WO2010044531A2 - Metal oxide catalysts for etherification, method for its preparation thereof, and method for the production of linear polyglycerol using the same - Google Patents

Metal oxide catalysts for etherification, method for its preparation thereof, and method for the production of linear polyglycerol using the same Download PDF

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WO2010044531A2
WO2010044531A2 PCT/KR2009/002948 KR2009002948W WO2010044531A2 WO 2010044531 A2 WO2010044531 A2 WO 2010044531A2 KR 2009002948 W KR2009002948 W KR 2009002948W WO 2010044531 A2 WO2010044531 A2 WO 2010044531A2
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polyglycerol
metal oxide
etherification
glycerol
catalyst
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French (fr)
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WO2010044531A3 (en
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Yoo Han Han
Hyung Rok Kim
In Sun Han
Hyun Oung Choi
Hyun Sic Kim
So Young An
Young Ho Youn
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Korea Research Institute Of Chemical Technology
Kci Limited.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/164—Calcium aluminates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Definitions

  • the present invention relates to a metal oxide catalyst used in the production of linear polyglycerol via estherification of glycerol and a method for its preparation thereof.
  • linear polyglycerols diglycerol, triglycerol and tetraglycerol have been used as raw material for esterification with fatty acid and trans-esterification with fatty acid ester.
  • Polyglycerols such as diglycerol and triglycerol have a broader spectrum of use than vegetable oil(triglyceride).
  • various hydroxyl groups of polyglycerol are used as a raw material for the condensation reaction with alkyd resin.
  • polyglycerols have been used as a high quality emulsifying agent for controlling the balance between lipophilicity and hydrophilicity in pharmaceutical, cosmetic and food industries.
  • polyglycerols Since it is derived from plants, polyglycerols are environment-friendly and nontoxic, and thus, its use has been on drastic increase. Besides, polyglycerols can be used as a fabric softener, a wetting agent, a thickening agent, an antifoaming agent, a dispersing agent and a lubricant.
  • diglycerol is manufactured by reacting glycerol with glycidol or epichlorohydrin [EP Patent No: 0 33 984 A1].
  • the reaction is not selective, and it is difficult to handle the reactants involved therein, glycidol and epichlorohydrin, thus having a very low cost effectiveness.
  • US Patent No. 3,637,774 discloses a method of preparing linear polyglycerols such as diglycerol and triglycerol by etherifying glycerol in the presence of an alkali catalyst such as caustic soda (sodium hydroxide).
  • an alkali catalyst such as caustic soda (sodium hydroxide).
  • Polyglycerols are synthesized by using an alkali catalyst in an anhydrous solvent at 100°C or higher, diluted by adding water, and decolorized by adding a decolorant at 100°C or below. Since polyglycerols prepared according to the above method show a high content of cyclic polyglycerol, their separation/purification from linear polyglycerols is difficult. Further, it requires neutralization of the alkali catalyst, which makes post-treatment steps more complex and results in decrease in the yield of linear polyglycerols.
  • US Patent No. 5,349,094 discloses a method of etherifying glycerol by using a catalyst such as zeolite NaA and zeolite NaX in the amount of 2.4 wt% at 240°C for 22 hours.
  • a catalyst such as zeolite NaA and zeolite NaX in the amount of 2.4 wt% at 240°C for 22 hours.
  • polyglycerol comprising 15.4 wt% of glycerol, 32.3 wt% of diglycerol, 20.5 wt% of triglycerol, and 31.8 wt% of high polyglycerol (tetraglycerol+pentaglycerol+hexaglycerol) was prepared.
  • the above method has advantages of having relatively high conversion rate and wide distribution of polyglycerol selectivity.
  • it has several problems that polyglycerol is decolorated due to a high content of cyclic polyglycerol, it requires a long reaction time and necessitates the removal of odors generated therefrom.
  • US Patent No. 5,721,305 discloses a method of preparing linear polyglycerol by using hydrotalcite, a basic clay compound, as a base solid catalyst instead of zeolite.
  • hydrotalcite a basic clay compound
  • zeolite a base solid catalyst
  • magnesium-based hydrotalcite [Mg 6 Al 2 (OH) 16 (CO 3 )4H 2 O] catalyst in the amount of 5 wt%
  • polyglycerol comprising 41.5 wt% of glycerol, 35.0 wt% of linear diglycerol, 12.0 wt% of linear triglycerol, 3.5 wt% of linear high polyglycerols (a higher mole number equal to or higher than tetraglycerol) and 5.5 wt% of cyclic polyglycerol was obtained.
  • polyglycerol comprising 52 wt% of glycerol, 30 wt% of linear diglycerol, 11 wt% of linear triglycerol, 4 wt% of linear high polyglycerol(a higher mole number equal to or higher than tetraglycerol) and 1 wt% of cyclic polyglycerol was obtained.
  • the content of cyclic polyglycerol is significantly reduced due to the use of the above catalyst, but there are still problems that polyglycerol is decolorated due to a low conversion rate, it requires a long reaction time and also necessitates the removal of odors generated therefrom.
  • US Patent No. 6,620,904 B2 introduced a method of dehydration performed under reduced pressure of 150 mmHg, thus reducing the reaction time to 15 hours.
