KR20160076780A - Continuous Reactor for Simultaneous Production and Distillation of Anhydrosugar Alcohol and Method of Preparing Anhydrosugar Alcohol Using the Same - Google Patents

Abstract

The present invention relates to a continuous reactor for simultaneous production and distillation of anhydrous sugar alcohol and a method for preparing anhydrous sugar alcohol. More particularly, the present invention relates to a reactor structure equipped with an impeller blade for carrying out a reaction for converting sorbitol into anhydrous sugar alcohol and a process for distillation and separation of the thus produced anhydrous alcohol in a single reactor. According to the continuous reactor for simultaneous production and distillation of anhydrous sugar alcohol and the method for preparing anhydrous sugar alcohol of the present invention, a reactor having properties both as a reactor and as a distillator is used, and thus production and distillation of anhydrous alcohol are carried out continuously in a single reactor. In addition, the reaction solution is subjected to surface renewal by a first impeller rotating vertically and the reaction solution is agitated by a second impeller rotating horizontally. Therefore, a high distillation efficiency of the anhydrous sugar alcohol is obtained so that the anhydrous sugar alcohol can be cost effectively produced.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a continuous reactor for simultaneous production and distillation of alcohol-free alcohol and a method for preparing alcohol-free alcohol using the same,

The present invention relates to a continuous reactor for simultaneous production and distillation of alcohol-free alcohol, and a method for preparing alcohol-free alcohol using the same, and more particularly, to a process for converting sugar alcohol such as sorbitol into alcohol- The present invention relates to a structure of a reactor having an impeller blade for performing a process of distilling and separating an alcohol with an alcohol therein in a single reactor.

The sugar alcohol is a sugar-derived alcohol and has mostly the structure of H (HCHO) _{n + 1} H. Such sugar alcohols are classified into tetritol, hexitol, and heptitol according to the number of carbon atoms. Among them, hexitol having six carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like. Among them, It is very useful because of the sweetener in the field.

Anhydrous alcohol is prepared through a dehydration reaction in which one or more water molecules are removed from the sugar alcohol molecule and has a completely new bonding structure completely different from sugar alcohol such as double bond, ether bond and cyclic bond. For example, when two water molecules are removed from hexitol, isosorbide (1,4-3,6-dianhydrosorbitol), isomannide (1,4-3,6-dianhydromannitol) Isoidide (1,4-3,6-dianhydroiditol), and the like. Such anhydrous alcohol is expected to be applied in many industries because of its wide variety of applications such as heart and blood vessel therapeutic agents, adhesives, mouthwashes, emulsifiers, additives for polymers, and bioplastics.

A conventional process for producing an anhydrous alcohol is a process in which sulfuric acid is used as a catalyst and the reaction is performed under reduced pressure (Korean Patent No. 10-1079518). However, when a strong acid such as sulfuric acid is used as a catalyst, it is necessary to use an expensive reactor to easily corrode the reactor and prevent corrosion, and since the decompression condition must be continuously achieved, a large amount of energy is consumed, . Also, it is not easy to produce continuous vacuum reactors with high reliability, and most processes use batch or semi-batch reactors.

On the other hand, alcohol-free alcohol has a high boiling point and is easily decomposed by heat at a high temperature. Therefore, when a normal atmospheric distillation is used, separation is difficult, and a vacuum distillation process is frequently used (US 6,639,067). However, the decompression condition must be maintained not only in the reaction process but also in the separation process, and the yield ratio of the alcohol without sugar is lowered every time the process of the multistage process is lowered.

In order to solve the disadvantages of such a multi-stage reactor, a reactor has been developed which simultaneously performs reaction and distillation in one reactor. This direct distillation method requires the simultaneous production and distillation of isosorbide in the reactor, and therefore it is necessary to have both the characteristics of the reactor and the characteristics of the distiller. In particular, surface renewal of the reaction solution is required to rapidly evaporate the isosorbide formed in the reaction solution.

Korean Patent No. 1376481 discloses a reactor which performs distillation simultaneously with the reaction. The present invention is advantageous in that the catalyst is easily separated and the yield and purity of isosorbide can be increased by distilling the isosobide generated simultaneously with the reaction using the solid acid catalyst. However, since the isosorbide is distilled Is distilled only on the surface of the liquid raw material, so that the overall reaction rate is slowed down.

