KR20230000940A - Preparation method for tetrahydrofuran, gammabutyrolactone and 1,4-butanediol - Google Patents

Abstract

The present invention relates to a method for manufacturing tetrahydrofuran, gamma-butyrolactone, or 1,4-butanediol. Specifically, according to one embodiment of the invention, polyhydroxyalkanoate (PHA) can be utilized to effectively control the yield of tetrahydrofuran, gamma-butyrolactone, or 1,4-butanediol without complicated additional processes, while being environmentally friendly due to excellent biodegradability and biocompatibility thereof.

Description

Method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol

The present invention relates to a method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol using polyhydroxyalkanoate (PHA).

Tetrahydrofuran is a widely used solvent in the field of organic chemistry and is widely used in the production of natural and synthetic resins on an industrial scale and is in high demand. In addition, gamma butyrolactone is a solvent widely used as a starting material in various synthesis methods. For example, it plays an important role in the production of materials such as N-methylpyrrolidone, butyric acid and its derivatives, and is known as an important solvent in the production of acrylates, sterine polymers, polymers, and synthetic resins.

Conventionally, a method for producing tetrahydrofuran or gamma butyrolactone using succinic acid, maleic acid, or an anhydride thereof has been used, but it is difficult to control side reactions and the yield of the target material is low. In addition, a method of producing tetrahydrofuran or gamma butyrolactone using butanediol has been used, but the price of butanediol is relatively high and the manufacturing process is complicated. Therefore, research on a manufacturing method capable of controlling the yield of a desired material and having excellent process efficiency is ongoing.

Meanwhile, polyhydroxyalkanoates (PHA) are biodegradable polymers composed of various types of hydroxycarboxylic acids produced by numerous microorganisms and used as intracellular storage materials. Polyhydroxyalkanoates are polybutylene adipate terephthalate (PBAT) derived from conventional petroleum, polybutylene succinate (PBS), and polybutylene succinate (polybutylene succinate). It has physical properties similar to synthetic polymers such as terephthalate (PBST) and polybutylene succinate adipate (PBSA), and exhibits complete biodegradability and excellent biocompatibility.

Korean Patent Publication No. 2001-0095500

Therefore, the present invention is environmentally friendly due to excellent biodegradability and biocompatibility by using polyhydroxyalkanoate (PHA), and effectively increases the yield of tetrahydrofuran, gamma butyrolactone, or 1,4-butanediol without complicated additional processes. It is intended to provide a method for producing controllable tetrahydrofuran, gamma butyrolactone or 1,4-butanediol.

A method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol according to an embodiment of the present invention comprises the steps of hydrogenating polyhydroxyalkanoate (PHA) using a copper-based catalyst in an aprotic solvent. includes

According to another embodiment of the present invention, the hydrogenation reaction may be performed at a temperature of 50 °C to 500 °C and a pressure of 1 bar to 100 bar.

A method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol according to an embodiment of the present invention includes mixing polyhydroxyalkanoate (PHA) and a copper-based catalyst in an aprotic solvent; and hydrogenating the mixture.

According to another embodiment of the present invention, prior to the hydrogenation reaction step, removing oxygen in the reactor; and adjusting the internal pressure of the reactor to 1 bar to 100 bar by injecting hydrogen gas.

According to another embodiment of the present invention, the weight ratio of the polyhydroxyalkanoate (PHA) to the copper-based catalyst may be 1:0.01 to 5.

According to another embodiment of the present invention, the hydrogenation reaction may be performed for 1 hour to 10 hours at a stirring speed of 200 rpm to 2,000 rpm.

A method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol according to an embodiment of the present invention includes dissolving polyhydroxyalkanoate (PHA) in an aprotic solvent; and passing the dissolved polyhydroxyalkanoate (PHA) through a catalyst layer containing a copper-based catalyst for a hydrogenation reaction.

According to another embodiment of the present invention, hydrogen gas is injected in the hydrogenation reaction step, and the hydrogen gas is injected in a mole number of 1 to 500 times the number of moles of the polyhydroxyalkanoate (PHA) monomer can

According to another embodiment of the present invention, the weight hourly space velocity (WHSV) of the copper-based catalyst relative to the polyhydroxyalkanoate (PHA) may be 0.1 h ^-1 to 10 h ^-1 there is.

According to another embodiment of the present invention, the copper-based catalyst is supported on a support, and the support is composed of carbon, zeolite, Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , MgO and Cr ₂ O ₃ It may include one or more selected from the group consisting of.

According to another embodiment of the present invention, the copper-based catalyst is a copper catalyst or a copper-metal composite catalyst, wherein the copper-metal composite catalyst is selected from the group consisting of Mn, Zn, Mg Co, Ni, Cr and Fe in addition to copper. A copper-metal complex including one or more selected metals may be included.

According to another embodiment of the present invention, the support may be Al ₂ O ₃ , SiO ₂ , TiO ₂ or ZrO ₂ , and the copper-based catalyst may be a Cu catalyst, a Cu-Mn catalyst, a Cu-Zn catalyst, or a Cu-Zn catalyst. Mg catalyst.

According to another embodiment of the present invention, the copper content of the copper-based catalyst supported on the support may be 0.1% by weight to 85% by weight based on the total weight of the support.

According to another embodiment of the present invention, the aprotic solvent is acetone, dioxane, methyl acetate, ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, aceto It may include at least one selected from the group consisting of nitrile, propionitrile, butyronitrile, benzonitrile, acrylonitrile, dimethyl sulfoxide, dichloromethane, dimethylpropylene urea, and hexamethylphosphate triamide.

According to another embodiment of the present invention, the yield of tetrahydrofuran, gamma butyrolactone or 1,4-butanediol may be greater than 65 mol%.

According to another embodiment of the present invention, prior to the hydrogenation reaction, further comprising pre-treating the polyhydroxyalkanoate (PHA), wherein the pre-treatment step includes purifying using a solvent extraction method can do.

According to another embodiment of the present invention, after the hydrogenation reaction, the step of treating the reaction product with one or more processes selected from the group consisting of a distillation process, an ion exchange process, a solvent extraction process, and an adsorption process may be further included. can

According to another embodiment of the present invention, the polyhydroxyalkanoate (PHA) may include 0.1% to 100% by weight of 4-hydroxybutyrate (4-HB) repeating units.

According to one embodiment of the present invention, the average particle size of the polyhydroxyalkanoate (PHA) may be 0.5 μm to 5 μm.

According to one embodiment of the present invention, the polyhydroxyalkanoate (PHA) may have a polydispersity index (PDI) of less than 2.5.

A method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol according to an embodiment of the present invention is a method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol through a hydrogenation reaction using polyhydroxyalkanoate (PHA). By producing 1,4-butanediol, it is environmentally friendly due to its excellent biodegradability and biocompatibility, and the yield of tetrahydrofuran, gamma butyrolactone, or 1,4-butanediol can be effectively controlled without complicated additional processes.

1 shows a schematic flow chart (S100) of a method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol according to an embodiment of the present invention.
2 shows a schematic flow chart (S200) of a method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol according to another embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The present invention is not limited to the contents disclosed below, and can be modified in various forms unless the gist of the invention is changed.

