KR20140076304A - A process for preparing 1,5-pentanediol and δ-valerolactone from tetrahydrofurfuryl alcohol - Google Patents

Abstract

The present invention provides a method to manufacture 1,5-pentanediol under mild reaction conditions using a copper nanocomposite oxide catalyst without chromium or to manufacture δ-valerolactone by directly making tetrahydrofurfuryl alcohol react not via 1,5-pentanediol under the same catalyst, and a catalyst being used therefor.

Description

[0001] The present invention relates to a process for the preparation of 1,5-pentanediol and < RTI ID = 0.0 > 8-valerolactone < / RTI > from tetrahydroperfuryl alcohol,

The present invention relates to a method for directly producing 1,5-pentanediol and? -Valerolactone from a bio-derived feedstock, tetrahydrofurfuryl alcohol (hereinafter referred to as THFA), and more particularly to a process for producing 1,5- Pentanediol under gentle reaction conditions using a copper nanocomposite oxide catalyst, or without using 1,5-pentanediol under the same catalyst for the preparation of < RTI ID = 0.0 > 8-valerolactone, Valerolactone by direct reaction with an alcohol.

Diols are intermediates for the synthesis of polymers and are important raw materials for use in polyester, polyurethane, coatings, adhesives and fibers, and are in high demand in various chemical industries. Diols are also used as raw materials for producing lactones. Lactone is a monomer of polylactone which is an aliphatic polyester-based biodegradable polymer, and is attracting much attention from the environmental industry in particular. Biodegradable polymers are attracting attention as polymers capable of decomposing by the action of microorganisms existing in nature such as bacteria, fungi, and green algae. In addition, derivatives can be synthesized through various chemical reactions using lactone derivative compounds, and compounds derived from lactones are used in various fields such as medicines, synthetic fibers, photosensitive resins, and films. In particular, the lactone compound having 4 to 6 carbon atoms synthesized from lactone serves as a raw material for nylon, and the δ-valerolactam produced from δ-valerolactone is a monomer of 5-nylon.

A common method for preparing general diol compounds in petrochemical processes is to esterify dicarboxylic acid with alcohols having 1 to 8 carbon atoms, such as methanol, ethanol, butanol, and to obtain the obtained esterified product with a catalyst containing copper or a noble metal To prepare a diol compound.

A method for producing 1,5-pentanediol using a copper-chromite catalyst by a method for producing 1,5-pentanediol using THFA which is easily supplied and received from a bio raw material is disclosed in the following prior art documents.

Paper "1,5-PENTANEDIOL"; Organic Syntheses, Coll. Vol. 3, p.693 (1955); Vol. 26, p. 83 (1946) discloses a method for producing 1,5-pentanediol under the condition that THFA (tetrahydrofurfuryl alcohol) is used as a reactant and the reaction temperature is 250 ° C and the hydrogen pressure is higher than 3200 psi. In US 2,768,978, tetrahydrofurfuryl alcohol (THFA) is fed continuously with hydrogen to a copper-chromite catalyst system mounted in a fixed-bed liquid-phase reactor at a temperature of 250 ° C and a hydrogen pressure of 4200 psi, Diol. ≪ / RTI >

