Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group

Definitions

• the present invention relates to a method of producing 1,2,4-butanetriol using continuous hydrogenation. More particularly, the present invention pertains to a method of economically producing 1,2,4-butanetriol in an environmentally friendly manner, in which 2,3-epoxy-l,4-butanediol, generated by epoxidation, as a reactant is continuously hydrogenated in the presence of a nickel-based catalyst having a large surface area, thereby assuring yield and productivity that are higher than those of a conventional process.
• 1,2,4-butanetriol is represented by the following Formula 1
• the above compound has been used as, for example, an intermediate of an explosive and an intermediate of polyurethane and alkyd resins or the like, and, recently, has also been used as an important intermediate in medicine and agricultural medicine fields.
• Many technologies for producing 1,2,4-butanetriol have been known, and conventional methods of producing 1,2,4-butanetriol are as follows: U.S. Pat. No.
• 3,629,341 discloses a method of producing 1,2,4-butanetriol, in which 1-methoxy- 1,3 -butadiene as organic peroxide is epoxidated and hydrated at pH 1-2 using water of about 60-100 °C for the conversion into 3,4- dihydroxybutyl aldehyde, which is then is hydrogenated in the presence of a hydrogenation catalyst (Raney nickel, Raney cobalt, platinum, palladium, or copper-chromium oxides) to produce 1,2,4-butanetriol.
• a hydrogenation catalyst Raney nickel, Raney cobalt, platinum, palladium, or copper-chromium oxides
• 59-70632 discloses a method of producing 1,2,4-butanetriol, in which 2-butene-l,4-diol is epoxidated and hydrogenated using a palladium-carbon catalyst.
• the above technology causes environmental pollution because a considerable amount of manganese dioxide should be used to decompose the excessive hydrogen peroxide after the epoxidation is finished, and is economically disadvantageous because a costly palladium catalyst is used for hydrogenation.
• 4,410,744 discloses a process of producing 1,2,4-butanetriol, in which 2,3-epoxy-l-propanol (glycidol) is subjected to a hydro formylation using a solvent and is then reduced in the presence of a hydrogenation catalyst, such as copper chromite.
• a hydrogenation catalyst such as copper chromite.
• U.S. Pat. No. 6,479,714 discloses a method of producing 1,2,4- butanetriol by reducing methyl dihydroxy butyric acid ester with a sodium borohydride catalyst.
• U.S. Pat. No. 4,973,769 discloses a process for producing 1,2,4-butanetriol through catalytic hydrogenation of malic ester using a copper-containing catalyst.
• European Pat. No. 0 297 444 discloses a method of producing 1,2,4-butanetriol, in which an aqueous 2,3-epoxy-l,4-butanediol solution is hydrogenated in the presence of a Raney nickel catalyst in a batch reactor under 200-300 atm.
• an object of the present invention is to provide a method of producing 1,2,4-butanetriol employing continuous hydrogenation, thereby solving problems encountered in the prior arts.
• Another object of the present invention is to provide a method of producing 1,2,4-butanetriol, in which 2,3-epoxy-l,4-butanediol having an epoxide moiety is used as a starting material for producing 1,2,4-butanetriol while adopting catalytic and operation conditions suitable for the continuous hydrogenation of said epoxide, thereby improving yield, productivity, and economic efficiency.
• an embodiment of the present invention provides a method of continuously producing 1,2,4-butanetriol.
• the method comprises feeding a liquid mixture comprising 2,3-epoxy-l,4-butanediol and a solvent into a continuous fixed-bed reaction system in which a nickel catalyst having a metal surface area of at least 3 m 2 /g is packed, and continuously hydrogenating the liquid mixture in a hydrogen (gas) atmosphere at conditions in which a reaction temperature is 10-250 ° C , a reaction pressure is 5-300 atm, and a liquid hourly space velocity (LHSN) is 0.1-30 hr "1 .
• a reaction temperature is 10-250 ° C
• a reaction pressure is 5-300 atm
• LHSN liquid hourly space velocity
• the present invention is advantageous in that 2,3-epoxy-l,4-butanediol having an epoxide moiety is used as a starting material for producing 1,2,4- butanetriol while adopting catalytic and reaction conditions suitable for the continuous hydrogenation of said epoxide, thereby economically producing 1,2,4- butanetriol at high yield and productivity.
• the present invention may be achieved by the following description.
• the present invention relates to a process in which a liquid mixture of 2,3-epoxy-l,4-butanediol and a solvent as a starting material are fed into a continuous reaction system and continuously converted into 1,2,4- butanetriol as a target material under hydrogen atmosphere.
• productivity and yield to a space time are high, a catalyst is repeatedly reused without an additional treatment process, it is easy to separate a product, and a continuous fixed-bed reaction system, which is capable of significantly simplifying the process, is adopted.
• the type of reactor and feeding and flowing directions of a reactant are not specifically limited.
• trickle-bed reactor having a device which is capable of enabling the liquid reactant and hydrogen gas to simultaneously flow from an upper part of the reactor to a lower part of the reactor and uniformly dispersing the reactant throughout the reactor so as to ensure smooth contact between the reactants.