In this specification, when a certain component is said to "include", this means that it may further include other components, not excluding other components, unless otherwise stated.

It should be understood that all numbers and expressions representing amounts of constituents, reaction conditions, etc. described herein are modified by the term "about" in all cases unless otherwise specified.

In this specification, when one component is described as being formed on or under another component, it means that one component is formed directly on or under another component, or indirectly through another component. include

A method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol according to an embodiment of the present invention comprises the steps of hydrogenating polyhydroxyalkanoate (PHA) using a copper-based catalyst in an aprotic solvent. includes

Conventionally used methods for producing tetrahydrofuran, gamma butyrolactone, or 1,4-butanediol have been difficult to selectively control the yield of a desired material. Specifically, when tetrahydrofuran, gamma butyrolactone, or 1,4-butanediol is produced using succinic acid, maleic acid, or anhydride thereof, although the yield of tetrahydrofuran can be increased, gamma butyrolactone or 1,4 -In order to increase the yield of butanediol, there was a problem in that a complicated additional process had to be performed. Specifically, since a process of converting succinic acid or maleic acid to an anhydride is additionally required or a process such as an esterification reaction is additionally required, process time and cost increase, resulting in low process efficiency.

For example, when succinic acid is used as a raw material, after biomass is removed to obtain succinic anhydride from the fermentation broth, hydrochloric acid is applied to acidify the pH to 3, and a high-temperature reduced pressure (180 ° C, 200 mbar) distillation process is additionally performed. Can be carried out to obtain succinic anhydride. In addition, when maleic acid is used as a raw material, specifically when diethyl maleate produced through esterification of ethanol is used as a raw material, acid and by-products generated during the esterification reaction may reduce the life of the catalyst. However, since ethanol can be produced again after the hydrogenation reaction, there is also a problem in that an ethanol separation and recovery process is additionally required.

However, the method for producing tetrahydrofuran, gamma butyrolactone, or 1,4-butanediol according to an embodiment of the present invention uses polyhydroxyalkanoate (PHA), which is excellent in biodegradability and biocompatibility, making it eco-friendly and , tetrahydrofuran, gamma butyrolactone, and 1,4-butanediol, the yield of the desired material can be controlled without a complicated additional process, and the process can be simplified, so the process efficiency is excellent.

First, the method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol according to an embodiment of the present invention is performed using polyhydroxyalkanoate (PHA).

The PHA is a thermoplastic natural polyester polymer that accumulates in microbial cells, and since it is a biodegradable material, it can be composted and can be finally decomposed into carbon dioxide, water, and organic waste without generating toxic waste.

Specifically, the PHA is a thermoplastic natural polyester polymer that accumulates in microbial cells, and when certain bacteria are supplied with nutrients (nitrogen source, phosphorus, etc.) unbalanced, PHA is accumulated in the cell to store carbon sources and energy. formed by doing

In addition, the PHA is derived from conventional petroleum-derived polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polybutylene succinate terephthalate (PBST), polybutylene succinate adipate ( It has properties similar to those of synthetic polymers such as PBSA), complete biodegradability, and excellent biocompatibility.

In particular, since the PHA can be synthesized with more than 150 types of monomers, unlike other eco-friendly plastic materials such as PBS, PLA, and PTT, hundreds of types of PHA can be produced depending on the type of monomer, and different types of PHA can be produced depending on the type of monomer. Hundreds of PHAs have completely different structures and physical properties.

The PHA may be composed of a single monomeric repeating unit in a living cell, and may be formed by polymerizing one or more monomeric repeating units. Specifically, the PHA may be a single polyhydroxyalkanoate (hereinafter referred to as HOMO PHA), or a copolymerized polyhydroxyalkanoate (hereinafter referred to as copolymerized PHA), that is, different repeating units in the polymer chain. may be a copolymer in which they are randomly distributed.

Examples of repeating units that may be included in the PHA include 2-hydroxybutyrate, lactic acid, glycolic acid, 3-hydroxybutyrate (hereinafter referred to as 3-HB), 3-hydroxypropionate (hereinafter referred to as 3 -HP), 3-hydroxyvalerate (hereinafter referred to as 3-HV), 3-hydroxyhexanoate (hereinafter referred to as 3-HH), 3-hydroxyheptanoate ( hereinafter referred to as 3-HHep), 3-hydroxyoctanoate (hereinafter referred to as 3-HO), 3-hydroxynonanoate (hereinafter referred to as 3-HN), 3-hydroxy Decanoate (hereinafter referred to as 3-HD), 3-hydroxydodecanoate (hereinafter referred to as 3-HDd), 4-hydroxybutyrate (hereinafter referred to as 4-HB), 4- Hydroxyvalerate (hereinafter referred to as 4-HV), 5-hydroxyvalerate (hereinafter referred to as 5-HV) and 6-hydroxyhexanoate (hereinafter referred to as 6-HH) are There may be, and the PHA may contain one or more repeating units selected from these.

Specifically, the PHA is 3-HB, 4-HB, 3-HP, 3-HH. It may include one or more repeating units selected from the group consisting of 3-HV, 4-HV, 5-HV and 6-HH.

More specifically, the PHA may include 0.1 wt% to 100 wt% of 4-HB repeating units. For example, the PHA includes 0.2 to 100% by weight, 0.5 to 100% by weight, 1 to 100% by weight, 5% to 100% by weight, 10% to 100% by weight, 20% by weight of the 4-HB repeating unit. to 100% by weight, 30% to 100% by weight, 40% to 100% by weight, 50% to 100% by weight, 60% to 100% by weight, 70% to 100% by weight, 80% to 100% by weight It may be included in wt% or 90 wt% to 100 wt%. That is, the PHA may be a HOMO PHA composed of only 4-HB repeating units, or may be a copolymerized PHA containing 4-HB repeating units.

For example, while the PHA includes a 4-HB repeating unit, it further includes one repeating unit different from the 4-HB, or two, three, four, five, six or more different from each other. It may be a copolymerized PHA further comprising the above repeating units. For example, the PHA may be poly 3-hydroxybutyrate-co-4-hydroxybutyrate (hereinafter referred to as 3HB-co-4HB).

In addition, the PHA may include isomers. For example, the PHA may include structural isomers, enantiomers or geometric isomers. Specifically, the PHA may include structural isomers.

The PHA may be preferably a HOMO PHA composed of only 4-HB repeating units in that it can maximize the yield control effect of tetrahydrofuran, gamma butyrolactone or 1,4-butanediol.

In addition, the PHA may be a copolymerized PHA having controlled crystallinity. For example, the PHA may include at least one 4-HB repeating unit, and the crystallinity of the PHA may be controlled by controlling the content of the 4-HB repeating unit.

For example, the PHA is 3-hydroxybutyrate (3-HB), 4-hydroxybutyrate (4-HB), 3-hydroxypropionate (3-HP), 3-hydroxyhexanoate ( 3-HH), 3-hydroxyvalerate (3-HV), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV) and 6-hydroxyhexanoate (6 -HH) may be a copolymerized polyhydroxyalkanoate (PHA) containing at least one repeating unit selected from the group consisting of.