"Preparation of Dihydropyran, δ-Hydroxyvaleraldehyde and 1,5-Pentanediol from Tetrahydrofurfuryl Alcohol"; J. Am. Chem. Soc. Tetrahydrofurfuryl alcohol (THFA) at 68 (8), 1646-1648 to produce dihydropyran at 300 to 350 ° C. and react under an acid catalyst to produce δ-hydroxyvaleric aldehyde, which is reacted under a copper- To give 1,5-pentanediol in a two-step process. However, the copper-chromite catalyst used in the above-mentioned prior art contains chromium (Cr) which is a heavy metal substance. There is a problem in that chromium (Cr) used in the production of the catalyst or in the treatment of the spent catalyst is treated, and since the chromium (Cr) belongs to the expensive metal among the transition metals, In addition, when a copper-chromite catalyst is used, as mentioned above, a very high hydrogen pressure is required. Therefore, in order to maintain process stability, a capital investment cost and a process operation cost are required. As the noble metal catalyst used in the method for producing 1,5-pentanediol using THFA as a reactant, Rh-MOx / SiO ₂ [M = Mo, Re, W , Ag, Cr, Mn, V, Zr] is and is disclosed in Japanese Laid-Open Patent Publication No. 2009-046417 arc, Rh-MOx / SiO ₂ [M = Mo, Re, W] is "Selective Hydrogenolysis of Polyols and Cyclic Ethers over Bifunctional Surface Sites on Rh-Re Catalysts"; J. Am. Chem. Soc. 133 (32), 12675-12689. In recent years, Ir-MOx / Support [M = Re, Mo, V, Support = Al ₂ O ₃ , SiO ₂ , Carbon] catalyst has been proposed as a noble metal catalyst capable of replacing rhodium, -098070 and "CO bond hydrogenolysis of cyclic ethers with OH groups over rhenium-modified supported iridium catalysts "; Journal of Catalysis 294 (2012) 171-183. The above prior arts produce 1,5-pentanediol at a high selectivity, but the noble metal material contained in the catalyst is expensive, resulting in high costs in commercialization. In addition, in the embodiments of the above techniques, only 1,5-pentanediol is produced through a batch reaction and there is no description of deactivation of the catalyst.

On the other hand, a general method for producing lactone is a method of producing a diol compound through a dehydrogenation reaction under a catalyst. "A catalytic method for synthesis of γ-butyrolactone, ε-caprolactone and 2-cumaranone in the presence of Preyssler's anion, [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , as a green and reusable catalyst"; J. Mol. Catal. A. Chem. 252 (2006) 90-95 suggests that 1,4-butanediol, 1,6-hexanediol and 1,2-benzenedimethanol are used as γ-butyrolactone, ε-capro Lactone and 2-coumaranone in a high yield. However, it is difficult to produce a large amount of a lactone compound under the above catalyst, and it is difficult to manufacture due to the characteristics of the catalyst and the cost is high.

U.S. Published Patent Application No. 2011-0237806 discloses a process comprising the steps of: a) evaporating 1,5-pentanediol under an inert gas stream, b) contacting a catalyst layer comprising two or more different copper- Passing an inert gas stream comprising a diol, and c) condensing the reaction product of the gas mixture obtained from said step b). However, this method has a problem in that two catalysts must be used simultaneously.

As mentioned in the above-mentioned prior art, in general, a diol should be used as a reaction raw material in order to produce a lactone. However, since the diol substance is widely used and expensive, there is a disadvantage in terms of commercial use or price in direct use as a raw material for producing lactone.

The present inventors have repeatedly studied to solve the problems of the prior art for preparing the above-mentioned diol or lactone. As a result, the present inventors have found that 1,5-pentanediol can be produced under mild conditions using THFA, which is a bio-derived raw material, and δ-valerolactone can be prepared directly using THFA without passing through 1,5-pentanediol Valerolactone, which has not been previously known, which can be used as a starting material, to complete the present invention.

Accordingly, an object of the present invention is to provide a process for producing 1,5-pentanediol under mild reaction conditions using a chromium-free copper nanocomposite oxide catalyst, or a process for producing 1,5-pentanediol under the same catalyst, Valerolactone by directly reacting ropur furyl alcohol and a catalyst used therefor.

In order to achieve the above object, the present invention provides a process for producing 1,5-pentanediol from a THFA-containing feed material by the hydrogenation ring-opening reaction in the presence of a catalyst represented by the following formula 1 or 2, , A process for producing [delta] -valerolactone directly without passing through 5-pentanediol.

[Chemical Formula 1]

_{CuO (a) SiO 2 (d} )

Wherein (a) and (d) are percentages based on the weight of the catalyst, ranging from 50 to 90% and from 10 to 50%, respectively.