Accordingly, the present inventors have made efforts to solve the above problems. As a result, the present inventors have found that a reactor having a first impeller rotating vertically and a second impeller rotating horizontally capable of stirring a reactant for surface renewing of a reaction solution , A reactor capable of simultaneously carrying out conversion of sugar alcohol to anhydrosugar alcohol and distillation of alcohol without sugar in a single reactor was developed and used as an anhydrosugar alcohol, The evaporation rate of the alcohol without sugar is increased and the half efficiency is improved. In addition, when the impeller blade for discharging the highly viscous byproduct is additionally provided, it is confirmed that the byproduct is easily discharged, .

It is an object of the present invention to provide a continuous reactor for simultaneous production and distillation of alcohol-free alcohol and a method for producing alcohol-free alcohol using the same.

In order to accomplish the above object, the present invention provides a continuous reactor for simultaneously performing production and distillation of an alcohol-free alcohol including a raw material supply portion, a gas outlet, a liquid outlet and a stirring means, wherein the stirring means includes (i) An impeller shaft rotated by the impeller; (ii) a first impeller installed at a middle portion of the impeller shaft and rotating in a vertical direction in accordance with the rotation of the impeller; And (iii) a second impeller positioned at a lower end of the impeller shaft and rotating in a horizontal direction in accordance with the rotation of the impeller.

The present invention also provides a process for producing anhydrosugar alcohol by dehydrating sugar alcohol in the presence of a catalyst, wherein the continuous reaction is used, wherein the continuous reaction is carried out simultaneously with distillation do.

Since the continuous reactor which simultaneously performs the production and distillation of anhydrosugar alcohol according to the present invention and the method for preparing anhydrosugar alcohol using the reactor according to the present invention uses a reactor having both the characteristics of the reactor and the characteristics of the distiller, The surface irreversibility of the reaction solution is smooth by the first impeller continuously rotating in one reactor and the reactant is stirred by the horizontally rotating second impeller, And is useful for the production of economical alcohol-free alcohol.

1 shows the overall structure of the reactor according to the present invention and the direction of rotation of the impeller.
Fig. 2 shows a detailed view of the first impeller.
Fig. 3 is a cross-sectional view of the first impeller.
FIG. 4 shows a state of the alcohol-free alcohol reactor equipped with the closure plate according to the present invention.
5 shows a gear used in a connecting portion of a first impeller used in the present invention. The worm gear b, the straight bevel gear c, the spiral bevel gear d, the helical bevel gear e, A combination of two gears and two gears arranged vertically, respectively.
FIG. 6 shows a view of an alcohol-free alcohol reactor having means for scraping heavy residues according to the present invention.
Figure 7 shows the means for scraping heavy residues and the outlet of the bottom of the reactor.
Figure 8 shows a view of a mercury free alcohol reactor having means for scraping heavy reactants extending to the wall of the reactor according to the invention.
FIG. 9 shows a state of the alcohol-free alcohol reactor having the second supply unit according to the present invention.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In the present invention, in the production of anhydrous alcohol using a continuous reaction of alcohol-free alcohol and a distillation apparatus, a reactor having a vertically rotating first impeller and a horizontally rotating second impeller and a reactor integrated with a still The product was distilled at a high rate and the continuous operation was possible.

In the present invention, the first impeller rotating in the vertical direction in accordance with the rotation of the stirring means, and the second impeller rotating in the horizontal direction in accordance with the rotation of the stirring means, Distillation was carried out in one reactor. As a result, the yield of an alcohol-free alcohol of the same level as that of the conventional sulfuric acid decompression reaction was achieved, and the distillation rate of anhydrosugar alcohol produced by stirring the surface of the reaction solution by the first impeller was improved Respectively.

Therefore, in one aspect of the present invention, there is provided a continuous reactor for simultaneously performing the production and distillation of an alcohol-free alcohol including a raw material supply portion, a gas outlet, a liquid outlet and a stirring means, wherein the stirring means comprises: (i) A rotating impeller shaft; (ii) a first impeller installed at a middle portion of the impeller shaft and rotating in a vertical direction in accordance with the rotation of the impeller; And (iii) a second impeller positioned at a lower end of the impeller shaft and rotating in a horizontal direction in accordance with the rotation of the impeller.

In the present invention, the gas outlet may be characterized in that water produced by the reaction and alcohol-free alcohol are discharged into the gas phase. In addition, heavy residues are mainly discharged to the liquid outlet, and unreacted alcohol and anhydrous alcohol and water which are not fully vaporized may be discharged together.