  • calcium hydroxide [Ca(OH) 2 ] is used in the amount of 0.1 wt% as a catalyst, and the etherification is performed at 230°C under reduced pressure of 150 mmHg for 15 hours.
  • polyglycerol comprising 43 wt% of glycerol, 33 wt% of linear diglycerol, 14 wt% of linear triglycerol, 7 wt% of linear high polyglycerols and 2.3 wt% of cyclic polyglycerol was obtained. Further, it can prevent the discoloration and odor generation of polyglycerol by reducing the reaction time and lowering the reaction temperature. However, thus prepared crude polyglycerol is subjected to distillation at 200°C, 4 mmHg to separate glycerol.
  • polyglycerol comprising 0.12 wt% of glycerol, 42 wt% of linear diglycerol, 23 wt% of triglycerol, 30 wt% of linear high polyglycerol (a higher mole number equal to or higher than tetraglycerol), and 4.5 wt% of cyclic polyglycerol was obtained.
  • the polyglycerol contains relatively high content of cyclic polyglycerol. Therefore, there is still a need to develop a catalyst which requires short reaction time so as to prevent the discoloration and odor generation of a product, is high reactive under mild reaction conditions, and shows high selectivity so as to prevent the generation of cyclic polyglycerol.
  • the present inventors have therefore endeavored to overcome the above-mentioned problems of the prior art and found that when a basic metal oxide catalyst prepared according to a method of synthesizing a catalyst precursor having a hydrocalumite structure in the production of linear polyglycerol, dispersibility and uniformity of calcium and aluminum are significantly improved, etherification activity and selectivity are increased, thereby effectively preventing the discoloration and odor generation of a product.
  • the present invention relates to a binary metal oxide catalyst for etherification of glycerol which is represented by the following Formula 1:
  • a refers to a weight ratio of CaO based on 100 parts by weight of the total catalyst.
  • the present invention also relates to a method for preparing the metal oxide catalyst, comprising the steps of:
  • the present invention further relates to a method for producing polyglycerol via etherification of glycerol, which is characterized by using the metal oxide catalyst in the etherification
  • the alkaline binary metal oxide catalyst according to the present invention When used in the glycerol etherification, it can produce a large amount of linear polyglycerol glycerol. Therefore, the metal oxide catalyst according to the present invention can be effectively used in the production of polyglycerol suitable as cosmetic or food additives.
  • Fig. 1 is the result of analyzing a metal hydroxide having a hydrocalucite structure prepared in Example 1 with an X-ray diffractometer;
  • Fig. 2 is the result of analyzing metal oxide powders after calcining in Example with an X-ray diffractometer.
  • a refers to a weight ratio of CaO based on 100 parts by weight of the total catalyst.
  • Ca 12 Al 14 O 33 refers to calcium aluminum oxide (Ca aluminates) having a mayenite structure.
  • a indicates an integer preferably in the range of 30 to 70, more preferably in the range of 35 to 60. If the content of calcium oxide (CaO) exceeds 70 wt%, its dispersibility and uniformity are decreased, thereby lowering catalytic activity and conversion rate in the etherification. On the other hand, if the content thereof is lower than 30 wt%, due to the increase in acidity of the catalyst, there are problems of incurring a side reaction of generating cyclic compounds, significantly reducing selectivity of linear compounds and deteriorating the inhibitory effect on discoloration or odor generation.
  • CaO calcium oxide
  • Another technical feature of the present invention resides in a method for preparing the metal oxide catalyst, comprising the steps of:
  • step (1) a solution (A) in which calcium salt and aluminum salt are dissolved is added to a sodium chloride solution together with an alkaline precipitating agent solution (B) so as to induce co-precipitation of particles in a hydroxide form.
  • an alkaline precipitating agent solution B
  • the alkaline precipitating agent suitable for the present invention may include sodium hydroxide, sodium potassium and the like.
  • the calcium salt and aluminum salt solution at a concentration of 25 to 45 wt% and the alkaline precipitating solution at a concentration of 10 to 20 wt%. Further, it is preferable to use the solution (A) and solution (B) in an equal volume.
  • pH of the slurry solution (C) it is preferable to maintain pH of the slurry solution (C) to the range of 9 to 12 and regulate pH thereof by the amount of the precipitating agent added thereto. If the pH of the solution is higher than 12, a mixture of metal hydroxide, not hydroxide of hydrocalumite, is generated therefrom. Meanwhile, if the pH is below 9, the precipitation of ingredients such as calcium and aluminum is not fully achieved.
  • the co-precipitation it is preferable to constantly maintain the temperature of the slurry solution (C) at a range of 15 to 30 °C so as to maintain its hydrogel form, and the co-precipitation is preferably carried out for 0.5 to 10 hours.
  • step (2) the slurry solution obtained in step (1) is stirred at a temperature of 40 to 80°C for 3 to 30 hours. During the stirring, hydrocalumite crystals are synthesized and grown.
  • Hydrocalumite is anionic clay having layered double-hydroxide characteristics and represented by the following Formula 2.
  • A is an interlayer anion such as chloride ion or nitrate ion, x is 2, and m is 4.
  • divalent calcium and trivalent aluminum of hydrocalumite are uniformly bonded in an atomic level, dispersibility and uniformity of active metal ingredients are very high.
