KR102262461B1 - Continuous Reaction and Distillation Apparatus for Anhydrosuger Alcohol - Google Patents

Abstract

The present invention relates to a continuous reaction and distillation apparatus for anhydrosugar alcohol, and more particularly, by heating the reactor wall while supplying a mixture of a catalyst and sugar alcohol along the reactor wall to produce anhydrosugar alcohol and at the same time to produce anhydrosugar alcohol After vaporization, it relates to a continuous reaction and distillation apparatus for anhydrosugar alcohol that recovers anhydrosugar alcohol from a condenser installed in the center of the reactor.
The continuous reaction and distillation apparatus for anhydrosugar alcohol according to the present invention performs the reaction and distillation simultaneously in one reactor, so the amount of energy required to maintain the reduced pressure is small, and it can be operated continuously, so that it is economical for the production of anhydrosugar alcohol useful.

Description

Continuous Reaction and Distillation Apparatus for Anhydrosuger Alcohol

The present invention relates to a continuous reaction and distillation apparatus for anhydrosugar alcohol, and more particularly, by heating the reactor wall while supplying a mixture of a catalyst and sugar alcohol along the reactor wall to produce anhydrosugar alcohol and at the same time to produce anhydrosugar alcohol After vaporization, it relates to a continuous reaction and distillation apparatus for anhydrosugar alcohol that recovers anhydrosugar alcohol from a condenser installed in the center of the reactor.

Sugar alcohols are alcohols derived from sugar, and most have the structure of H(HCHO)n+1H. These sugar alcohols are classified into tetritol, hexitol, heptitol, etc. according to the number of carbons. Among them, hexitol having 6 carbons includes sorbitol, mannitol, iditol, galactitol, and the like. Of these, sorbitol and mannitol are food and beverage It is very useful as a sweetener in the field.

Anhydrosugar alcohol is a molecule having the form of a diol having two hydroxyl groups (-OH) in the molecule, and is generally prepared by dehydrating hexitol. Such anhydrosugar alcohol has a wide range of applications, such as cardiac and vascular treatment agents, adhesives, mouthwashes, emulsifiers, polymer additives, and bioplastics, and is expected to be applied in many industries.

The existing method for producing anhydrosugar alcohol is widely used using sulfuric acid as a catalyst and reacting under reduced pressure conditions (Korean Patent No. 10-1079518). However, when a strong acid such as sulfuric acid is used as a catalyst, the reactor is easily corroded, and an expensive reactor must be used to prevent corrosion, and a large amount of energy is consumed because a continuous pressure condition must be achieved, thereby increasing the overall production cost. . In addition, since it is not easy to manufacture a continuous vacuum reactor with high reliability, most processes use batch or semi-batch reactors.

On the other hand, since anhydrosugar alcohol has a high boiling point and is easily decomposed by high temperature heat, when using general atmospheric distillation, it is difficult to separate, so a reduced pressure distillation process is widely used (US 6,639,067). However, it is necessary to maintain a reduced pressure condition in the separation process as well as the reaction process, and since the yield ratio of anhydrosugar alcohol is lowered every time the multi-step process is performed, there is a disadvantage in that the manufacturing cost is rapidly increased.

Therefore, in order to solve the above problems, the present inventors supply a mixture of a catalyst and sugar alcohol along the reactor wall, heating the reactor wall to produce anhydrosugar alcohol, and at the same time vaporize the anhydrosugar alcohol, which is installed in the center of the reactor. Developed a continuous reaction and distillation device for anhydrosugar alcohol that recovers anhydrosugar alcohol from a condenser, and as a result of manufacturing anhydrosugar alcohol using this, the reduced pressure operation cost is reduced by integrating a reactor and a distillation device having a reduced pressure condition, It was confirmed that continuous reaction and distillation are possible, and the present invention was completed.

An object of the present invention is to provide an apparatus for continuous reaction and distillation of anhydrosugar alcohol.

Another object of the present invention is to provide a continuous reaction and distillation method of anhydrosugar alcohol using the apparatus.