(2)

CuO (a) M ₁ (b) M ₂ (c) SiO ₂ (d)

In this formula,

M1 represents an oxide of at least one metal selected from the group consisting of Co, Ni, Zn, Mn, Ag and Ru;

M2 represents an oxide of at least one metal selected from the group consisting of magnesium (Mg), calcium (Ca), barium (Ba), tellurium (Te) and selenium (Se);

(a), (b), (c) and (d) are percentages based on the weight of the catalyst, ranging from 50 to 90%, 0 to 15%, 0 to 5% and 5 to 40%, respectively.

The present invention relates to a novel production process for producing 1,5-pentanediol by using THFA as a bio-derived raw material under mild conditions and for producing δ-valerolactone directly using THFA without passing through 1,5-pentanediol ≪ / RTI > According to the present invention, it is possible to simplify the process via 1,5-pentanediol required in the existing δ-valerolactone production process. In addition, 1,5-pentanediol can be prepared through the hydrogenation ring-opening reaction of the resulting δ-valerolactone or, if necessary, δ-valerolactone can be prepared from 1,5-pentanediol by dehydrogenation reaction It can cope effectively with market demand and situation change. In addition, since Cr is not contained in the components of the catalyst represented by Chemical Formula 1 or Chemical Formula 2, it is possible to provide an environmentally-friendly and economical catalyst production method. Further, by replacing the expensive 1,5-pentanediol charged as a raw material for producing δ-valerolactone with THFA, which is more advantageous in price, by producing δ-valerolactone directly from THFA by the present invention, , And 1,5-pentanediol and? -Valerolactone are produced using a bio-derived raw material, so that it can be recognized as an environment-friendly process. The method for preparing 1,5-pentanediol and δ-valerolactone according to the present invention has an advantage that it is excellent in commercial production application by reducing facility cost, operation cost, raw material cost and environmental cost to be inputted into the process.

Hereinafter, the present invention will be described in detail.

The present invention relates to a process for the preparation of 1,5-pentanediol using Tetrahydrofurfuryl alcohol (THFA) obtained by hydrogenation of furfural which can be easily obtained from hemicellulose hemicelluloses In order to improve the problems of conventional copper-chromite catalysts, 1,5-pentanediol can be prepared from THFA as shown in the reaction path (a) of Scheme 1 below under mild reaction conditions, Pentanediol and 隆 -valerolactone, which can directly produce 隆 -valerolactone from THFA without passing through 1,5-pentanediol as shown in the reaction path (b) of Scheme 1 below, and To the catalyst used.

According to the present invention, it is also possible to prepare 1,5-pentanediol by the hydrogenation ring-opening reaction of δ-valerolactone produced as shown in the reaction path (c) of the following reaction scheme 1 under the same catalyst,隆 -valerolactone can be prepared from 5-pentanediol by dehydrogenation reaction.

[Reaction Scheme 1]

The catalyst used in the process for preparing 1,5-pentanediol and 隆 -valerolactone from THFA according to the present invention is represented by the following formula (1).

[Chemical Formula 1]

_{CuO (a) SiO 2 (d} )

Wherein (a) and (d) are percentages based on the weight of the catalyst, ranging from 50 to 90% and from 10 to 50%, respectively.

It is also useful as a hydrogenation-dehydrogenation catalyst of THFA in the composition range of CuO-SiO ₂ catalysts containing copper and silica components in the reaction for preparing 1,5-pentanediol and 隆 -valerolactone from THFA according to the invention , It is possible to prepare 1,5-pentanediol and? -Valerolactone.

In the present invention, a catalyst represented by the following formula (2) is preferably used to improve the catalytic performance and to improve the selectivity and stability of the reaction.

(2)

CuO (a) M ₁ (b) M ₂ (c) SiO ₂ (d)

In this formula,

M1 represents an oxide of at least one metal selected from the group consisting of Co, Ni, Zn, Mn, Ag and Ru;

M2 represents an oxide of at least one metal selected from the group consisting of magnesium (Mg), calcium (Ca), barium (Ba), tellurium (Te) and selenium (Se);

(a), (b), (c) and (d) are percentages based on the weight of the catalyst, ranging from 50 to 90%, 0 to 15%, 0 to 5% and 5 to 40%, respectively.