  • a stirring temperature if the stirring is carried out at a temperature lower than 40°C, the synthesis and growth of hydrocalumite crystals are subjected to restriction, which results in generating fine calcium crystals, thereby incurring a side reaction of generating cyclic polyglycerol.
  • the stirring is carried out at a temperature higher than 80°C, the synthesis and growth thereof are proceeded too fast, the size of calcium crystals become un-uniform, thus resulting in the decrease of catalytic activity.
  • step (3) the precipitate obtained in step (2) is separated, washed and dried, to thereby obtain hydrocalumite metal hydroxide powders.
  • the washed precipitate is dried at a temperature of 100 to 120°C for 5 to 30 hours, followed by pulverizing into a particle size of 5 to 100 micrometer in a pulverizer, or drying in the form of powders in a spray dryer.
  • step (4) the hydrocalumite metal hydroxide powders obtained in step (3) is calcined at a temperature of 400 to 800°C, preferably 500 to 700°C for 2 to 6 hours. If the calcination temperature exceeds 800°C, calcium metal oxide particles are calcined, thereby lowering of catalytic activity. If the calcination temperature is lower than 400°C, calcium oxide (CaO) particles are formed incompletely, thereby lowering its conversion rate.
  • the present invention is characterized by the method using the metal oxide catalyst as a catalyst for the etherification.
  • polyglycerol refers to diglycerol, triglycerol, tetraglycerol and higher oligomerization glycerol.
  • the polyglycerol prepared according to the method contains 98 wt% of linear polyglycerol, its odor and color are excellent, thus being suitable for cosmetic ingredients and food additives.
  • the etherification by using the binary metal oxide catalyst in the method according to the present invention is characterized in a slurry type reaction using a batch reactor.
  • the reaction is carried out discontinuously in a batch reactor or continuously in several continuous flow stirred reactors.
  • the metal oxide catalyst is used in the amount of 0.2 to 7.0 parts by weight, preferably 0.5 to 5.0 parts by weight based on 100 parts by weight of glycerol. If the amount of the catalyst used exceeds 7.0 parts by weight, the content of cyclic polyglycerol is significantly increased. Meanwhile, if its content is lower than 0.2 parts by weight, the resulting conversion rate becomes lowered, thereby conducting the reaction under harsh conditions.
  • the etherification is carried out at a temperature of 200 to 250°C, preferably at 220 to 240°C. If the reaction temperature exceeds 250°C, there is a high risk of discoloration and odor generation of polyglycerol. Meanwhile, if that is lower than 200°C, its conversion rate is greatly lowered, resulting in increase in the reaction time.
  • the etherification is carried out by adding the reactants and catalyst into a reactor, removing oxygen and moisture from the reactor with nitrogen gas, and elevating a temperature of the reactor to the desired reaction temperature.
  • the slurry solution obtained above was stirred at 60°C for 12 hours and filtered. After 1,000 ml distilled water was added thereto, the mixture was dispersed, stirred and filtered, the entire process of which was repeated four times.
  • the hydroxide obtained by the filtration was dried at 100°C for 10 hours.
  • the dried hydroxide was pulverized into a particle size of 10 to 60 micrometer in a pulverizer and analyzed with an X-ray diffraction spectroscopy (XRD). As a result, it was found that the hydroxide was a compound having a hydrocalumite structure (Fig. 1).
  • the hydroxide having a hydrocalumite structure is represented by the following Formula: Ca 4 Al 2 (OH) 12 (NO 3 ) 2 x H 2 O.
  • the dried powders were calcined at 600°C for 6 hours in air.
  • etherification reactor As an etherification reactor, a batch reactor equipped with a stirring rate controller, nitrogen generator, a packed column, a reflux separator, a temperature controller, a heater and a collector was used. After glycerol (1,000 g) was added to the reactor, the catalyst 20 g prepared in Example 1 was added thereto. The inside of the reactor was then replaced with nitrogen by supplying nitrogen gas into the reactor. After elevating a temperature of the reactor to 230°C, the etherification was initiated. Product samples were collected from the reactor according to reaction times and filtered to remove the catalyst.
  • polyglycerol was composed of 0.6wt% of glycerol, 56wt% of linear diglycerol, 30 wt% of linear triglycerol, 12 wt% of linear high polyglycerol (equal to or greater than mole number of tetraglycerol), and 1.4 wt% of cyclic polyglycerol. Further, it was found that its content of linear polyglycerol was 98 wt%, and its color was transparent under APHA 50.
  • Test Example 2 Etherification test depending on the difference in a weight ratio of CaO and Ca 12 Al 14 O 33
  • the weight ratio between calcium nitrate and aluminum nitrate used in the preparation of a catalyst was varied, to thereby prepare several kinds of metal oxide catalysts having different a values.
  • Each of the metal oxide catalysts having different values was subjected to etherification as described in Test Example 1, and the results of the etherification after 24 hours are shown in Table 2.
  • polyglycerol was composed of 0.7 wt% of glycerol, 52.2 wt% of linear diglycerol, 32 wt% of linear triglycerol, 13 wt% of linear high polyglycerol (equal to or greater than mole number of tetraglycerol), and 2.1 wt% of cyclic polyglycerol. Further, it was found that its content of linear polyglycerol is 97.2 wt%, and its color is transparent under APHA 50.
