier, the amount of the active ingredient of the hydrogenation catalyst is preferably 3% by weight or less, 2% by weight or less, or 1% by weight or less, and 0.1% by weight or more, or 0.3% by weight or more, based on 100% by weight of the carrier. If the amount of the hydrogenation catalyst is more than 3% by weight based on 100% by weight of the carrier, the reaction may rapidly proceed on the surface of the catalyst and in the process, side reactions may also increase and by-products may rapidly increase, while if less than 0.1% by weight, the yield of the hydrogenation reaction may decrease due to an insufficient amount of the catalyst, and thus the above range is preferable.

The hydrogenation reaction conditions are not particularly limited, and for example, the reaction pressure may be 50 bar or more, or 100 bar or more, or 130 bar or more, and 220 bar or less, or 200 bar or less, or 180 bar or less. If the reaction pressure is less than 50 bar, the reaction may not easily occur, and thus an excessive amount of catalyst may be consumed, the residence time may be excessively prolonged, thereby increasing by-products and acid values, while if it is more than 200 bar, excessive energy may be required during the operation of the process, and the manufacturing cost of a reactor or the like may be significantly increased, and thus, the above range is preferable.

Further, the reaction temperature may be 100 ℃ or more, or 120 ℃ or more, or 130 ℃ or more, and 300 ℃ or less, or 250 ℃ or less, or 200 ℃ or less. If the reaction temperature is less than 100 c, the reaction rate may be too slow and the reaction may not proceed smoothly, while if the reaction temperature is more than 300 c, the by-products may rapidly increase, thereby significantly increasing the acid value of the product. Also, the reaction temperature may also affect the catalyst life, and therefore, the above range is preferable.

By this hydrogenation reaction, the aromatic ring of the phthalate compound is hydrogenated and the phthalate compound is converted into the corresponding cyclohexanedicarboxylate compound.

The reactor is controlled such that a temperature deviation in the reactor is maintained at 0 to 30 ℃, preferably 0 to 20 ℃, more preferably 0 to 10 ℃ during the hydrogenation reaction, thereby minimizing side reactions and improving reaction efficiency. Wherein the temperature deviation refers to a difference between the highest temperature and the lowest temperature in the reactor, which can be measured by a plurality of temperature sensors installed according to the height of the reactor.

Alternatively, the reactor is controlled such that the temperature deviation per unit length (m) of the reactor is kept below 10 ℃, or below 5 ℃ during the hydrogenation reaction, thereby avoiding local heating. Therefore, side reactions other than hydrogenation can be suppressed, and the amount of acidic by-products produced can be reduced, and therefore, the hydrogenated product can have a low acid value, and a product of high purity and high quality can be obtained. The lower the temperature deviation per unit length of the reactor, the better, the lower limit is not limited, but for example, the lower limit may be 3 ℃ or more, preferably 0 ℃. The temperature deviation may be measured by a plurality of temperature sensors installed according to the height of the reactor.

In addition, according to an embodiment of the present invention, during the hydrogenation reaction, the reactor filled with the catalyst has a volume per actual reaction volume (m) ³) Is kept below 100kmol/h, or below 50kmol/h, preferably below 30kmol/h, in order to avoid local heating in the reactor and thus to suppress side reactions. Wherein the reaction amount can be measured by the concentration variation value of the product sampled according to the height of the reactor And (4) calculating.

To control the amount of reaction in the reactor, the mass flux or concentration of the reactants may be controlled as described above, or for this purpose, an inert gas or an inert liquid may be added together with the reactants, and the amount may be controlled.

The method for controlling the temperature deviation and the reaction amount in the reactor is not particularly limited, and any method known in the art may be used. For example, a method of installing a cooling member in which a coolant is circulated inside or outside the reactor to diffuse reaction heat may be used.

Among them, as the coolant, any coolant known in the art, for example, cooling water, a methane-based coolant, a mixed coolant of fluorine substituted or unsubstituted C1 to 5 lower alkane and ether, and the like, may be used without limitation. The kind of the cooling member is not particularly limited, and indirect cooling methods such as a heat exchanger, a cooling jacket, and the like, and direct cooling methods such as an inert gas, an inert liquid, and the like can be used.