A catalyst selected from the group consisting of cobalt (Co), nickel (Ni), zinc (Zn), manganese (Mn), silver (Ag) and ruthenium (Ru) At least one metal selected from the group consisting of magnesium (Mg), calcium (Ca), barium (Ba), tellurium (Te) and selenium (Se) (M2 in the formula (1)), excellent selectivity is exhibited when the δ-valerolactone is directly produced from THFA, and the advantage of the long-term reaction activity is confirmed by improving the durability of the catalyst.

In this case, it is effective to improve the M1 component in the catalyst represented by the above formula (2) by adding the catalyst in a range of 0 to 15%, preferably 1 to 12%, as a percentage based on the weight of the catalyst. If the amount is less than this, the effect of improvement is small, and if it is large, the activity of the catalyst may be lowered. In the catalyst represented by Formula 2, it is effective to improve the M2 component by adding the catalyst in a range of 0 to 5%, preferably 0.05 to 3%, as a percentage based on the weight of the catalyst. If the amount is smaller, the effect of modifying is small, and if it is large, the activity of the catalyst may be lowered.

Although not wishing to be bound by theory, the improvement effect of the M1 and M2 components described above can be attained by increasing the selectivity by suppressing the side reaction by the improvement of the catalyst characteristics by the addition of the above components, or by alleviating or suppressing the carbon deposition rate or the component movement of the copper component To improve performance and durability. The catalyst of Formula 2 prepared under the above composition and composition ratio exhibited high activity, selectivity and reaction stability, and thus it was possible to enhance the utility as an industrial catalyst.

In the catalyst having the composition represented by Chemical Formula 1 or Chemical Formula 2, the copper component is the main active component for inducing the hydrogenation-dehydrogenation reaction, and its content is 50 to 90%, preferably 60 to 85% based on copper oxide . If the content of copper in the catalyst is small, the activity of the catalyst may not be exhibited properly and conversion rate may be lowered. If the content of copper is too high, thermal stability may not be secured, thereby preventing sintering of fine copper particles. The side reaction may proceed or the pore which is the contact path of the reaction material may be shielded, so that the deactivation may occur rapidly. In this case, in order to achieve the object of the present invention, it is preferable to produce copper oxide having a particle size of 50 nm or less, preferably 25 nm or less in a composite catalyst containing a copper component.

The silica (SiO ₂ ) in the catalyst represented by the above Chemical Formula 1 or Chemical Formula 2 is a main component for securing the thermal stability of the nano-sized copper particles, and the nano-sized silica particles are compounded between the nano- It is possible to prevent or suppress the sintering between the copper particles by the copper particles. Accordingly, the silica used may have a particle size of 4 to 50 nm, preferably 25 nm or less, and the content may range from 5 to 40%, preferably from 10 to 30%. If the amount of the silica is less than the above range, the effect is small, and if the amount is too large, the silica component may lower the activity due to the shielding of the copper particles as the catalytically active component.

The catalyst useful for the hydrogenation-dehydrogenation reaction of the THFA having the composition represented by the above Chemical Formula 1 or 2 is prepared by adjusting the particle size of the copper oxide, which is the main component of the catalyst, in the complex catalyst containing the copper component to be controlled to 50 nm or less However, in order to achieve the object of the present invention, the homogeneity of the multi-component should be maintained, and in particular, it is preferable to prepare by coprecipitation because uniform homogeneity of the copper particles and silica particles is important.

In a preferred embodiment of the present invention, the copper, M1 and silica components in the formula (2) are prepared by coprecipitating aqueous solutions (A, B) containing the respective components by using sodium hydroxide or potassium hydroxide aqueous solution as a co- Followed by hydrothermal aging, followed by washing. Herein, the copper and M1 components may be water-soluble salts such as nitrate, hydrochloride and sulfate, preferably nitrate (aqueous solution A). Silica can be colloidal silica having a particle size of 25 nm or less stabilized with sodium or ammonium ions (aqueous solution B). At this time, the copper oxide crystals are produced in the form of a rod, and a shape regulating agent can be used to control the particle size, shape and the like.