Specifically, the copolymerized PHAs include 4-HB repeating units, 3-HB repeating units, 3-HP repeating units, 3-HH repeating units, 3-HV repeating units, 4-HV repeating units, and 5-HV repeating units. unit and at least one repeating unit selected from the group consisting of 6-HH repeating units. More specifically, the copolymerized PHA may include 4-HB repeating units and 3-HB repeating units.

For example, the copolymerized PHA contains 20% by weight or more, 35% by weight or more, 40% by weight or more, or 50% by weight or more, 60% by weight or more, or 70% by weight of 3-HB repeating units based on the total weight of the copolymerized PHA. or 75 wt% or more, 99 wt% or less, 98 wt% or less, 97 wt% or less, 96 wt% or less, 95 wt% or less, 93 wt% or less, 91 wt% or less, 90 wt% Or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 55% by weight or less may be included.

The crystallinity-controlled PHA may have crystallinity and amorphousness controlled by increasing irregularity in molecular structure, and specifically, the type or ratio of monomers or the type or content of isomers may be controlled.

According to one embodiment of the present invention, the PHA may include two or more types of PHAs having different crystallinity. Specifically, the PHA may be adjusted to have a content of 4-HB repeating units within the specific range by mixing two or more types of PHAs having different crystallinity.

Specifically, the PHA may include a first PHA that is a semi-crystalline PHA.

The first PHA is a semi-crystalline PHA having controlled crystallinity (hereinafter referred to as scPHA), and may include 0.1% to 30% by weight of 4-HB repeating units. For example, the first PHA contains 0.1% to 30% by weight, 0.5% to 30% by weight, 1% to 30% by weight, 3% to 30% by weight, or 1% by weight of the 4-HB repeating unit. to 28 wt%, 1 wt% to 25 wt%, 1 wt% to 24 wt%, 1 wt% to 15 wt%, 2 wt% to 25 wt%, 3 wt% to 25 wt%, 3 wt% to 24 wt% 5% to 24% by weight, 7% to 20% by weight, 10% to 20% by weight, 15% to 25% by weight or 15% to 24% by weight.

The glass transition temperature (Tg) of the first PHA is -30 ° C to 80 ° C, -30 ° C to 10 ° C, -25 ° C to 5 ° C, -25 ° C to 0 ° C, -20 ° C to 0 ° C or -15 ° C to 0°C. The crystallization temperature (Tc) of the first PHA may be 70 ° C to 120 ° C, 75 ° C to 120 ° C or 75 ° C to 115 ° C, and the melting temperature (Tm) is 105 ° C to 165 ° C, 110 ° C to 160 ° C, It may be 115 °C to 155 °C or 120 °C to 150 °C.

The weight average molecular weight of the first PHA is 10,000 g / mol to 1,200,000 g / mol, 50,000 g / mol to 1,100,000 g / mol, 100,000 g / mol to 1,000,000 g / mol, 100,000 g / mol to 900,000 g / mol, 200,000 g /mol to 800,000 g/mol, 200,000 g/mol to 600,000 g/mol or 200,000 g/mol to 400,000 g/mol.

In addition, the PHA may include a second PHA that is an amorphous PHA having controlled crystallinity.

The second PHA is an amorphous PHA (hereinafter referred to as aPHA) having controlled crystallinity, and contains 15% to 60% by weight, 15% to 55% by weight, or 20% to 55% by weight of 4-HB repeating units. %, 25% to 55%, 30% to 55%, 35% to 55%, 20% to 50%, 25% to 50%, 30% to 50%, It may be included in 35% to 50% by weight or 20% to 40% by weight.

The glass transition temperature (Tg) of the second PHA may be -45°C to -10°C, -35°C to -15°C, -35°C to -20°C, or -30°C to -20°C.

In addition, the crystallization temperature (Tc) of the second PHA may not be measured, or may be 60 ° C to 120 ° C, 60 ° C to 110 ° C, 70 ° C to 120 ° C, or 75 ° C to 115 ° C. The melting temperature (Tm) of the second PHA may not be measured, or may be 100 ° C to 170 ° C, 100 ° C to 160 ° C, 110 ° C to 160 ° C, or 120 ° C to 150 ° C.

The weight average molecular weight of the second PHA is 10,000 g / mol to 1,200,000 g / mol, 10,000 g / mol to 1,000,000 g / mol, 50,000 g / mol to 1,000,000 g / mol, 200,000 g / mol to 1,200,000 g / mol, 300,000 g/mol to 1,000,000 g/mol, 100,000 g/mol to 900,000 g/mol, 500,000 g/mol to 900,000 g/mol, 200,000 g/mol to 800,000 g/mol or 200,000 g/mol to 400,000 g/mol there is.

The first PHA and the second PHA may be distinguished according to the content of the 4-HB repeating unit, selected from the group consisting of the glass transition temperature (Tg), the crystallization temperature (Tc), and the melting temperature (Tm). It may have at least one characteristic. Specifically, the first PHA and the second PHA may be distinguished according to the content of 4-HB repeating units, glass transition temperature (Tg), crystallization temperature (Tg), melting temperature (Tm), and the like.

According to one embodiment of the present invention, the PHA may include the first PHA or may include both the first PHA and the second PHA.

Specifically, the PHA includes the first PHA of semi-crystalline PHA or includes both the first PHA of semi-crystalline PHA and the second PHA of amorphous PHA, and more specifically, the content of the first PHA and the second PHA. By adjusting, it is possible to more effectively control the yield of the desired material.

In addition, the glass transition temperature (Tg) of the PHA is -45 ℃ to 80 ℃, -35 ℃ to 80 ℃, -30 ℃ to 80 ℃, -25 ℃ to 75 ℃, -20 ℃ to 70 ℃, -35 ℃ to 5°C, -25°C to 5°C, -35°C to 0°C, -25°C to 0°C, -30°C to -10°C, -35°C to -15°C, -35°C to -20°C, - 20°C to 0°C, -15°C to 0°C or -15°C to -5°C.

The crystallization temperature (Tc) of the PHA is not determined or is 60 ° C to 120 ° C, 60 ° C to 110 ° C, 70 ° C to 120 ° C, 75 ° C to 120 ° C, 75 ° C to 115 ° C, 75 ° C to 110 ° C or 90 ° C °C to 110 °C.

The melting temperature (Tm) of the PHA is not measured, 100 ° C to 170 ° C, 105 ° C to 170 ° C, 105 ° C to 165 ° C, 110 ° C to 160 ° C, 115 ° C to 155 ° C, 110 ° C to 150 ° C, 120 °C to 150 °C or 120 °C to 140 °C.