  • polyglycerol was composed of 0.8 wt% of glycerol, 53.4 wt% of linear diglycerol, 28 wt% of linear triglycerol, 13 wt% of linear high polyglycerol (equal to or greater than mole number of tetraglycerol), and 4.8 wt% of cyclic polyglycerol. Further, it was found that its content of linear polyglycerol was 94.4 wt%, and its color was light yellow under APHA 150.
  • polyglycerol was composed of 0.8 wt% of glycerol, 59.1 wt% of linear diglycerol, 24 wt% of linear triglycerol, 11 wt% of linear high polyglycerol (equal to or greater than mole number of tetraglycerol), and 5.1 wt% of cyclic polyglycerol. Further, it was found that its content of linear polyglycerol was 94.1 wt%, and its color was yellow under APHA 250.
  • Test Example 3 Etherification test depending on the amount of a catalyst and a reaction temperature
  • the etherification was carried out according to the same method as described in Example 1 except that the catalyst prepared in Example 1 was used and the amount of a catalyst and a reaction temperature varied as shown in Table 3. The results obtained 24 hours after the eterification are shown in Table 3.
  • the product sample obtained after the etherification was subjected to evaporation under reduced pressure at 200°C, 4 mmHg, to obtain polyglycerol.
  • the analysis of its composition revealed that the content of linear polyglycerol in the polyglycerol obtained in Example 3 was 97.6 wt%, the polyglycerol obtained in Example 4 was 98.1 wt%, and the polyglycerol obtained in Example 5 was 97.8 wt%.
  • the binary metal oxide catalyst according to the present invention can produce 96wt% or more of linear polyglycerol from glycerol.

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Abstract

The present invention relates to a metal oxide catalyst represented by the following Formula 1, which is useful for the production of linear polyglycerol via etherification of glycerol, and a method for its preparation thereof: [Formula 1] (CaO)a˙Ca12Al14O33)100-a wherein a refers to a weight ratio of CaO based on 100 parts by weight of the total catalyst. When the alkaline binary metal oxide catalyst according to the present invention is used in the glycerol etherification, it can produce a large amount of linear polyglycerol glycerol. Therefore, the metal oxide catalyst prepared according to the present invention can be effectively used in the production of polyglycerol suitable as cosmetic or food additives.

Description

METAL OXIDE CATALYSTS FOR ETHERIFICATION, METHOD FOR ITS PREPARATION THEREOF, AND METHOD FOR THE PRODUCTION OF LINEAR POLYGLYCEROL USING THE SAME
The present invention relates to a metal oxide catalyst used in the production of linear polyglycerol via estherification of glycerol and a method for its preparation thereof.
Among linear polyglycerols, diglycerol, triglycerol and tetraglycerol have been used as raw material for esterification with fatty acid and trans-esterification with fatty acid ester. Polyglycerols such as diglycerol and triglycerol have a broader spectrum of use than vegetable oil(triglyceride). Typically, for the production of polyurethane foam, various hydroxyl groups of polyglycerol are used as a raw material for the condensation reaction with alkyd resin. Further, polyglycerols have been used as a high quality emulsifying agent for controlling the balance between lipophilicity and hydrophilicity in pharmaceutical, cosmetic and food industries. Since it is derived from plants, polyglycerols are environment-friendly and nontoxic, and thus, its use has been on drastic increase. Besides, polyglycerols can be used as a fabric softener, a wetting agent, a thickening agent, an antifoaming agent, a dispersing agent and a lubricant.
Among polyglycerols, diglycerol is manufactured by reacting glycerol with glycidol or epichlorohydrin [EP Patent No: 0 33 984 A1]. However, the reaction is not selective, and it is difficult to handle the reactants involved therein, glycidol and epichlorohydrin, thus having a very low cost effectiveness.
As a way to solve the above problems, US Patent No. 3,637,774 discloses a method of preparing linear polyglycerols such as diglycerol and triglycerol by etherifying glycerol in the presence of an alkali catalyst such as caustic soda (sodium hydroxide). Polyglycerols are synthesized by using an alkali catalyst in an anhydrous solvent at 100℃ or higher, diluted by adding water, and decolorized by adding a decolorant at 100℃ or below. Since polyglycerols prepared according to the above method show a high content of cyclic polyglycerol, their separation/purification from linear polyglycerols is difficult. Further, it requires neutralization of the alkali catalyst, which makes post-treatment steps more complex and results in decrease in the yield of linear polyglycerols.
As an alternative for the water-soluble alkali catalyst, there have been reported a few methods using a solid base catalyst. US Patent No. 5,349,094 discloses a method of etherifying glycerol by using a catalyst such as zeolite NaA and zeolite NaX in the amount of 2.4 wt% at 240℃ for 22 hours. As a result, polyglycerol comprising 15.4 wt% of glycerol, 32.3 wt% of diglycerol, 20.5 wt% of triglycerol, and 31.8 wt% of high polyglycerol (tetraglycerol+pentaglycerol+hexaglycerol) was prepared. The above method has advantages of having relatively high conversion rate and wide distribution of polyglycerol selectivity. However, it has several problems that polyglycerol is decolorated due to a high content of cyclic polyglycerol, it requires a long reaction time and necessitates the removal of odors generated therefrom.