• This well-known trickle-bed reactor has a characteristic in which gas/liquid flows to a lower part of the reactor through a bed having catalyst particles packed therein while the catalyst particles are fixed.
• 2,3-epoxy-l,4-butanediol which is used as the starting material in the present invention, is typically produced from 2-butene-l,4-diol, and the production of 2,3-epoxy-l,4-butanediol may be exemplified by the following Reaction equation 1 (e.g., cis type).
• 2,3-epoxy-l,4-butanediol as the reactant is fed in the form of a liquid mixture with a solvent into the continuous fixed-bed reaction system.
• the solvent be an organic solvent which does not react with 2,3-epoxy-l,4-butanediol as the reactant or with the hydrogen gas.
• the solvent may be one or more selected from the group consisting of alcohols, such as methanol, ethanol, propanol, and isopropanol, and ethers, such as tetrahydrofuran (THF), dioxane, and diglyme.
• 2,3-epoxy-l,4-butanediol is mixed with the solvent in a concentration of about 3-50 wt%, and more preferably, about 5-30 wt% based on a weight of the liquid mixture.
• a catalyst for hydrogenation should hydrogenate the epoxy moiety in 2,3-epoxy-l,4-butanediol as the reactant, thereby producing 1,2,4-butanetriol with high selectivity.
• a nickel-based catalyst is selected.
• inorganic oxide is used as a supporter or a binder.
• alumina, silica, zirconia, and titania may be used alone or in combination as inorganic oxide.
• the nickel content is not specifically limited. However, it is preferably at least about 5 wt%, and more preferably, about 5-80 wt%, based on the total weight of the catalyst.
• a metal surface area of the nickel-based catalyst is at least 3 m 2 /g, and preferably, at least 5 m 2 /g. When the metal surface area is less than 3 m 2 /g, it is unsuitable as a continuous hydrogenation catalyst because reactivity and selectivity are reduced.
• the "metal surface area” may be measured by a hydrogen adsorption method, which is disclosed in Journal of Catalysis 197, 210-219(2001), which is incorporated in the present invention as a reference.
• the catalyst may have any shape, including a sphere, cylinder, or granule. However, it is preferable that the catalyst be formed in the shape of a sphere or cylinder so as to have desirable mechanical properties.
• the liquid reactant as described above is fed into the reaction system and then converted into 1,2,4-butanetriol in the hydrogen atmosphere through hydrogenation. In this regard, it is important to control operation conditions so as to maximally suppress the generation of by-products and the reduction of conversion efficiency.
• reaction conditions be set to a temperature of about 10-250 U , a reaction pressure of about 5-300 atm, and a weight space velocity of about 0.1-30 hr "1 (liquid mixture). More preferably, the conversion is implemented under conditions of a reaction temperature of about 50-150 ° C , a reaction pressure of about 10-200 atm, and a weight space velocity of about 0.5-10 hr "1 (liquid mixture). Most preferably, the conversion is implemented under conditions of a reaction temperature of about 60- 130 °C, a reaction pressure of about 10-200 atm, and a weight space velocity of about 0.5-8 hr "1 (liquid mixture).
• a molar ratio of hydrogen to 2,3-epoxy-l,4-butanediol is adjusted to at least 1 or more, and preferably, to about 1-10 in consideration of economic efficiency of the process.
• the present invention is advantageous in that it is possible to separate products, which are exhausted from the fixed-bed reaction system after they are hydrogenated, using only a distillation operation without an additional catalyst filtration to recover desired target products, thus a recovery of the products is simplified after the reaction is finished.
• the same reactant was hydrogenated under the same conditions except that the metal surface areas of the nickel -based catalyst were 11 m 2 /g (Example 2), 5 m 2 /g (Example 3), 4 m 2 /g (Example 4), and 2 m 2 /g (Comparative Example 1). Conversion of 2,3-epoxy-l,4-butanediol and selectivity of 1,2,4-butanetriol according to the hydrogenation are described in the following Table 1.
• EXAMPLE 7 Hydrogenation was conducted through the same procedure as Example 1 except that a reaction temperature and a liquid hourly space velocity were respectively set to 90 ° C and 3.0 hr "1 , thereby producing 1,2,4-butanetriol.
• the analysis results were that the conversion of 2,3-epoxy-l,4-butanediol was 100 % and the selectivity of 1,2,4-butanetriol was increased to 99 %.
• the present invention is advantageous in that 2,3- epoxy-l,4-butanediol having an epoxide moiety is used as a starting material for producing 1,2,4-butanetriol while adopting catalytic and operation conditions suitable for the continuous hydrogenation of said epoxide, thereby economically producing 1 ,2,4-butanetriol at high yield and productivity. It should also be understood that the foregoing relates only to the scope of the invention as defined by the appended claims rather than by the description preceding them, and all changes that fall within scopes and bounds of the claims, or equivalence of such scopes and bounds are therefore intended to be embraced by the claims.

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• 2003
  • 2003-12-24 KR KR1020030096499A patent/KR100718767B1/ko not_active IP Right Cessation
• 2004
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