In addition, the weight average molecular weight of the PHA may be 10,000 g / mol to 1,200,000 g / mol. For example, the weight average molecular weight of the PHA is 50,000 g / mol to 1,200,000 g / mol, 100,000 g / mol to 1,200,000 g / mol, 50,000 g / mol to 1,000,000 g / mol, 100,000 g / mol to 1,000,000 g / mol , 200,000 g/mol to 1,200,000 g/mol, 250,000 g/mol to 1,150,000 g/mol, 300,000 g/mol to 1,100,000 g/mol, 350,000 g/mol to 1,000,000 g/mol, 350,000 g/mol to 950,000 g/mol , 100,000 g/mol to 900,000 g/mol, 200,000 g/mol to 800,000 g/mol, 200,000 g/mol to 700,000 g/mol, 250,000 g/mol to 650,000 g/mol, 200,000 g/mol to 400,000 g/mol , 300,000 g/mol to 800,000 g/mol, 300,000 g/mol to 600,000 g/mol, 500,000 g/mol to 1,200,000 g/mol, 500,000 g/mol to 1,000,000 g/mol 550,000 g/mol to 1,050,000 g/mol, 550,000 g/mol to 900,000 g/mol, 600,000 g/mol to 900,000 g/mol or 500,000 g/mol to 900,000 g/mol.

The crystallinity of the PHA measured by differential scanning calorimeter (DSC) may be 90% or less. For example, the crystallinity of the PHA may be measured by differential scanning calorimetry, and may be 90% or less, 85% or less, 80% or less, 75% or less, or 70% or less.

In addition, the average particle size of the PHA may be 0.5 μm to 5 μm. For example, the average particle size of the PHA may be 0.5 μm to 5 μm, 0.5 μm to 4.5 μm, 0.7 μm to 4 μm, 1 μm to 3.5 μm, or 1.2 μm to 3.5 μm.

The average particle size of the PHA may be measured with a nano particle size analyzer (ex. Zetasizer Nano ZS). Specifically, the average particle size of the PHA was measured using a Zetasizer Nano ZS (manufacturer: Marven) at a temperature of 25° C. and a measurement angle of 175° through the principle of dynamic light scattering (DLS). At this time, the value of the peak derived through the polydispersity index (PDI) in the confidence interval of 0.5 was measured as the particle size.

The polydispersity index (PDI) of the PHA may be less than 2.5. For example, the polydispersity index of the PHA may be less than 2.5, less than 2.3, less than 2.1, or less than 2.0.

When the average particle size and polydispersity index of PHA satisfy the above ranges, the yield of the desired material can be more effectively controlled.

In addition, the PHA may be obtained by cell disruption using a non-mechanical method or a chemical method. Specifically, the PHA is a thermoplastic natural polyester polymer that accumulates in microbial cells and has a relatively large average particle size. it could be

A method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol according to an embodiment of the present invention is performed through a hydrogenation reaction using polyhydroxyalkanoate (PHA).

Specifically, the hydrogenation reaction may be performed using a copper-based catalyst in an aprotic solvent. More specifically, the hydrogenation reaction may be carried out using PHA, an aprotic solvent and a copper-based catalyst in the presence of hydrogen.

The hydrogenation reaction may be performed at a temperature of 50 °C to 500 °C and a pressure of 1 bar to 100 bar. For example, the hydrogenation reaction is 55 ℃ to 480 ℃, 80 ℃ to 460 ℃, 100 ℃ to 420 ℃, 150 ℃ to 400 ℃, 200 ℃ to 360 ℃, 220 ℃ to 350 ℃, 250 ℃ to 350 ℃, 270°C to 310°C, 275°C to 300°C, 280°C to 290°C, 50°C to 300°C, 80°C to 250°C, 100°C to 220°C, 120°C to 205°C, 155°C to 200°C or 175°C 5 bar to 75 bar, 10 bar to 100 bar, 10 bar to 65 bar, 1 bar to 55 bar, 5 bar to 35 bar, 10 bar to 30 bar, 15 bar to 55 bar, 30 bar at a temperature of 195 ° C. to 90 bar, 45 bar to 80 bar or 45 bar to 65 bar. By controlling the temperature and pressure of the hydrogenation reaction within the above ranges, it is possible to selectively control the yield of a desired material, improve process stability, and reduce process cost.

According to another embodiment of the present invention, hydrogen gas is injected in the hydrogenation reaction step, and the hydrogen gas is injected in a mole number of 1 to 500 times the number of moles of the polyhydroxyalkanoate (PHA) monomer can

Specifically, the hydrogenation reaction can be performed in the presence of hydrogen, and more specifically, it can be performed by injecting hydrogen gas in the hydrogenation reaction step.

For example, in the hydrogenation reaction step, the hydrogen gas is 1 to 350 times, 2 times to 250 times, 5 times to 100 times, 10 times to 80 times the number of moles of the monomers of the polyhydroxyalkanoate (PHA) Alternatively, it may be injected in a molar number of 30 to 60 times.

The aprotic solvent is acetone, dioxane, methyl acetate, ethyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, propionitrile, butyronitrile, It may include at least one selected from the group consisting of benzonitrile, acrylonitrile, dimethylsulfoxide, dichloromethane, dimethylpropylene urea, and hexamethylphosphate triamide. The aprotic solvent may be selectively used depending on the desired material.

In addition, the copper-based catalyst may be a catalyst supported on a support. Specifically, the copper-based catalyst is a catalyst supported on a support, and the support is at least one selected from the group consisting of carbon, zeolite, Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , MgO and Cr ₂ O ₃ can include

In addition, the copper-based catalyst may be a copper catalyst or a copper-metal composite catalyst, and the copper-metal composite catalyst may include at least one metal selected from the group consisting of Mn, Zn, Mg, Co, Ni, Cr, and Fe in addition to copper. It may include a copper-metal complex comprising a.

More specifically, the copper-based catalyst is a copper-based catalyst supported on a support, wherein the support is Al ₂ O ₃ , SiO ₂ , TiO ₂ or ZrO ₂ , and the copper-based catalyst is a Cu catalyst, a Cu-Mn catalyst, Cu -Zn or Cu-Mg catalyst. For example, the copper-based catalyst is Cu/Al ₂ O ₃ , CuZn/Al ₂ O ₃ , CuMn/Al ₂ O ₃ , Cu/SiO ₂ , Cu/ZrO ₂ , Cu/TiO ₂ , CuMn/SiO ₂ , CuMn/ZrO ₂ or CuMn/TiO ₂ It may be, but is limited thereto It is not.

In addition, the content of the copper or copper-metal complex of the copper-based catalyst supported on the support may be 0.1% to 85% by weight based on the total weight of the support. For example, the copper-based catalyst may be a catalyst supported with 85% by weight or less of copper or copper-metal complex based on the total weight of the support, and more specifically, the content of the copper or copper-metal complex is 80% or less, 75% or less, 70% or less, 65% or less, 64% or less, 30% or less, 10% or less, 8% or less, 7% or less, based on total weight 6 wt% or less or 5.5 wt% or less, 0.1 wt% or more, 0.5 wt% or more, 1.5 wt% or more or 2 wt% or more, 0.1 wt% to 85 wt%, 0.5 wt% to 75 wt%, 1% to 70%, 2% to 68%, 5% to 66%, 8% to 64%, 0.1% to 25%, 0.2% to 20%, 0.5% % to 13%, 1% to 10%, 1.5% to 8% or 2% to 5%.