In the catalyst represented by the above formula (2), the M2 component compound can not simultaneously be prepared by coprecipitation because it has some solubility in water, and the M2 component aqueous solution is mixed with the slurry containing the washed copper, M1 oxide and silica component Followed by spray drying, and the like. In this case, components such as magnesium, calcium and barium can be nitrate or acetate, preferably nitrate, and tellurium and cerium are ammonium salts or acid compounds such as ammonium tellurate, ammonium selenate, Tellurium acid, selenious acid, etc.] can be used.

The dried catalyst powder can be formed by a conventional molding method such as an extrusion method, a pressing method, a loading method, and the catalyst form can be formed into any shape such as a spherical shape, a rod shape, a pellet shape, a hollow cylinder type Can also be molded. Thereafter, the formed catalyst can be calcined at 300 to 1000 캜, preferably 400 to 900 캜, in an air atmosphere.

In order to effectively achieve the object of the present invention in the production of the catalyst of the above formula 2 by the above-mentioned method, it is preferable to clean the catalyst so that the sodium or potassium component used as the co-precipitant remains in the catalyst to a minimum, It is necessary to adjust the content of the alkali metal to not more than 500 ppm, preferably not more than 200 ppm. If it is higher than that, the durability of the catalyst may be deteriorated, the conversion rate may be decreased, and the byproduct may increase in the reaction.

The method of preparing the catalyst used in the present invention has been described with reference to the catalyst represented by the formula (2). However, the method of preparing the catalyst represented by the formula (1) will be apparent to those skilled in the art.

The preparation of 1,5-pentanediol and < RTI ID = 0.0 > 8-valerolactone < / RTI > using the catalysts described herein has the advantage of being more environmentally and commercially advantageous.

The catalyst according to the invention can be prepared by hydrogenation-dehydrogenation of a liquid or gaseous THFA-containing feed under a flow of hydrogen gas or hydrogen-containing inert gas to produce 1,5-pentanediol and 隆 -valerolactone have. In addition to the object of the present invention, 1,5-pentanediol having a high yield can be prepared by carrying out a hydrogenation reaction using δ-valerolactone as a reactant on a catalyst having the composition of Formula 2, -Pentanediol can also be used additionally because it is possible to prepare? -Valerolactone through dehydrogenation reaction.

The above reaction is carried out by first charging the catalyst represented by the above formula (1) or (2) into a fixed-bed reactor and activating the catalyst at 150 to 300 ° C for about 1 to 20 hours using hydrogen gas or hydrogen- , A THFA-containing, 隆 -valerolactone-containing or 1,5-pentanediol-containing reaction is fed into the reactor depending on the desired product. The reactants may be supplied in pure form or may be mixed with a solvent if necessary.

The solvent is preferably a substance which is stable at the reaction temperature and pressure, and is preferably a substance which can be easily separated. For example, organic substances such as 1,3-dioxane, 1,4-dioxane, alcohols having 1 to 4 carbon atoms, ether and heterocyclic compounds, or water can be used, and 1,4- It is better to use oxalic acid.

In the reaction, hydrogen or a hydrogen-containing gas is used for the purpose of transporting reactants or preventing carbon deposition on the surface of the catalyst. However, in the case of a hydrogen-containing gas, inert gas such as nitrogen, argon, It is preferable that the gas contains hydrogen, and it is preferable to use a gas containing hydrogen in the amount of nitrogen.

The reaction conditions for producing 1,5-pentanediol or 隆 -valerolactone from THFA will be described in detail as follows.

[Equation 1]

1) Preparation of 1,5-pentanediol from THFA

The reaction temperature is preferably in the range of 180 to 300 ° C, more preferably 210 to 280 ° C. The reaction pressure is in the range of 15 to 50 bar, preferably in the range of 20 to 40 bar. The weighted space velocity (WHSV, h ^-1 ) according to Equation ( ¹ ) is in the range of 0.1 to 2 h ^-1 , preferably in the range of 0.2 to 1 h ^-1 . In the case of the THFA-containing reactant and the hydrogen-containing gas fed to the reactor, the molar ratio of H ₂ / THFA is preferably in the range of 10 to 100, preferably 20 to 70.