US Patent No. 5,721,305 discloses a method of preparing linear polyglycerol by using hydrotalcite, a basic clay compound, as a base solid catalyst instead of zeolite. As a result of reacting at 240℃ for 20 hours by using magnesium-based hydrotalcite [Mg6Al2(OH)16(CO3)4H2O] catalyst in the amount of 5 wt%, polyglycerol comprising 41.5 wt% of glycerol, 35.0 wt% of linear diglycerol, 12.0 wt% of linear triglycerol, 3.5 wt% of linear high polyglycerols (a higher mole number equal to or higher than tetraglycerol) and 5.5 wt% of cyclic polyglycerol was obtained.
In order to reduce the content of cyclic polyglycerol, as a result of reacting at 240℃ for 28 hours by using hydrocalcite having the general formula of Mg6Al2.04Si1.95 in the amount of 5 wt%, polyglycerol comprising 52 wt% of glycerol, 30 wt% of linear diglycerol, 11 wt% of linear triglycerol, 4 wt% of linear high polyglycerol(a higher mole number equal to or higher than tetraglycerol) and 1 wt% of cyclic polyglycerol was obtained. The content of cyclic polyglycerol is significantly reduced due to the use of the above catalyst, but there are still problems that polyglycerol is decolorated due to a low conversion rate, it requires a long reaction time and also necessitates the removal of odors generated therefrom.
In order to solve the problem due to the long reaction time, US Patent No. 6,620,904 B2 introduced a method of dehydration performed under reduced pressure of 150 mmHg, thus reducing the reaction time to 15 hours. Here, calcium hydroxide [Ca(OH)2] is used in the amount of 0.1 wt% as a catalyst, and the etherification is performed at 230℃ under reduced pressure of 150 mmHg for 15 hours. As a result, polyglycerol comprising 43 wt% of glycerol, 33 wt% of linear diglycerol, 14 wt% of linear triglycerol, 7 wt% of linear high polyglycerols and 2.3 wt% of cyclic polyglycerol was obtained. Further, it can prevent the discoloration and odor generation of polyglycerol by reducing the reaction time and lowering the reaction temperature. However, thus prepared crude polyglycerol is subjected to distillation at 200℃, 4 mmHg to separate glycerol. After the distillation, polyglycerol comprising 0.12 wt% of glycerol, 42 wt% of linear diglycerol, 23 wt% of triglycerol, 30 wt% of linear high polyglycerol (a higher mole number equal to or higher than tetraglycerol), and 4.5 wt% of cyclic polyglycerol was obtained. The polyglycerol contains relatively high content of cyclic polyglycerol. Therefore, there is still a need to develop a catalyst which requires short reaction time so as to prevent the discoloration and odor generation of a product, is high reactive under mild reaction conditions, and shows high selectivity so as to prevent the generation of cyclic polyglycerol.
The present inventors have therefore endeavored to overcome the above-mentioned problems of the prior art and found that when a basic metal oxide catalyst prepared according to a method of synthesizing a catalyst precursor having a hydrocalumite structure in the production of linear polyglycerol, dispersibility and uniformity of calcium and aluminum are significantly improved, etherification activity and selectivity are increased, thereby effectively preventing the discoloration and odor generation of a product.
The present invention relates to a binary metal oxide catalyst for etherification of glycerol which is represented by the following Formula 1:
[Formula 1]
(CaO)a˙Ca12Al14O33)100-a
wherein a refers to a weight ratio of CaO based on 100 parts by weight of the total catalyst.
Further, the present invention also relates to a method for preparing the metal oxide catalyst, comprising the steps of:
(1) adding a solution in which calcium salt and aluminum salt are dissolved and an alkaline precipitating agent to a sodium chloride solution at the same time, to thereby generate a precipitate in the form of a composite metal hydroxide;
(2) stirring the reaction solution at a temperature of 40 to 80℃ after the generation of the precipitate;
(3) separating, washing and drying the precipitate, to thereby obtain hydrocalumite metal hydroxide powders; and
(4) calcining the metal hydroxide powders in the air at a temperature of 400 to 800℃.
Further, the present invention further relates to a method for producing polyglycerol via etherification of glycerol, which is characterized by using the metal oxide catalyst in the etherification
When the alkaline binary metal oxide catalyst according to the present invention is used in the glycerol etherification, it can produce a large amount of linear polyglycerol glycerol. Therefore, the metal oxide catalyst according to the present invention can be effectively used in the production of polyglycerol suitable as cosmetic or food additives.
The above and other features of the present invention will now be described in detail with reference to certain exemplary embodiments thereof illustrated the accompanying drawings which are given herein below by way of illustration only, and thus are not limitative of the present invention, and wherein:
Fig. 1 is the result of analyzing a metal hydroxide having a hydrocalucite structure prepared in Example 1 with an X-ray diffractometer; and
Fig. 2 is the result of analyzing metal oxide powders after calcining in Example with an X-ray diffractometer.
It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various preferred features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.
Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the drawings attached hereinafter, wherein like reference numerals refer to like elements throughout. The embodiments are described below to explain the present invention by referring to the figures.
The technical feature of the present invention resides in a binary metal oxide catalyst for etherification of glycerol which is represented by the following Formula 1:
[Formula 1]
(CaO)a˙Ca12Al14O33)100-a
wherein a refers to a weight ratio of CaO based on 100 parts by weight of the total catalyst.
Ca12Al14O33 refers to calcium aluminum oxide (Ca aluminates) having a mayenite structure.
In Formula 1, a indicates an integer preferably in the range of 30 to 70, more preferably in the range of 35 to 60. If the content of calcium oxide (CaO) exceeds 70 wt%, its dispersibility and uniformity are decreased, thereby lowering catalytic activity and conversion rate in the etherification. On the other hand, if the content thereof is lower than 30 wt%, due to the increase in acidity of the catalyst, there are problems of incurring a side reaction of generating cyclic compounds, significantly reducing selectivity of linear compounds and deteriorating the inhibitory effect on discoloration or odor generation.
Another technical feature of the present invention resides in a method for preparing the metal oxide catalyst, comprising the steps of:
(1) adding a solution in which calcium salt and aluminum salt are dissolved and an alkaline precipitating agent to a sodium chloride solution at the same time, to thereby generate a precipitate in the form of a composite metal hydroxide;
(2) stirring the reaction solution at a temperature of 40 to 80℃ after the generation of the precipitate;
(3) separating, washing and drying the precipitate, to thereby obtain hydrocalumite metal hydroxide powders; and
(4) calcining the metal hydroxide powders in the air at a temperature of 400 to 800℃.
In step (1), a solution (A) in which calcium salt and aluminum salt are dissolved is added to a sodium chloride solution together with an alkaline precipitating agent solution (B) so as to induce co-precipitation of particles in a hydroxide form. There is no limitation to the kinds of calcium salt and aluminum salt to be used in the present invention as long as they do not hamper the objects of the present invention, and their representative examples include water-soluble nitrate, hydrochloride, acetate and the like. In case of nitrate, since anions remained after washing can be effectively removed in the course of calcining, it is most preferably.
The alkaline precipitating agent suitable for the present invention may include sodium hydroxide, sodium potassium and the like.
It is preferable to use the calcium salt and aluminum salt solution at a concentration of 25 to 45 wt% and the alkaline precipitating solution at a concentration of 10 to 20 wt%. Further, it is preferable to use the solution (A) and solution (B) in an equal volume.
After the co-precipitation, it is preferable to maintain pH of the slurry solution (C) to the range of 9 to 12 and regulate pH thereof by the amount of the precipitating agent added thereto. If the pH of the solution is higher than 12, a mixture of metal hydroxide, not hydroxide of hydrocalumite, is generated therefrom. Meanwhile, if the pH is below 9, the precipitation of ingredients such as calcium and aluminum is not fully achieved.
During the co-precipitation, it is preferable to constantly maintain the temperature of the slurry solution (C) at a range of 15 to 30 ℃ so as to maintain its hydrogel form, and the co-precipitation is preferably carried out for 0.5 to 10 hours.
Then, in step (2), the slurry solution obtained in step (1) is stirred at a temperature of 40 to 80℃ for 3 to 30 hours. During the stirring, hydrocalumite crystals are synthesized and grown.
Hydrocalumite is anionic clay having layered double-hydroxide characteristics and represented by the following Formula 2.
[Formula 2]
[Ca4Al2(OH)12][Ax mH2O]
wherein A is an interlayer anion such as chloride ion or nitrate ion, x is 2, and m is 4.
Since divalent calcium and trivalent aluminum of hydrocalumite are uniformly bonded in an atomic level, dispersibility and uniformity of active metal ingredients are very high.
Regarding to a stirring temperature, if the stirring is carried out at a temperature lower than 40℃, the synthesis and growth of hydrocalumite crystals are subjected to restriction, which results in generating fine calcium crystals, thereby incurring a side reaction of generating cyclic polyglycerol. On the other hand, if the stirring is carried out at a temperature higher than 80℃, the synthesis and growth thereof are proceeded too fast, the size of calcium crystals become un-uniform, thus resulting in the decrease of catalytic activity.
In step (3), the precipitate obtained in step (2) is separated, washed and dried, to thereby obtain hydrocalumite metal hydroxide powders.
During the washing, it is important to regulate the residual amount of cationic substances such as sodium or potassium derived from the alkaline precipitating agent added in step (1). It is preferable to regulate the concentration of the cationic substance to 1,000 ppm and below as compared with that of the catalyst in an oxidized state. The washed precipitate is dried at a temperature of 100 to 120℃ for 5 to 30 hours, followed by pulverizing into a particle size of 5 to 100 micrometer in a pulverizer, or drying in the form of powders in a spray dryer.　
Next, in step (4), the hydrocalumite metal hydroxide powders obtained in step (3) is calcined at a temperature of 400 to 800℃, preferably 500 to 700℃ for 2 to 6 hours. If the calcination temperature exceeds 800℃, calcium metal oxide particles are calcined, thereby lowering of catalytic activity. If the calcination temperature is lower than 400℃, calcium oxide (CaO) particles are formed incompletely, thereby lowering its conversion rate.