The copper-based catalyst may have an average particle diameter of 10 μm to 2000 μm. For example, the copper-based catalyst may have an average particle diameter of 25 μm to 1500 μm, 50 μm to 1000 μm, 100 μm to 800 μm, or 200 μm to 500 μm.

In addition, the surface area of the copper-based catalyst may be 500 m ² /g or less. For example, the copper-based catalyst may have a surface area of 350 m ² /g or less, 300 m ² /g or less, 100 m ² /g or less, or 80 m ² /g or less.

batch reaction

A method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol according to an embodiment of the present invention includes mixing polyhydroxyalkanoate (PHA) and a copper-based catalyst in an aprotic solvent; and hydrogenating the mixture.

In addition, before the hydrogenation reaction step, removing oxygen in the reactor; and adjusting the internal pressure of the reactor to 1 bar to 100 bar by injecting hydrogen gas. The removing of oxygen may be performed using hydrogen gas, but is not limited thereto.

The injection amount of the hydrogen gas may be 1 to 500 times the weight of the polyhydroxyalkanoate (PHA). For example, the injection amount of the hydrogen gas is 1 to 350 times, 2 times to 250 times, 5 times to 100 times, 10 times to 80 times, or 30 times to 30 times the weight of the polyhydroxyalkanoate (PHA). It can be 60 times.

In addition, in the batch reaction, the weight ratio of the polyhydroxyalkanoate (PHA) to the copper-based catalyst may be 1:0.01 to 5. For example, the weight ratio of the polyhydroxyalkanoate (PHA) to the copper-based catalyst is 1:0.02 to 4.5, 1:0.05 to 2.5, 1:0.08 to 2.2, 1:0.1 to 2, 1:0.1 to 1.2, 1: 0.1 to 1, 1: 0.1 to 0.8, 1: 0.1 to 4, 1: 0.5 to 3.5, 1: 1 to 3, 1: 1.2 to 2.5, or 1: 1.5 to 2.2. By adjusting the weight ratio of the polyhydroxyalkanoate (PHA) and the copper-based catalyst within the above range, the yield of the desired material can be effectively controlled.

In addition, the hydrogenation reaction may be performed for 1 hour to 10 hours at a stirring speed of 200 rpm to 2,000 rpm. For example, the stirring speed may be 250 rpm to 1,500 rpm, 300 rpm to 1,200 rpm, 400 rpm to 1,000 rpm, 450 rpm to 900 rpm, 500 rpm to 750 rpm, or 520 rpm to 700 rpm, and the reaction time may be performed for 1 hour to 9 hours, 2 hours to 7.5 hours, 4.5 hours to 7 hours, or 5.5 hours to 6.5 hours.

continuous reaction

According to another embodiment of the present invention, a method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol includes dissolving polyhydroxyalkanoate (PHA) in an aprotic solvent; and passing the dissolved polyhydroxyalkanoate (PHA) through a catalyst layer containing a copper-based catalyst for a hydrogenation reaction.

The dissolving step may be a step of dissolving PHA in an aprotic solvent to be 0.1 wt% to 30 wt%. For example, the content of the dissolved PHA is 0.1% to 20% by weight, 0.2% to 16% by weight, 0.5% to 10% by weight, 0.6% to 8% by weight, 0.7% to 6% by weight. , 0.8% to 3% or 0.9% to 2% by weight.

In addition, in the continuous reaction, the weight hourly space velocity (WHSV) of the copper-based catalyst relative to the polyhydroxyalkanoate (PHA) may be 0.1 h ⁻¹ to 10 h ⁻¹ . For example, the weight hourly space velocity (WHSV) of the copper-based catalyst relative to the polyhydroxyalkanoate (PHA) is 0.02 h ^-1 to 5 h ^-1 , 0.05 h ^-1 to 2 h ^-1 , 0.1 h ^-1 to 1 h ^-1 or 0.2 h ^-1 to 0.5 h ^-1 .

According to one embodiment of the present invention, the yield of tetrahydrofuran, gamma butyrolactone or 1,4-butanediol may be greater than 65 mol%. For example, the yield of tetrahydrofuran, gamma butyrolactone or 1,4-butanediol is 67 mol% or more, 69 mol% or more, 70 mol% or more, 71 mol% or more, 80 mol% or more, 85 mol% or more , 90 mol% or more, 91 mol% or more, 93 mol% or more, 95 mol% or more, 97 mol% or more, or 99 mol% or more. The yield may be measured using gas chromatography (GC) for the final product obtained through the hydrogenation reaction.

Specifically, the yield of tetrahydrofuran may be greater than 65 mol%. For example, the yield of tetrahydrofuran may be 67 mol% or more, 69 mol% or more, 70 mol% or more, 71 mol% or more, 80 mol% or more, 95 mol% or more, or 97 mol% or more.

More specifically, when the copper-based catalyst is Cu/Al ₂ O ₃ or Cu-Mn/Al ₂ O ₃ supported with 6 wt% to 85 wt% of copper, the yield of tetrahydrofuran is 65 mol%. may be excessive. For example, the copper-based catalyst is 6 wt% to 80 wt%, 7 wt% to 75 wt%, 6 wt% to 65 wt%, or 8 wt% to 64 wt% of copper supported catalyst Cu / Al ₂ When O ₃ or Cu-Mn/Al ₂ O ₃ , the yield of tetrahydrofuran may be greater than 65 mol%.

In addition, the hydrogenation reaction is 55 ℃ to 480 ℃, 80 ℃ to 460 ℃, 100 ℃ to 420 ℃, 150 ℃ to 400 ℃, 200 ℃ to 360 ℃, 220 ℃ to 350 ℃, 250 ℃ to 350 ℃, 270 ℃ to 310 °C, 275 °C to 300 °C or 280 °C to 290 °C and at a pressure of 10 bar to 100 bar, 30 bar to 90 bar, 45 bar to 80 bar or 45 bar to 65 bar, the tetramer The yield of hydrofuran may be greater than 65 mol%.

Alternatively, the yield of gamma butyrolactone may be greater than 65 mol%. For example, the yield of gamma butyrolactone may be 67 mol% or more, 69 mol% or more, 70 mol% or more, 80 mol% or more, 85 mol% or more, 95 mol% or more, or 99 mol% or more.

Specifically, when the hydrogenation reaction is performed at a pressure of 1 bar to 75 bar, the yield of gamma butyrolactone may be greater than 65 mol%. For example, the hydrogenation reaction is performed at 5 bar to 75 bar, 10 bar to 65 bar, 15 bar to 55 bar, 1 bar to 35 bar, 10 bar to 25 bar, 30 bar to 65 bar, or 45 bar to 55 bar. When carried out, the yield of gamma butyrolactone may be greater than 65 mole %.

In addition, when the support of the copper-based catalyst includes SiO ₂ or TiO ₂ , the yield of gamma butyrolactone may be greater than 65 mol%.