2) Preparation of 隆 -valerolactone from THFA

The reaction temperature is preferably in the range of 220 to 350 ° C, more preferably 250 to 300 ° C. The reaction pressure ranges from atmospheric pressure to 15 bar, preferably atmospheric pressure to 5 bar. The weighted space velocity (WHSV, h ^-1 ) according to Equation ( ¹ ) is in the range of 0.1 to 2 h ^-1 , preferably in the range of 0.2 to 1 h ^-1 . In the case of the hydrogen-containing gas supplied to the reactor together with the THFA-containing reactant, the molar ratio of H ₂ / THFA is preferably in the range of 10 to 50, preferably in the range of 15 to 40.

The process for preparing δ-valerolactone from 1,5-pentanediol on the same catalyst or for producing 1,5-pentanediol from δ-valerolactone is usually carried out at a reaction temperature, pressure , Weight space velocity (h ^-1 ), and H ₂ / mole ratio of reactants.

 The present invention will be more clearly understood from the following examples, which are for illustrative purposes only and are not intended to limit the scope of the invention.

Hereinafter, the content of each component of the catalyst means a weight% based on the total weight of the catalyst.

< Example >

< Catalyst preparation >

Manufacturing example  One: CuO (80) / SiO ₂ (20)

Solution A was prepared by dissolving 24.29 g of copper nitrate [Cu (NO ₃ ) ₂ 3H ₂ O] in 200 ml of deionized water. To 80 ml of deionized water, a sodium hydroxide solution was added to adjust the pH to 9.2, and 6.667 g of colloidal silica Ludox AS-30 (manufactured by Grace Davision) was dissolved therein. To 200 ml of deionized water was added 8.41 g of sodium hydroxide Solution C was prepared. 100 ml of deionized water was added to a 1 L beaker, and the solutions A, B and C were simultaneously added thereto while stirring, and the coacervation process was performed at 20 ° C or less. At this time, the pH was adjusted by adjusting the supply amount of solution C, and the final pH of the slurry solution after completion of coprecipitation was adjusted to 9.3. To this was added 2.08 g of a 0.5 wt% aqueous solution of polyvinylpyrrolidone having an average molecular weight of 10,000, and the temperature was slowly raised. After hydrothermal aging at 85 캜 for 6 hours, the pH of the resulting solution was found to be 7, Washed thoroughly with ionized water, filtered and the precipitate was recovered. The obtained precipitate was thoroughly dried at room temperature and dried at 120 DEG C for 4 hours to remove moisture. The powder was compressed and pulverized and separated into a size of 20 to 40 mesh.

Thereafter, the mixture was firstly calcined at 300 ° C and calcined at 600 ° C for 6 hours under air flow to obtain a catalyst in an oxide state.

The copper oxide particle size of the catalyst was 6.5 nm as measured by the X-ray diffraction method (XRD line broadening method). In addition, the content of sodium component remaining in the catalyst was 43 ppm as determined by elemental analysis (ICP-MS).

Manufacturing example  2: CuO (74.28) CoO (3.0) ZnO (0.2) CaO (0.25) MgO (0.25) TeO ₂ (0.02) SiO ₂ (22)

Deionized water, 10 L of copper nitrate to the _{[Cu (NO 3) 2 ·} 3H 2 O] 3,500 g, of cobalt nitrate _{[Co (NO 3) 2 ·} 6H 2 O] 180.8 g, zinc nitrate _{[Zn (NO 3) 2 ·} 6H ₂ O] (1137.6 g). To 4 L of deionized water, a solution of sodium hydroxide was added to adjust the pH to 9.2, and 1137.6 g of colloidal silica Ludox AS-30 (manufactured by Grace Davision) was dissolved therein. To 10 L of deionized water, 1212 g of sodium hydroxide Solution C was prepared. 10 L of deionized water was added to a 50 L reactor equipped with a stirrer, and the solutions A, B, and C were simultaneously added while stirring, followed by coacervation at 20 ° C or less. At this time, the pH was adjusted by adjusting the supply amount of solution C, and the final pH of the slurry solution after completion of coprecipitation was adjusted to 9.3. 300 g of a 0.5 wt% aqueous solution of polyvinylpyrrolidone having an average molecular weight of 10,000 was added, and the temperature was slowly raised to hydrothermally aged at 85 캜 for 6 hours. After confirming that the pH of the resulting solution was 7, Washed thoroughly with ionized water, filtered and the precipitate was recovered. After that dispersing the obtained precipitate in deionized water, acetic acid, calcium here _{[Ca (OAc) 2 · H} 2 O] 11.18 g and magnesium acetate _{[Mg (OAc) 2 · 4H} 2 O] 20.63 g and telru ryumsan [Te ( OH) ₆ ] in deionized water was mixed and then dried by spray drying.