In order to achieve the above object, the present invention is (a) a reactor that has a distributor installed on the upper part, the raw material flows down along the inner wall surface and reacts; (b) a raw material supply unit installed on one side of the upper part of the reactor; (c) separation/recovery means for unreacted raw materials and by-products, which are spaced apart from the bottom of the reactor by a certain distance and installed inside the reactor; (d) a condenser located in the center of the reactor and installed through the separation/recovery means; (e) located on one side of the lower end of the reactor, means for lowering the pressure inside the reactor; And (f) located in the center of the lower end of the reactor, it provides a continuous reaction and distillation apparatus for anhydrosugar alcohol comprising a product outlet for discharging the product flowing down from the condenser.

The present invention also provides a method for producing anhydrosugar alcohol by dehydrating sugar alcohol in the presence of an acid catalyst, characterized in that the continuous reaction and distillation apparatus is used, and a method for producing anhydrosugar alcohol through continuous reaction and distillation. .

The continuous reaction and distillation apparatus for anhydrosugar alcohol according to the present invention performs the reaction and distillation simultaneously in one reactor, so the amount of energy required to maintain the reduced pressure is small, and it can be operated continuously, so that it is economical for the production of anhydrosugar alcohol useful.

1 is a view showing the inside of anhydrosugar-alcohol continuous reaction and distillation apparatus according to the present invention.

Unless defined otherwise, 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 those well known and commonly used in the art.

In the present invention, in the production of anhydrosugar alcohol using a continuous reaction and distillation apparatus of anhydrosugar alcohol, when using the apparatus in which the reactor and the distillation unit are integrated, the energy used during depressurization is small and continuous operation is possible. did.

In the present invention, anhydrosugar alcohol is produced by heating the reactor wall while supplying a mixture of catalyst and sugar alcohol along the reactor wall, and the anhydrosugar alcohol is vaporized at the same time, and then the anhydrosugar alcohol is recovered in the condenser installed in the center of the reactor. A continuous reaction and distillation apparatus for anhydrosugar alcohol was developed, and the production of anhydrosugar alcohol was performed using this. As a result, it was confirmed that the yield of anhydrosugar alcohol at the same level as that of the conventional sulfuric acid reduced pressure reaction was achieved, and continuous operation was possible.

Therefore, the present invention, in one view, (a) the distributor 140 is installed on the upper part, the reactor 100 that reacts by flowing down the raw material along the inner wall; (b) a raw material supply unit 110 installed on one side of the upper part of the reactor; (c) separated by a certain distance from the bottom of the reactor and installed inside the reactor, unreacted raw material and by-product separation / recovery means (300); (d) a condenser 200 located in the center of the reactor and installed through the separation/recovery means; (e) located on one side of the reactor, means 500 for lowering the pressure inside the reactor; And (f) located in the center of the lower end of the reactor, it relates to anhydrosugar-alcohol continuous reaction and distillation apparatus comprising a product outlet 130 for discharging the product flowing down from the condenser 200.

In the present invention, the reactor 100 is preferably manufactured in a cylindrical shape to resist changes in internal pressure, but is not limited thereto. In addition, it is preferable that the distributor 140 is installed at the top of the reactor so that the raw material supplied from the raw material supply unit is dispersed and flowed down toward the wall of the reactor. When using the disk-shaped distributor 140 smaller than the inner diameter of the reactor, the raw material supplied from the upper part of the disk-shaped distributor 140 flows into the gap between the disk and the inner wall of the reactor, and the raw material flowing down from the gap flows along the reactor wall will come down This distributor can be used without limitation as long as it is a distributor capable of distributing raw materials to the wall of the reactor, such as a cone-shaped structure and a circular porous injection nozzle, as well as the disk-shaped distributor 140 .

In the present invention, the raw material may be characterized in that the sugar alcohol and acid catalyst. An acid catalyst is used in the process of converting sugar alcohols into anhydrous sugar alcohols. In the conventional continuous reaction, a solid acid catalyst is used to prevent loss due to volatilization of the catalyst, but in the present invention, a catalyst having a higher boiling point (BP) than an anhydrosugar alcohol evaporated at the same time as the reaction is used for evaporation. Minimize the loss caused by Therefore, the acid catalyst has a boiling point of 160° C. or higher at 10 mmHg, a pKa of -3.0 to 3.0, and it is preferable to react in the same manner as the raw material.