Further, in a method of preparing polyglycerol by etherifying glycerol, the present invention is characterized by the method using the metal oxide catalyst as a catalyst for the etherification.
The term "polyglycerol" as used herein refers to diglycerol, triglycerol, tetraglycerol and higher oligomerization glycerol.
Since the polyglycerol prepared according to the method contains 98 wt% of linear polyglycerol, its odor and color are excellent, thus being suitable for cosmetic ingredients and food additives.
The etherification by using the binary metal oxide catalyst in the method according to the present invention is characterized in a slurry type reaction using a batch reactor. The reaction is carried out discontinuously in a batch reactor or continuously in several continuous flow stirred reactors.
In the etherification, the metal oxide catalyst is used in the amount of 0.2 to 7.0 parts by weight, preferably 0.5 to 5.0 parts by weight based on 100 parts by weight of glycerol. If the amount of the catalyst used exceeds 7.0 parts by weight, the content of cyclic polyglycerol is significantly increased. Meanwhile, if its content is lower than 0.2 parts by weight, the resulting conversion rate becomes lowered, thereby conducting the reaction under harsh conditions.
The etherification is carried out at a temperature of 200 to 250℃, preferably at 220 to 240℃. If the reaction temperature exceeds 250℃, there is a high risk of discoloration and odor generation of polyglycerol. Meanwhile, if that is lower than 200℃, its conversion rate is greatly lowered, resulting in increase in the reaction time.
The etherification is carried out by adding the reactants and catalyst into a reactor, removing oxygen and moisture from the reactor with nitrogen gas, and elevating a temperature of the reactor to the desired reaction temperature.
[Examples]
The following examples illustrate the present invention but they should not be construed as limiting the scope of the present invention.
Example 1: Preparation of metal oxide catalyst [(CaO)a˙Ca12Al14O33)100-a; a=39.3]
Calcium nitrate [Ca(NO3)2˙H2O] (94.5 g) and aluminum nitrate [Al(NO3)3˙H2O] (75.0 g) were dissolved in distilled water, to prepare a 500 ml solution (solution A). Further, sodium hydroxide [NaOH] (72 g) was dissolved in distilled water, to prepare a 500 ml solution (solution B). Sodium chloride [NaCl] (5.8 g) was dissolved in distilled water, to prepare a 200 ml solution (solution C). After the solution C was added to a 2 L beaker equipped with a pH electrode, the solutions A and B were added thereto at the same flow rate for 1 hour while stirring. Here, the final pH of the resulting mixture was adjusted to 11 by regulating the amount of the solution B added.
The slurry solution obtained above was stirred at 60℃ for 12 hours and filtered. After 1,000 ml distilled water was added thereto, the mixture was dispersed, stirred and filtered, the entire process of which was repeated four times. The hydroxide obtained by the filtration was dried at 100℃ for 10 hours. The dried hydroxide was pulverized into a particle size of 10 to 60 micrometer in a pulverizer and analyzed with an X-ray diffraction spectroscopy (XRD). As a result, it was found that the hydroxide was a compound having a hydrocalumite structure (Fig. 1). The hydroxide having a hydrocalumite structure is represented by the following Formula: Ca4Al2(OH)12(NO3)2 xH2O. The dried powders were calcined at 600℃ for 6 hours in air. As a result of analyzing the catalyst calcined in air with XRD, it was found the formation of calcium oxide and calcium aluminate crystals (Fig. 2).　
Test Example 1: Etherification
As an etherification reactor, a batch reactor equipped with a stirring rate controller, nitrogen generator, a packed column, a reflux separator, a temperature controller, a heater and a collector was used. After glycerol (1,000 g) was added to the reactor, the catalyst 20 g prepared in Example 1 was added thereto.　 The inside of the reactor was then replaced with nitrogen by supplying nitrogen gas into the reactor. After elevating a temperature of the reactor to 230℃, the etherification was initiated. Product samples were collected from the reactor according to reaction times and filtered to remove the catalyst.
To 10 to 50 mg of the polyglycerol sample was added 5 ml of a silane coupling agent [hexamethyldisilazane : trimethlychlorosilane : pyridine = 3:1:9, weight ratio] to be silanized, and then, analyzed with a gas chromatography. The results are shown in Table 1.
Table 1
Figure PCTKR2009002948-appb-I000001
Further, the product sample obtained after 24 hours of reaction was subjected to evaporation under reduced pressure at 200℃, 4 mmHg, to obtain polyglycerol. The analysis of its composition revealed that thus obtained polyglycerol was composed of 0.6wt% of glycerol, 56wt% of linear diglycerol, 30 wt% of linear triglycerol, 12 wt% of linear high polyglycerol (equal to or greater than mole number of tetraglycerol), and 1.4 wt% of cyclic polyglycerol. Further, it was found that its content of linear polyglycerol was 98 wt%, and its color was transparent under APHA 50.
Test Example 2: Etherification test depending on the difference in a weight ratio of CaO and Ca12Al14O33
In the metal oxide catalyst of a (CaO)˙Ca12Al14O33)100-a catalyst, the weight ratio between calcium nitrate and aluminum nitrate used in the preparation of a catalyst was varied, to thereby prepare several kinds of metal oxide catalysts having different a values. Each of the metal oxide catalysts having different values was subjected to etherification as described in Test Example 1, and the results of the etherification after 24 hours are shown in Table 2.