The dried powder was dried at 120 ° C. for 12 hours, and then calcined at 300 ° C., and 5% by weight of graphite powder was mixed with other additives, molded into a pellet in an automatic tablet machine, And then calcined at 600 DEG C for 6 hours to obtain a catalyst in an oxide state.

The copper oxide particle size of the catalyst was 5.5 nm as measured by the X-ray diffraction method (XRD line broadening method). In addition, the content of sodium component remaining in the catalyst was 75 ppm by elemental analysis (ICP-MS).

Example  One

The catalyst prepared according to Preparation Example 1 having a size of 20 to 40 mesh was charged with 2.0 g of catalyst in the center of a 10 mm SUS fixed bed tubular reactor and the voids in the upper and lower portions of the catalyst bed in the reactor were quartz wool, . The temperature of the catalyst layer was controlled through a temperature sensor located between the furnace jacket and the catalyst layer. The gas flow rate was controlled through a mass flow controller. Also, the supplied reactant is supplied from the upper end of the reactor to the lower end, and the product is recovered through the condenser at the lower end of the reactor. Catalyst activation was carried out with 2.0 g of catalyst loaded in the reactor while maintaining a gas mixture of 5% H ₂ / N ₂ at 42 ml / min. The activation temperature starts at room temperature and is first reduced at 170 ° C for 1 hour and then reduced to 270 ° C for 4 hours. The temperature raising rate was maintained at 1.5 캜 / min. The reaction was initiated when the activation of the catalyst was completed. The reaction temperature was fixed at 230 占 폚 and the reaction pressure was fixed at a hydrogen pressure of 40 bar. Then, THFA / 1,4-Dioxane (1/1 vol%) mixture was injected into contact with the catalyst. At this time, the weight hourly space velocity (WHSV) was 0.3 h ^{- 1} , and the supplied hydrogen was injected so that the molar ratio of H ₂ / THFA was 65 mol.

After 20 hours from the initiation of the reaction, the conversion of THFA was 45.1%, and in the case of selectivity, 66.3% of 1,5-pentanediol, 3.2% of 1-pentanol and 2.9% of δ- valerolactone, 42.9%. The selectivity was 66.9% for 1,5-pentanediol, 3.6% for 1-pentanol and 1.6% for δ-valerolactone.

Example  2

Except that the catalyst prepared in Preparation Example 2 was used. As a result, the conversion of THFA after 50 hours from the initiation of the reaction was 47.1%, the selectivity was 73.3% for 1,5-pentanediol, Pentafluorobutanol, 0.2% of 1-pentanol, and 4.9% of delta-valerolactone. After 100 hours from the start of the reaction, the conversion of THFA was 46.9%, and in the case of selectivity, Valerolactone was 4.8%.

Example  3

(WHSV, h- ¹ ) was supplied to the reactor at a reaction temperature of 260 ° C and a reaction pressure of atmospheric pressure, and the reactant was fed to pure THFA at a weight hourly space velocity (WHSV, h ^-1 ) of 0.6 h ^-1 . ₂ / THFA molar ratio was 17.5. As a result, the conversion of THFA was 47.4% and the selectivity of δ-valerolactone was 75.8% after 20 hours from the initiation of the reaction. The conversion was 40.4% and the δ-valerolactone selectivity was 75.6%.