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

(a) boiling point

In order to maintain catalytic activity without evaporation of the catalyst during the reaction, a catalyst having a higher boiling point than child carbide (160℃ at 10mmHg) is selected. That is, the boiling point at 10 mmHg is 160°C or higher.

(b) acidity (pKa)

A catalyst having an appropriate acidity to reduce the formation of by-products such as polymers or coke under high-temperature reaction conditions is used. The pKa range for increasing the yield may be -3.0 <pKa<3.0, preferably the range is -2.0 <pKa<2.5, and more preferably the range is -1.0 <pKa<1.9.

(3) homogeneous phase

A catalyst is used that 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. To this end, the melting point may be 180° C. or less, preferably 160° C. or less, more preferably 140° C. or less, and still more preferably 120° C. or less.

The catalyst may be naphthalenesulfonic acid. Specific compounds of naphthalene sulfonic acid include 2-naphthalene sulfonic acid or 1-naphthalene sulfonic acid, and these compounds are isomers formed when naphthalene is sulfonated. 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, b.p.=392°C.

In the present invention, the separation/recovery means 300 has a certain inclination so that the anhydrosugar alcohol flowing down the condenser 200 and unreacted sugar alcohol flowing down the reactor wall and by-products do not mix with each other. It may be characterized in that it is installed in a linear manner so that the separated sugar alcohol and by-products flow to one side and are separated. The separation/recovery means 300 is preferably installed at a certain distance from the lower end of the reactor in order to recover unreacted raw materials, catalysts and by-products flowing down from the walls of the reactor. At this time, there is a hole through which the condenser 200 passes at the center of the separation/recovery means, and the unreacted products and by-products flowing down the wall are collected at one side and collected 120 , forming an angle with the central axis of the reactor.

In the present invention, the condenser 200 may be characterized in that the anhydrosugar alcohol evaporated at the same time as the reaction on the wall of the reactor is condensed to flow to the lower part of the separation/recovery means 300 . The condenser 200 of the present invention is installed in the center of the reactor, and it is preferable to have a length to the lower end of the reactor through the separation/recovery means 300 . The condenser of the present invention is preferably a condenser 200 composed of several pipes so that the condensed anhydrosugar alcohol can flow down to the lower end of the reactor, but is not limited thereto. The anhydrosugar alcohol evaporated at the same time as the reaction on the wall of the reactor is cooled in the condenser 200 in the center of the reactor and liquefied. The cooled anhydrosugar alcohol moves to the lower part on the condenser 200 , passes through the through hole of the separation/recovery means 300 , and is recovered 130 at the lower part of the reactor. The condenser of the present invention preferably has a temperature of 0-100° C., but can be freely adjusted according to the pressure production rate of the reactor.

In the present invention, the reactor is located on one side of the reactor, it may be characterized in that it includes a means 500 for lowering the pressure inside the reactor. The production reaction of the anhydrosugar alcohol of the present invention occurs under reduced pressure, and since distillation proceeding simultaneously with the reaction also uses reduced pressure distillation, it is preferable to lower the pressure inside the reactor by using the means 500 for lowering the pressure. At this time, the pressure inside the reactor is preferably 10 to 40 bar, but is not limited thereto.

In the present invention, the reactor is located in the center of the lower end, it may be characterized in that it includes a product outlet 130 for discharging the product flowing down from the condenser.

In the present invention, it is installed along the outer wall of the reactor, it may be characterized in that it further comprises a means 400 for heating the reactor to convert the sugar alcohol on the inner wall of the reactor into anhydrosugar alcohol. The conversion reaction of anhydrosugar alcohol takes place at a high temperature of 150 ~ 250 ℃. Also, a means 400 for heating the walls of the reactor is required since it must be distilled simultaneously with the reaction. It is preferable to use a heating medium as the heating means, but is not limited thereto. In addition, the reactor wall is preferably maintained at 150 ~ 220 ℃, but can be adjusted according to variables such as the temperature of the reactor and control of the evaporation amount.

As used herein, the term 'heating media' refers to a medium that transfers heat, and the fruit heated from the heat source is transported and serves to transfer heat to the inside or surface of the object. In general, a liquid material is often used, but gas or solid can also transfer heat, and it can be used under transportable conditions.