Table 2
Figure PCTKR2009002948-appb-I000002
Further, after the etherification using the catalyst prepared in Example 2 for 24 hours, thus obtained product sample was subjected to evaporation under reduced pressure at 200℃, 4 mmHg, to obtain polyglycerol. The analysis of its composition revealed that thus obtained polyglycerol was composed of 0.7 wt% of glycerol, 52.2 wt% of linear diglycerol, 32 wt% of linear triglycerol, 13 wt% of linear high polyglycerol (equal to or greater than mole number of tetraglycerol), and 2.1 wt% of cyclic polyglycerol. Further, it was found that its content of linear polyglycerol is 97.2 wt%, and its color is transparent under APHA 50.
In addition, after the etherification using the catalyst prepared in Comparative Example 1 for 24 hours, thus obtained product sample was subjected to evaporation under reduced pressure at 200℃, 4 mmHg, to obtain polyglycerol. The analysis of its composition revealed that thus obtained polyglycerol was composed of 0.8 wt% of glycerol, 53.4 wt% of linear diglycerol, 28 wt% of linear triglycerol, 13 wt% of linear high polyglycerol (equal to or greater than mole number of tetraglycerol), and 4.8 wt% of cyclic polyglycerol. Further, it was found that its content of linear polyglycerol was 94.4 wt%, and its color was light yellow under APHA 150.
Further, after the etherification using the catalyst prepared in Comparative Example 2 for 24 hours, thus obtained product sample was subjected to evaporation under reduced pressure at 200℃, 4 mmHg, to obtain polyglycerol. The analysis of its composition revealed that thus obtained polyglycerol was composed of 0.8 wt% of glycerol, 59.1 wt% of linear diglycerol, 24 wt% of linear triglycerol, 11 wt% of linear high polyglycerol (equal to or greater than mole number of tetraglycerol), and 5.1 wt% of cyclic polyglycerol. Further, it was found that its content of linear polyglycerol was 94.1 wt%, and its color was yellow under APHA 250.
Test Example 3: Etherification test depending on the amount of a catalyst and a reaction temperature
The etherification was carried out according to the same method as described in Example 1 except that the catalyst prepared in Example 1 was used and the amount of a catalyst and a reaction temperature varied as shown in Table 3. The results obtained 24 hours after the eterification are shown in Table 3.
Table 3
Figure PCTKR2009002948-appb-I000003
Further, the product sample obtained after the etherification was subjected to evaporation under reduced pressure at 200℃, 4 mmHg, to obtain polyglycerol. The analysis of its composition revealed that the content of linear polyglycerol in the polyglycerol obtained in Example 3 was 97.6 wt%, the polyglycerol obtained in Example 4 was 98.1 wt%, and the polyglycerol obtained in Example 5 was 97.8 wt%.
From the results obtained in the Examples and Test Examples, it was found that the binary metal oxide catalyst according to the present invention can produce 96wt% or more of linear polyglycerol from glycerol.
The invention has been described in detail with reference to preferred embodiments thereof. However, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

  1. A binary metal oxide catalyst for glycerol etherification represented by the following Formula 1:
    [Formula 1]
    (CaO)a˙Ca12Al14O33)100-a
    wherein a refers to a weight ratio of CaO based on 100 parts by weight of the total catalyst.　
  2. The metal oxide catalyst according to Claim 1, wherein a is an integer of from 30 to 70.
  3. A method for preparing the metal oxide catalyst represented by the following Formula 1, comprising the steps of:
    (1) adding a solution in which calcium salt and aluminum salt are dissolved and an alkaline precipitating agent to a sodium chloride solution at the same time, to thereby generate a precipitate in the form of a composite metal hydroxide;
    (2) stirring the reaction solution at a temperature of 40 to 80℃ after the generation of the precipitate;
    (3) separating, washing and drying the precipitate, to thereby obtain hydrocalumite metal hydroxide powders; and
    (4) calcining the metal hydroxide powders in the air at a temperature of 400 to 800℃.
    [Formula 1]
    (CaO)a˙Ca12Al14O33)100-a
    wherein a refers to a weight ratio of CaO based on 100 parts by weight of the total catalyst.
  4. The method according to Claim 3, wherein the mixed solution prepared in step (1) has a pH in the range of from 9 to 12.
  5. A method for producing polyglycerol via etherification of glycerol, which is characterized by using a metal oxide catalyst represented by the following Formula 1 during the etherification:
    [Formula 1]
    (CaO)a˙Ca12Al14O33)100-a
    wherein a refers to a weight ratio of CaO based on 100 parts by weight of the total catalyst.
  6. The method according to Claim 5, wherein the polyglycerol contains 96wt% or more of linear polyglycerol.
  7. The method according to Claim 5, wherein the metal oxide catalyst metal oxide catalyst is used in the amount of 0.2 to 7.0 parts by weight based on 100 parts by weight of glycerol.
  8. The method according to Claim 5, wherein the etherification is carried out at a temperature of 200 to 250℃.
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