Example  4

As a result, the conversion of THFA was 58.4% and the selectivity of δ-valerolactone was 87.9% after 20 hours from the initiation of the reaction, and the conversion of 50 After the reaction time, the conversion of THFA was 55.4% and the selectivity of δ-valerolactone was 88.6%.

Example  5

In Example 4, THFA / 1,4-Dioxane (1/1 vol%) was used as a reactant and the reaction was carried out at a weight hourly space velocity (WHSV) of 0.3 h ^-1 . The molar ratio of H ₂ / THFA was 35 The conversion of THFA was 75.4% and the selectivity of δ-valerolactone was 83.5% after 20 hours from the initiation of the reaction. The conversion of THFA was 75.2% after 50 hours from the initiation of the reaction, And the δ-valerolactone selectivity was 86.8%.

Referring to the above Examples 1 to 5, it can be seen that 1,5-pentanediol and δ-valerolactone can be selectively prepared from THFA using the catalyst according to the present invention.

The technical idea of the present application should not be construed as being limited to the specific embodiments and examples described above. It will be readily appreciated by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the following claims is to be construed as including all such modifications, substitutions, additions, and combinations thereof, within the scope of the technical idea disclosed in this application.

Claims (12)

A catalyst represented by the following formula (1) for producing 1,5-pentanediol and? -Valerolactone from THFA:
[Chemical Formula 1]
_{CuO (a) SiO 2 (d} )
Wherein (a) and (d) are percentages based on the weight of the catalyst, ranging from 50 to 90% and from 10 to 50%, respectively.
A catalyst according to claim 1, wherein the catalyst is represented by the following formula (2), which further comprises a catalytically active component:
(2)
CuO (a) M ₁ (b) M ₂ (c) SiO ₂ (d)
In this formula,
M1 represents an oxide of at least one metal selected from the group consisting of Co, Ni, Zn, Mn, Ag and Ru;
M2 represents an oxide of at least one metal selected from the group consisting of magnesium (Mg), calcium (Ca), barium (Ba), tellurium (Te) and selenium (Se);
(a), (b), (c) and (d) are percentages based on the weight of the catalyst, ranging from 50 to 90%, 0 to 15%, 0 to 5% and 5 to 40%, respectively.
The catalyst according to claim 1 or 2, wherein the particle size of the copper oxide constituting the catalyst is 50 nm or less.
The catalyst according to claim 1 or 2, wherein the particle size of the silica constituting the catalyst is 50 nm or less.
A process for the preparation of 1,5-hexanediol from THFA in the presence of a catalyst according to claim 1 or 2.
A process for preparing δ-valerolactone from THFA in the presence of a catalyst according to claim 1 or 2.
6. The process according to claim 5, wherein the reaction is carried out by activating the catalyst at a temperature in the range of 150 to 300 DEG C under the condition of supplying hydrogen or a hydrogen-containing inert gas to the catalyst before initiation of the reaction.
7. The process according to claim 6, wherein the reaction is carried out by activating the catalyst at a temperature in the range of 150 to 300 DEG C under the condition of supplying hydrogen or a hydrogen-containing inert gas to the catalyst before initiation of the reaction.
7. The method according to claim 5 or 6, wherein the reactor is charged with a catalyst, the reactant reacting with the catalyst is supplied in pure form, or the reactant is reacted with water, 1,3-dioxane, 1,4-dioxane, Wherein the solvent is mixed with one or more solvents selected from the group consisting of alcohols having 1 to 4 carbon atoms, ether and heterocyclic compounds, and the like.
7. Process according to claim 5 or 6, characterized in that the weight hourly space velocity (WHSV, h- ¹ ) of THFA is supplied in the range of 0.1 to 2 h &lt; ^{-1 &} gt ;.
6. The process according to claim 5, wherein the reaction is carried out at a hydrogen pressure in the range of 180 to 300 DEG C and a reaction pressure in the range of 15 to 50 bar.
The process according to claim 6, wherein the reaction is carried out at a hydrogen pressure in the range of 220 to 350 ° C and a reaction pressure in the range of atmospheric pressure to 5 bar.