In the case where the reaction is performed while controlling the temperature deviation inside the reactor, the reaction may occur uniformly inside the reactor, and the catalyst of the upper/lower portion of the reactor may be uniformly loaded, thereby remarkably extending the life of the catalyst. Further, an increase in side reactions due to the generation of hot spots can be significantly improved, thereby obtaining a hydrogenated product having a low acid value of 0.3KOHmg or less and a high purity.

After the completion of the reaction, the liquid-phase hydrogenation product and the unreacted gas-phase raw material are separated. The separated gas phase feed can be recycled to the hydrogenation process. In addition, the recovered hydrogenation product may be subjected to a decompression and cooling process and finally separated.

According to the hydrogenation process of the present invention, side reactions other than hydrogenation can be minimized, the amount of acid by-products produced can be reduced, and therefore, the hydrogenated product can exhibit a low acid value, thereby obtaining a product of high purity and high quality.

FIG. 1 is a diagram illustrating a hydrogenation apparatus used in the hydrogenation process of the present invention.

Referring to fig. 1, the hydrogenation apparatus may consist of heat exchangers (a, b), a reactor (c), a gas-liquid phase separator (d), and the like.

The heat exchangers (a, b) are used to raise the temperature before introducing the gas-phase feedstock (1) and the liquid-phase feedstock (3) into the reactor (c), and may be omitted as required.

The gas-phase raw material (2) and the liquid-phase raw material (4) are introduced into a tubular reactor (c) filled with a hydrogenation catalyst inside, thereby carrying out a hydrogenation reaction. The reactor may further comprise an outer jacket for removing heat to remove reaction heat. Wherein, the gas phase raw material (2) can be fed from the upper part or the lower part of the reactor, and the liquid phase raw material (4) can be fed from the upper part of the reactor.

The reaction mixture (5) discharged from the reactor (c) is transferred to a gas-liquid phase separator (d) in which the liquid phase reaction product (7) and the gas phase unreacted material (6) are separated. The separated reaction product (7) can be recovered and subjected to additional purification processes, while the gas-phase unreacted material (6) can be recycled for discharge or reuse.

However, in FIG. 1, the location of each apparatus may be varied and other apparatus not shown in FIG. 1 may be included if desired, and thus, the hydrogenation process of the present invention is not limited to the apparatus and process sequence shown in FIG. 1.

According to the hydrogenation process of the present invention, side reactions can be suppressed, and therefore, the acid value of the hydrogenated product can be controlled to be low, the catalytic activity can be improved and the catalyst life can be extended, thereby improving the quality of the product and improving the economic feasibility of a commercial process.

The hydrogenated phthalate or terephthalate compound thus produced can be effectively used as a plasticizer. Specifically, the plasticizer containing the phthalate or terephthalate compound may be used as a stabilizer, a coating, an ink, a liquid foaming agent (masterbatch type), an adhesive, or the like.

The phthalate or terephthalate compound prepared according to the above method has excellent purity and low acid value, and thus has excellent quality as a plasticizer. Therefore, it can be suitably used as a plasticizer for a resin selected from ethylene-vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polybutadiene, silicone, thermoplastic elastomer, or a copolymer thereof.

The resin composition comprising the phthalate or terephthalate compound prepared according to the above method as a plasticizer and comprising the above resin may be used for various products. For example, it can be used for preparing a film for food packaging (e.g., wrapping paper), an industrial film, a composite, a decorative sheet, a decorative tile, a soft sheet, a hard sheet, an electric wire and cable, wallpaper, a foam pad, artificial leather, a floor, tarpaulin, gloves, a sealant, a refrigerator gasket, a hose, a medical instrument, a geogrid, a net tarpaulin, a toy, stationery, an insulating tape, a coat of clothing, a PVC label for clothing or stationery, a plug liner, a plug for industrial or other uses, artificial baits, parts in electronic devices (e.g., a sleeve), an automotive interior material, an adhesive, a coating, and the like, but is not limited thereto.

Hereinafter, the action and effect of the present invention will be described in more detail by specific examples. However, these embodiments are merely exemplary, and the scope of the present invention is not determined thereby.

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