In the present invention, the first impeller 220 may have a plurality of grooves 221 formed on its surface. The first impeller 220 is preferably located on the upper portion of the raw material filled in the reactor, but is not limited thereto. The first impeller 220 is rotated about an axis orthogonal to the impeller shaft 210, thereby continuously stirring the upper portion of the raw material (Surface Renewal), and the free alcohol produced by the reaction of raw materials is easily vaporized . At this time, a plurality of grooves 221 are formed on the surface of the first impeller 220 so that the surface area of the first impeller 220 is increased to accelerate the vaporization of alcohol without alcohol.

In the present invention, the first impeller 220 may be provided with an electric heating means 222 therein. Since the inside of the reactor is maintained at a high temperature of 150 ° C. or higher and a low pressure of 200 torr or lower, the produced alcohol without alcohol is naturally evaporated. However, in order to increase the efficiency of evaporation, the first impeller is preferably provided with an electric heating means 222 therein. At this time, the plurality of grooves that increase the surface area serve to increase the surface area of the impeller in contact with the alcohol-free alcohol, thereby facilitating evaporation by heat.

In the present invention, the gas outlet 120 may further include reaction solution blocking means for preventing discharge of the reaction solution. When the sugar alcohol is reacted under reduced pressure, boiling occurs due to rapid vaporization of anhydrous alcohol and water produced. Due to this boiling phenomenon, a part of the reaction solution may be discharged (310) through the gas outlet port to lower the concentration of the product. Also, by rotating the first impeller, a part of the liquid may be scattered toward the gas discharge port 310 and may be discharged. In order to prevent this phenomenon, it is preferable to provide a reaction solution blocking means for separating the liquid, which is scattered or boiled by the first impeller, from the generated vapor. At this time, the means for isolating the reaction solution can be used without any restriction on the means for separating the gas and the liquid, but it is preferable to use the closure plate 300 or the cyclone separator which can cover the gas outlet.

In the present invention, the first impeller 220 may be connected to the impeller shaft by a worm gear, a straight bevel gear, a spiral bevel gear, or a helical bevel gear. Worm gears or bevel gears are commonly used to transmit rotation between two orthogonal axes. Particularly, the bevel gear is classified into a straight bevel gear, a spiral bevel gear or a helical bevel gear according to the type of engagement. In the present invention, in order to transmit the rotation of the impeller shaft to the first impeller, It is preferable to use gears. At this time, it is preferable that the first impeller is composed of a pair of both sides, and the second impeller is connected to the lower part, so that it is preferable that the second impeller is composed of a combination of two horizontally arranged gears and two vertically arranged gears.

In the present invention, the impeller may further include means (240) disposed at the lower portion of the second impeller (230) for scraping heavy residues having a high viscosity on the bottom surface of the reactor have. When a non-hydrogenated alcohol is prepared by a depressurization reaction, a side reaction product such as a polymer or a carbohydrate having a high viscosity is produced. These side reactants are discharged to the liquid outlet at the lower portion of the reactor. However, since the non-reactant has low fluidity, it is difficult to discharge it smoothly. Therefore, it is preferable to discharge the non-reactant using a means for scraping the highly viscous non-reactant on the bottom surface of the reactor. At this time, the means for scraping off the by-products is preferably made of silicon or plastic (241) at the lower end which is in contact with the bottom of the reactor and is stable at a high temperature to prevent the bottom of the reactor from being damaged. It is also preferred that the means for scraping off the by-products move along the curve of the bottom of the reactor and minimize the spacing from the bottom of the reactor.

In the present invention, the means for scraping the side reactant may extend along the bottom surface of the reactor to the reactor wall surface. The secondary reactant is mainly formed in the bottom portion of the reactor, but it is also formed on the wall surface of the reactor and interferes with the rotation of the impeller, so that the means for scraping the side reactant preferably extends to the reactor wall along the bottom of the reactor. Further, the means for scraping off the by-products includes a protrusion at a portion close to the bottom and the wall surface of the reactor, so that it can be positioned closer to the inner surface of the reactor and more effectively scraped off by the protrusion when the side reactants are precipitated on the inner surface of the reactor desirable.

In the present invention, the reactor may further include a second supply unit 140 for supplying steam or a part of the product to the reactor. The supplied steam serves to evaporate the alcohol-free alcohol produced inside the reactor and serves to maintain the temperature inside the reactor. It is also possible to increase the purity of anhydrous alcohol produced by recycling a portion of the product. At this time, the sparger is installed in the reactor of the second supply part, and it is preferable that the steam and the product to be supplied are uniformly supplied to the inside of the reactor by using the sparger. In addition, it is preferable that the inside of the reactor of the raw material supply portion to which the raw material is supplied is also equipped with a sparger.