In addition, when the catalyst is a catalyst Cu/Al ₂ O ₃ supported with less than 8 wt% of copper, the yield of gamma butyrolactone may be greater than 65 mol%. For example, the catalyst is less than 8%, less than 7%, less than 6%, 0.1% to 7%, 0.5% to 8%, 1% to 6%, or 1.5% to 7% by weight. When the catalyst Cu/Al ₂ O ₃ supported with 5.5 wt % of copper, the yield of gamma butyrolactone may be greater than 65 mol %.

Alternatively, the yield of 1,4-butanediol may be greater than 65 mol%. For example, the yield of 1,4-butanediol may be 70 mol% or more, 85 mol% or more, 90 mol% or more, 91 mol% or more, or 93 mol% or more.

For example, the hydrogenation reaction is performed at a temperature of 50 ° C to 300 ° C, 80 ° C to 250 ° C, 100 ° C to 220 ° C, 120 ° C to 205 ° C, 155 ° C to 200 ° C or 175 ° C to 195 ° C at a temperature of 10 bar to 100 ° C. bar, 30 bar to 90 bar, 45 bar to 80 bar or 45 bar to 65 bar, the yield of 1,4-butanediol may be greater than 65 mol%.

According to another embodiment of the present invention, a step of pre-treating the polyhydroxyalkanoate (PHA) may be further included before the hydrogenation reaction.

Specifically, the pretreatment step may include a step of purification using a solvent extraction method, and the solvent extraction method may be performed using one or more solvents selected from the group consisting of dioxane, chloroform, and methylene chloride.

For example, the solvent extraction method may be performed by mixing dry matter obtained from PHA, that is, a PHA culture broth or fermentation broth with the solvent to extract PHA, separating cell residues, and then adding them dropwise to ethanol to recover them.

In addition, after the hydrogenation reaction, a step of treating the reaction product with at least one process selected from the group consisting of a distillation process, an ion exchange process, a solvent extraction process, and an adsorption process may be further included. By additionally performing such a treatment process, the yield can be more effectively controlled.

The distillation may be performed using a commonly used distillation method, and the ion exchange, solvent extraction and adsorption may also be performed by a commonly used method as long as the effect of the present invention is not impaired.

For example, the distillation may be performed by heating the reaction product using a receiver of the distillation column, condensing vapor generated from the top of the distillation column with a condenser to separate the product, and recovering the product.

The distillation may be performed at a temperature of 50 °C to 250 °C and under reduced pressure conditions of 10 torr to 760 torr. For example, the distillation may be performed at a temperature of 50 °C to 200 °C or 80 °C to 200 °C and under reduced pressure conditions of 20 torr to 700 torr or 30 torr to 500 torr.

The above will be described in more detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited only to these.

[Example]

Preparation of polyhydroxyalkanoate (PHA) pellets

Preparation Example 1-1

400 ml of the polyhydroxyalkanoate (PHA) culture medium was stirred at 3,800 ppm for 20 minutes using a high-speed centrifuge to remove the supernatant. Thereafter, 400 ml of distilled water was added and mixed, and the supernatant was removed once more using a high-speed centrifuge under the same conditions. Thereafter, after freeze-drying at a temperature of -70 ° C. and vacuum, the homogenizer (product name: homomixer mark2, manufacturer: primix) was used to uniformly pulverize the average particle diameter of 1 μm.

50 g of the pulverized material was mixed with 1 L of chloroform (manufacturer: Daejeong Chemical), and stirred at 55° C. for 1.5 hours. The cell residue was removed by filtration, and the chloroform filtrate was added dropwise to 5 L of ethanol. Thereafter, the precipitated PHA was recovered and dried in a vacuum oven at 40 ° C. to prepare PHA pellets (recovery: 90%, purity: 99%, content of 4-hydroxybutyrate (4-HB): 100% by weight).

Preparation of Catalyst

Preparation Example 2-1: Catalyst Cu/Al ₂ O ₃ manufacture of

Alumina (Al ₂ O ₃ , Strem) and 1.52 g of copper nitrate trihydrate (Cu(NO ₃ ) ₂ 3H ₂ O, manufacturer: Daejung Chemical Gold) were stirred at room temperature for 10 hours to prepare a slurry. After removing the solvent from the slurry using a vacuum rotary evaporator, it was dried in a circulation oven maintained at 105° C. for 12 hours.

Thereafter, the dried copper-alumina composite was calcined at 500° C. for 4 hours under an air atmosphere, and then reduced at 500° C. for 2 hours under a 5% hydrogen and nitrogen atmosphere. Thereafter, after sufficiently cooling at room temperature, stabilization was performed for 0.5 hour under a 1% oxygen and nitrogen atmosphere to prepare a catalyst Cu/Al ₂ O ₃ in which 8% by weight of copper was supported on an alumina carrier.

Preparation Example 2-2: Catalyst Cu/Al ₂ O ₃ manufacture of

Copper nitrate trihydrate (Cu(NO ₃ ) ₂ 3H ₂ O, manufacturer: Daejeong Chemical Gold) was carried out in the same manner as in Preparation Example 2-1, except that 0.38 g was used, and 2% by weight of copper was supported. Catalyst Cu/Al ₂ O ₃ was prepared.

Preparation Example 2-3: Catalyst Cu/Al ₂ O ₃ manufacture of

Copper nitrate trihydrate (Cu(NO ₃ ) ₂ 3H ₂ O, manufacturer: Daejeong Chemical Gold) was carried out in the same manner as in Preparation Example 2-1, except that 0.95 g was used, and 5% by weight of copper was supported. Catalyst Cu/Al ₂ O ₃ was prepared.

Preparation Example 2-4: Catalyst Cu/Al ₂ O ₃ manufacture of

Copper nitrate trihydrate (Cu(NO ₃ ) ₂ 3H ₂ O, manufacturer: Daejeong Chemical Gold) was carried out in the same manner as in Preparation Example 2-1, except that 3.04 g was used, and 16% by weight of copper was supported. Catalyst Cu/Al ₂ O ₃ was prepared.

Preparation Example 2-5: Catalyst Cu/Al ₂ O ₃ manufacture of

Copper nitrate trihydrate (Cu(NO ₃ ) ₂ 3H ₂ O, manufacturer: Daejeong Chemical Gold) was carried out in the same manner as in Preparation Example 2-1, except that 6.08 g was used, and 32% by weight of copper was supported. Catalyst Cu/Al ₂ O ₃ was prepared.

Preparation Example 2-6: Catalyst Cu/Al ₂ O ₃ manufacture of

Copper nitrate trihydrate (Cu(NO ₃ ) ₂ 3H ₂ O, manufacturer: Daejeong Chemical Gold) was carried out in the same manner as in Preparation Example 2-1, except that 12.16 g was used, and 64% by weight of copper was supported. Catalyst Cu/Al ₂ O ₃ was prepared.

Preparation Example 2-7: Catalyst Cu—Zn/Al ₂ O ₃ manufacture of

8 to an alumina carrier in the same manner as in Preparation Example 2-1, except that 1.8 g of zinc precursor zinc nitrate hexahydrate (Zn(NO ₃ ) ₂ 6H ₂ O, manufacturer: Sigma-aldrich) was additionally used. Catalyst CuZn/Al ₂ O ₃ loaded with 8% by weight of copper and 8% by weight of zinc was prepared.