In the present invention, the raw material may be characterized by being a sugar alcohol and an acid catalyst. An acid catalyst is used in the conversion of the sugar alcohol to the alcohol free alcohol. In the conventional continuous reaction, a solid acid catalyst is used to prevent the loss due to the volatilization of the catalyst. However, in the present invention, a catalyst having a higher boiling point (BP) than that of anhydrous alcohol To minimize losses due to Therefore, it is preferable that the acid catalyst has a boiling point of at least 160 ° C at 10 mmHg, a pKa of 3.0 to 3.0, and reacts with the raw material in a homogeneous manner.

The catalyst suitable for the present invention satisfies the following conditions.

(a) Boiling point

To maintain the catalytic activity without catalyst evaporation during the reaction, a catalyst having a boiling point higher than isosoboid (160 ° C at 10 mmHg) is selected. That is, the boiling point at 10 mmHg is 160 캜 or higher.

(b) acidity (pKa)

A catalyst having an acidity suitable for reducing the formation of byproducts such as polymers or coke at high temperature reaction conditions is used. The pKa range for the yield increase is -3.0 < pKa < 3.0, preferably the range is -2.0 < pKa < 2.5 and more preferably the range is -1.0 < pKa <

(3) homogeneous phase

A catalyst is used which increases the contact efficiency between the catalyst and the feed, reacts in a homogeneous phase under the reaction conditions, and maintains its activity without evaporation of the catalyst. For this purpose, the melting point may be 180 占 폚 or lower, preferably 160 占 폚 or lower, more preferably 140 占 폚 or lower, even more preferably 120 占 폚 or lower.

The catalyst may be naphthalenesulfonic acid. Specific compounds of naphthalenesulfonic acid include 2-naphthalenesulfonic acid or 1-naphthalenesulfonic acid, and these compounds are isomers which are formed by sulfonation of naphthalene. The 2-naphthalenesulfonic acid has pKa = 0.27, m.p. = 91 ° C, b.p. = 391.6 ° C, and 1-naphthalenesulfonic acid has pKa = 0.17, m.p. = 90 ° C and b.p. = 392 ° C.

In the present invention, the number of the first impeller and the number of the second impeller are two to five, respectively. The first impeller serves to stir the surface, and the second impeller serves to stir the raw material. Therefore, it is preferable to install 2 to 5 depending on the size and capacity of the reactor. At this time, the first impeller and the second impeller can be installed vertically on one impeller shaft, and it is also possible to install the first impeller and the second impeller on a plurality of impeller shafts, respectively.

In another aspect of the present invention, there is provided a process for preparing an alcohol-free alcohol by dehydrating sugar alcohol in the presence of a catalyst, wherein the continuous reactor is used to produce an alcohol-free alcohol .

The method for preparing an alcohol-free alcohol according to the present invention comprises the steps of: (a) feeding a sugar alcohol and an acid catalyst into a reactor; (b) heating the first impeller, rotating the impeller shaft to rotate the first impeller and the second impeller, and stirring the reactant; (c) recovering the product evaporated by the heated first impeller at the gas outlet; And (d) discharging the highly viscous byproduct from the liquid outlet.

In the present invention, the raw material may be characterized by being a sugar alcohol and an acid catalyst.

In the present invention, the acid catalyst may have a boiling point of at least 160 ° C at 10 mmHg, a pKa of 3.0 to 3.0, and reacting with the raw material in a homogeneous state.

In the present invention, the acid catalyst may be a naphthalenesulfonic acid (NAS).

In the present invention, it may further comprise the step of recycling the product recovered in the step (c) to the reactor. It is possible to produce high-purity alcohol-free alcohol when the produced alcohol-free alcohol is fed back to the reactor to increase the content of alcohol-free alcohol in the reactor. Therefore, it is preferable to increase the purity of the alcohol without reacting with a part of the product by recycling part of the product. It is more preferable to further supply steam to maintain the temperature inside the reactor and to help evaporate alcohol without alcohol.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereto will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

100: Reactor 110: Feedstock
120: gas outlet 130: liquid outlet
140: second supply unit 200: driving means
210: impeller shaft 220: first impeller
221: first impeller groove 222: electric heating means
230: second impeller
240: scraping means for scraping off secondary reactants
241: Lower part of the means for scraping the secondary reactant Silicon or plastic
300: blocking plate 310: scattering reaction solution