Preparation Example 2-8: Catalyst Cu-Mn/Al ₂ O ₃ manufacture of

8% by weight was added to the alumina carrier in the same manner as in Preparation Example 2-1, except that 2.1 g of manganese precursor manganese nitrate hexahydrate (Mn(NO ₃ ) ₂ 6H ₂ O, manufacturer: Junsei) was additionally used. A catalyst CuMn/Al ₂ O ₃ loaded with copper and 8% by weight of manganese was prepared.

Preparation Example 2-9: Catalyst Cu/SiO ₂ manufacture of

Except for using silica (SiO ₂ , manufacturer: Strem) instead of alumina, a catalyst Cu/SiO ₂ in which 8% by weight of copper was supported on a silica carrier was prepared in the same manner as in Preparation Example 2-1.

Preparation Example 2-10: Catalyst Cu/ZrO ₂ manufacture of

Except for using zirconia (ZrO ₂ , manufacturer: sigma-aldrich) instead of alumina, a catalyst Cu / ZrO ₂ in which 8% by weight of copper was supported on a zirconia carrier was prepared in the same manner as in Preparation Example 2-1 did

Preparation Example 2-11: Catalyst Cu/TiO ₂ manufacture of

Except for using titania (TiO ₂ , manufacturer: sigma-aldrich) instead of alumina, a catalyst Cu/TiO ₂ in which 8% by weight of copper was supported on a titania support was prepared in the same manner as in Preparation Example 2-1 did

Preparation Example 2-12: Catalyst Cu-Mn/SiO ₂ manufacture of

8% by weight was added to the silica carrier in the same manner as in Preparation Example 2-7, except that 2.1 g of manganese precursor manganese nitrate hexahydrate (Mn(NO ₃ ) ₂ 6H ₂ O, manufacturer: Junsei) was additionally used. A catalyst CuMn/SiO ₂ loaded with copper and 8% by weight of manganese was prepared.

Preparation Example 2-13: Catalyst Cu-Mn/ZrO ₂ manufacture of

8% by weight was added to the zirconia carrier in the same manner as in Preparation Example 2-8, except that 2.1 g of manganese precursor manganese nitrate hexahydrate (Mn(NO ₃ ) ₂ 6H ₂ O, manufacturer: Junsei) was additionally used. A catalyst CuMn/ZrO ₂ loaded with copper and 8% by weight of manganese was prepared.

Preparation Example 2-14: Catalyst Cu-Mn/TiO ₂ manufacture of

8% by weight was added to the titania carrier in the same manner as in Preparation Example 2-9, except that 2.1 g of manganese precursor manganese nitrate hexahydrate (Mn(NO ₃ ) ₂ 6H ₂ O, manufacturer: Junsei) was additionally used. A catalyst CuMn/TiO ₂ loaded with copper and 8% by weight of manganese was prepared.

Manufacture of products using a hydrogenation reaction

Example 1-1

In an autoclave reactor, 1 g of the PHA pellets prepared in Preparation Example 1-1, 40 g of dioxane, and 0.5 g of the catalyst Cu/Al ₂ O ₃ prepared in Preparation Example 2-1 were mixed together. After the introduction, oxygen in the reactor was removed three or four times using hydrogen gas. Thereafter, the pressure was raised to 50 bar by injecting hydrogen gas, and the mixture was heated to a reaction temperature of 280°C. The time when the reaction temperature was reached was set as the reaction start time, and the reaction was carried out for a total of 6 hours at a stirring speed of 600 rpm. After the reaction was completed, the temperature was lowered to room temperature, the final product was recovered, and the yield of the final product was analyzed using gas chromatography (GC), and the results are shown in Table 2.

Examples 1-2 to 1-14 and Comparative Examples 1-1 to 1-7

The final product was recovered in the same manner as in Preparation Example 3-1, except that the components and process conditions were changed as shown in Table 1 below. Then, the yield of the final product was analyzed using gas chromatography (GC), and the results are shown in Table 2. At this time, Comparative Example 1-1 was performed using pretreated succinic anhydride (trade name: Succinic anhydride, manufacturer: Sigma-aldrich).

division profit catalyst menstruum Temperature
(℃) enter
(bar) Kinds Content (g) Example 1-1 Preparation Example 1-1 Preparation Example 2-1 0.5 dioxane 280 50 Example 1-2 Preparation Example 1-1 Preparation Example 2-1 0.1 dioxane 280 50 Example 1-3 Preparation Example 1-1 Preparation Example 2-1 0.1 dioxane 310 50 Example 1-4 Preparation Example 1-1 Preparation Example 2-1 0.1 dioxane 280 80 Example 1-5 Preparation Example 1-1 Preparation Example 2-4 0.1 dioxane 280 50 Example 1-6 Preparation Example 1-1 Preparation Example 2-5 0.1 dioxane 280 50 Examples 1-7 Preparation Example 1-1 Production Example 2-6 0.1 dioxane 280 50 Examples 1-8 Preparation Example 1-1 Production Example 2-8 0.1 dioxane 280 50 Examples 1-9 Preparation Example 1-1 Preparation Example 2-1 0.1 dioxane 220 50 Examples 1-10 Preparation Example 1-1 Preparation Example 2-1 0.1 dioxane 280 20 Examples 1-11 Preparation Example 1-1 Preparation Example 2-11 0.1 dioxane 280 50 Examples 1-12 Preparation Example 1-1 Preparation Example 2-2 0.1 dioxane 280 50 Examples 1-13 Preparation Example 1-1 Production Example 2-14 0.1 dioxane 280 50 Examples 1-14 Preparation Example 1-1 Preparation Example 2-12 0.1 dioxane 190 50 Comparative Example 1-1 succinic acid
anhydride Preparation Example 2-1 0.1 dioxane 280 50 Comparative Example 1-2 Preparation Example 1-1 Preparation Example 2-1 0.1 ethanol 280 50

division Yield of product (mol %) tetrahydrofuran gamma butyrolactone 1,4-butanediol butanol Example 1-1 97.1 1.3 0.2 1.2 Example 1-2 71.2 27.2 0.8 0.5 Examples 1-3 95.5 0.7 0.0 3.0 Example 1-4 80.8 0.5 15.7 2.4 Example 1-5 73.3 25.6 0.4 0.6 Example 1-6 74.3 23.4 0.6 0.8 Examples 1-7 73.2 10.3 0.7 14.9 Examples 1-8 81.2 12.2 5.6 0.7 Examples 1-9 16.1 80.6 3.1 0.0 Examples 1-10 12.8 87.2 0.0 0.0 Example 1-11 0.0 99.9 0.0 0.0 Examples 1-12 30.2 69.1 0.3 0.3 Examples 1-13 18.9 70.1 10.5 0.0 Examples 1-14 0.0 5.4 93.5 0.0 Comparative Example 1-1 65.0 30.1 4.3 0.1 Comparative Example 1-2 33.5 29.0 0.0 0.0

As shown in Table 2, the PHA pellets, the aprotic solvent and the catalyst are reacted in the presence of hydrogen, and at this time, by controlling the process temperature and pressure and the content of copper supported on the catalyst, and selectively controlling the carrier of the catalyst, It was confirmed that the yield of hydrofuran, gamma butyrolactone or 1,4-butanediol can be adjusted to more than 65 mol%.