Claims (25)

In a continuous reactor which simultaneously performs the production and distillation of anhydrous alcohol including a raw material supply portion, a gas outlet portion, a liquid outlet portion and an agitating means,
The stirring means includes (i) an impeller shaft rotated by the driving means; (ii) a first impeller installed at a middle portion of the impeller shaft and rotating in a vertical direction in accordance with the rotation of the impeller; And (iii) a second impeller positioned at a lower end of the impeller shaft and rotating in a horizontal direction in accordance with the rotation of the impeller.
The continuous reactor according to claim 1, wherein the first impeller has a plurality of grooves formed on a surface thereof.
The continuous reactor according to claim 1, wherein the first impeller is provided with an electric heating means therein.
The continuous reactor according to claim 1, wherein the gas outlet further comprises reaction solution blocking means for preventing the discharge of the reaction solution.
5. The continuous reactor according to claim 4, wherein the reaction solution blocking means is a closure plate or a cyclone.
The continuous reactor according to claim 1, wherein the first impeller is connected to the impeller shaft by a worm gear, a straight bevel gear, a spiral bevel gear, or a helical bevel gear.
7. The method of claim 6, wherein the straight bevel gear, the spiral bevel gear, or the helical bevel gear comprises a combination of two horizontally arranged gears and two vertically arranged gears. A continuous reactor performing.
The method according to claim 1,
And further comprises a means for scraping up the viscous high-reactivity material on the bottom surface of the reactor, provided downstream of the second impeller.
9. The continuous reactor according to claim 8, wherein the means for scraping off the byproducts comprises the production of distilled alcohol without distillation and the distillation simultaneously with the production of distilled alcohol.
9. The continuous reactor according to claim 8, wherein the means for scraping the side reactant extends along the bottom surface of the reactor to the reactor wall surface.
11. The continuous reactor according to claim 10, wherein the means for scraping off the byproducts comprises a plurality of protrusions in the vicinity of the bottom and the wall of the reactor.
The continuous reactor according to claim 1, wherein the reactor further comprises a second supply unit for supplying steam or a part of the product to the reactor at the other side of the lower end.
The continuous reactor according to claim 1, wherein a sparger is installed inside the reactor of the raw material supply unit.
13. The continuous reactor according to claim 12, wherein a sparger is mounted inside the reactor of the second supply part.
The continuous reactor according to claim 1, wherein the raw material is a sugar alcohol and an acid catalyst.
16. The continuous reactor according to claim 15, wherein the acid catalyst has a boiling point of at least 160 DEG C at 10 mmHg and a pKa of 3.0 to 3.0, and is reacted with the raw material in a homogeneous manner.
16. The continuous reactor according to claim 15, wherein the acid catalyst is naphthalenesulfonic acid (NAS).
16. The method according to claim 1 or 15, wherein the raw material supply unit is provided with a sugar alcohol supply unit and a catalyst supply unit, or a sugar alcohol supply unit and a catalyst supply unit are separately provided. Continuous reactor.
A process for producing anhydrosugar alcohol by dehydrating sugar alcohol in the presence of a catalyst, characterized by using a continuous reactor which simultaneously performs the production and distillation of anhydrosugar alcohol according to any one of claims 1 to 18 A process for the production of anhydrosugar alcohol by simultaneous reaction and distillation.
20. The method of claim 19,
A process for the production of anhydrosugar alcohol by simultaneous sequential reaction and distillation comprising the steps of:
(a) feeding a raw material into a reactor;
(b) heating the first impeller, rotating the impeller shaft to rotate the first impeller and the second impeller, and stirring the reactant;
(c) recovering the product to be evaporated at the gas outlet; And
(d) discharging a high-viscosity byproduct from the liquid outlet.
21. The process according to claim 20, wherein the starting material is a sugar alcohol and an acid catalyst.
The process according to claim 21, wherein the acid catalyst has a boiling point of 160 ° C or more at 10 mmHg and a pKa of 3.0 to 3.0, and reacts with the raw material in a homogeneous manner. Way.
22. The method of claim 21, wherein the acid catalyst is a naphthalenesulfonic acid (NAS).
21. The method of claim 20, further comprising recycling a portion of the product recovered in step (c) to the reactor.
25. The process according to claim 24, wherein the steam is further fed in the recycle step.

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