In particular, in Comparative Example 1-2 using ethanol rather than an aprotic solvent, the yields of tetrahydrofuran, gamma butyrolactone, and 1,4-butanediol were all very low due to side reactions.

Example 2-1

2.0 g of the catalyst prepared in Preparation Example 2-7 was put into a continuous fixed bed reactor made of SUS316 to form a catalyst layer, and glass fibers were placed on and under the catalyst layer to fix the catalyst layer. Thereafter, the catalyst was activated by flowing hydrogen gas at 300° C. for 2 hours. Thereafter, the flow rate of hydrogen gas was increased to 40 bar to increase the pressure inside the reactor, and then the temperature was adjusted to 280°C.

Thereafter, after dissolving the PHA pellets prepared in Preparation Example 1-1 in dioxane at 1% by weight, the solution was injected into the reactor at a rate of 1 ml/min, and at the same time, hydrogen gas was supplied to the polyhydroxy The reaction was carried out by injecting 50 times the number of moles of alkanoate (PHA) monomer. The product was recovered every hour and the yield was analyzed using gas chromatography (GC), and the results are shown in Table 3.

Example 2-2

The reaction was carried out in the same manner as in Example 2-1, except that the catalyst prepared in Preparation Example 2-1 was used. The product was recovered every hour and the yield was analyzed using gas chromatography (GC), and the results are shown in Table 3.

As shown in Table 3, the catalyst CuZn/Al ₂ O ₃ After fixing the catalyst layer, Example 2-1, in which a solution in which PHA pellets were dissolved in an aprotic solvent, was introduced and reacted, showed excellent tetrahydrofuran yield. Specifically, the yield of tetrahydrofuran at the initial stage of the reaction was 98.6 mol%, and even after 18 hours, the yield of tetrahydrofuran was excellent at 97.0 mol%. In addition, since the yield reduction rate of tetrahydrofuran per hour was about 0.089 mol%, stable activity was exhibited.

In addition, Example 2-2, in which a solution of PHA pellets dissolved in an aprotic solvent was added and reacted after fixing the catalyst layer with the catalyst Cu/Al ₂ O ₃ , compared to Example 2-1, tetrahydrofuran over time Although the yield decrease rate tends to decrease, the yield of tetrahydrofuran at the beginning of the reaction was excellent at 95.1 mol%.

Claims (18)

A method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, comprising hydrogenating polyhydroxyalkanoate (PHA) using a copper-based catalyst in an aprotic solvent. According to claim 1,
Method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, wherein the hydrogenation reaction is carried out at a temperature of 50 ° C to 500 ° C and a pressure of 1 bar to 100 bar. According to claim 1,
Injecting hydrogen gas in the hydrogenation reaction step,
Method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, wherein the hydrogen gas is injected in a mole number of 1 to 500 times the number of moles of the polyhydroxyalkanoate (PHA) monomer. According to claim 1,
Mixing polyhydroxyalkanoate (PHA) and a copper-based catalyst in an aprotic solvent; and
A method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, comprising hydrogenating the mixture. According to claim 4,
Prior to the hydrogenation reaction step,
removing oxygen in the reactor; and
A method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, comprising the step of adjusting the pressure inside the reactor to 1 bar to 100 bar by injecting hydrogen gas. According to claim 4,
The method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, wherein the weight ratio of the polyhydroxyalkanoate (PHA): the copper-based catalyst is 1:0.01 to 5. According to claim 4,
Method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, wherein the hydrogenation reaction is carried out for 1 hour to 10 hours at a stirring speed of 200 rpm to 2,000 rpm. According to claim 1,
Dissolving polyhydroxyalkanoate (PHA) in an aprotic solvent; and
Method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, comprising the step of hydrogenating the dissolved polyhydroxyalkanoate (PHA) by passing it through a catalyst layer containing a copper-based catalyst. According to claim 8
The weight hourly space velocity (WHSV) of the copper-based catalyst relative to the polyhydroxyalkanoate (PHA) is 0.1 h ^-1 to 10 h ^-1 , tetrahydrofuran, gamma butyrolactone or 1 A method for producing ,4-butanediol. According to claim 1,
As a catalyst in which the copper-based catalyst is supported on a support,
The support includes at least one selected from the group consisting of carbon, zeolite, Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , MgO and Cr ₂ O ₃ ,
The copper-based catalyst is a copper catalyst or a copper-metal composite catalyst,
The copper-metal composite catalyst includes a copper-metal composite containing at least one metal selected from the group consisting of Mn, Zn, Mg, Co, Ni, Cr and Fe in addition to copper, tetrahydrofuran, gamma butyrolactone or a method for producing 1,4-butanediol. According to claim 10,
The support is Al ₂ O ₃ , SiO ₂ , TiO ₂ or ZrO ₂ ,
The copper-based catalyst is a Cu catalyst, a Cu-Mn catalyst, a Cu-Zn catalyst or a Cu-Mg catalyst, a method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol. According to claim 10,
Preparation of tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, wherein the content of copper or copper-metal complex of the copper catalyst supported on the support is 0.1% to 85% by weight based on the total weight of the support method. According to claim 1,
The aprotic solvent is acetone, dioxane, methyl acetate, ethyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, propionitrile, butyronitrile, benzonitrile, acrylonitrile, dimethyl sulfoxide, dichloromethane, dimethylpropylene urea and hexamethyl phosphate triamide, including tetrahydrofuran, gamma butyrolactone or 1,4-butanediol containing at least one selected from the group consisting of manufacturing method. According to claim 1,
A method for producing tetrahydrofuran, gammabutyrolactone or 1,4-butanediol, wherein the yield of tetrahydrofuran, gammabutyrolactone or 1,4-butanediol is greater than 65 mol%. According to claim 1,
Prior to the hydrogenation reaction,
Further comprising the step of pre-treating the polyhydroxyalkanoate (PHA),
Method for producing tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, wherein the pretreatment step comprises purifying using a solvent extraction method. According to claim 1,
After the hydrogenation reaction,
of tetrahydrofuran, gamma butyrolactone or 1,4-butanediol, further comprising treating the reaction product with at least one process selected from the group consisting of a distillation process, an ion exchange process, a solvent extraction process, and an adsorption process. manufacturing method. According to claim 1,
The polyhydroxyalkanoate (PHA) contains 0.1% to 100% by weight of 4-hydroxybutyrate (4-HB) repeating units, tetrahydrofuran, gamma butyrolactone or 1,4-butanediol manufacturing method. According to claim 1,
The polyhydroxyalkanoate (PHA) has an average particle size of 0.5 μm to 5 μm and a polydispersity index (PDI) of less than 2.5, tetrahydrofuran, gamma butyrolactone or 1,4-butanediol manufacturing method.

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