In the present invention, the reaction device may be characterized in that it further comprises a means for re-injecting the unreacted raw material into the reactor by separating the unreacted raw material and the by-product recovered from the unreacted raw material and by-product separation/recovery means. . The unreacted raw materials and by-products in the reactor are collected on one side of the middle part of the reactor by the separation/recovery means, and they are recovered (120) to separate the by-products, and the unreacted raw materials and catalysts are introduced into the raw material supply unit (110). It is preferable to play

In the present invention, it may be characterized in that the reactor rotation means is additionally provided to mix the raw materials flowing down along the inner wall of the reactor. When the reactor is rotated, the reaction and distillation efficiency can be increased because the reactants can be continuously mixed while flowing down the inner wall of the reactor.

In the present invention, it may be characterized in that it further comprises a means for scraping the inner wall surface inside the reactor to move to the separation/recovery means. The means for scraping the inner wall makes it easy to flow down by-products with poor fluidity generated as the reaction proceeds, and makes the movement speed of the raw material uniform so that the reaction and distillation occur at a constant rate.

In another aspect, in a method for producing anhydrosugar alcohol by dehydrating sugar alcohol in the presence of an acid catalyst, the method for producing anhydrosugar alcohol through continuous reaction and distillation, characterized in that using the continuous reaction and distillation apparatus is about

In the present invention, the method for producing anhydrosugar alcohol through the continuous reaction and distillation comprises the steps of (i) introducing a sugar alcohol and an acid catalyst into a reactor; (ii) reacting the introduced enteric alcohol and acid catalyst while flowing along the reactor wall, heating the reactor wall to evaporate the product at the same time as the reaction; (iii) condensing the evaporated product in a condenser at the center of the reactor; (iv) recovering the product flowing down the condenser; and (v) recovering unreacted raw materials and reaction by-products in step (ii) to separate unreacted sugar alcohols and acid catalysts, and then reintroducing them into the reactor.

As the specific parts of the present invention have been described in detail above, for those of ordinary skill in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.

100: reactor
110: raw material supply unit
120: Unreacted raw material and by-product outlet
130: product outlet
140: divider
200: condenser
300: separation / recovery means
400: heating means
410: fruit (Heating Media) inlet
420: fruit outlet
500: means of lowering the pressure

Claims (13)

A continuous reaction and distillation apparatus for anhydrosugar alcohol comprising:
(a) a reactor with a distributor installed at the top, and reacting by flowing down the raw material along the inner wall;
(b) a raw material supply unit installed on one side of the upper part of the reactor;
(c) separation/recovery means for unreacted raw materials and by-products, which are spaced apart from the bottom of the reactor by a certain distance and installed inside the reactor;
(d) a condenser located in the center of the reactor and installed through the separation/recovery means;
(e) located on one side of the reactor, means for lowering the pressure inside the reactor; and
(f) a product outlet located in the center of the lower end of the reactor and discharging the product flowing down from the condenser;
The separation/recovery means is installed in an oblique shape with a certain inclination so that the anhydrosugar alcohol flowing down the condenser and unreacted sugar alcohol and by-product flowing down the reactor wall do not mix with each other so that the separated sugar alcohol and by-product It is characterized in that it flows to one side and separates.
The continuous reaction and distillation apparatus for anhydrosugar alcohols according to claim 1, wherein the raw materials are sugar alcohols and acid catalysts.
The continuous reaction and distillation apparatus for anhydrosugar alcohol according to claim 2, wherein the acid catalyst has a boiling point of 160° C. or higher at 10 mmHg, a pKa of -3.0 to 3.0, and reacts homogeneously with the raw material.
The apparatus of claim 3, wherein the acid catalyst is naphthalenesulfonic acid (NAS).
delete The continuous reaction and distillation apparatus of claim 1, wherein the condenser condenses the anhydrosugar alcohol evaporated at the same time as the reaction on the wall of the reactor to flow to the lower part of the separation/recovery means.
The continuous reaction and distillation of anhydrosugar alcohol according to claim 1, further comprising means for heating the reactor installed along the outer wall of the reactor and converting the sugar alcohol on the inner wall of the reactor into anhydrosugar alcohol. Device.
The continuous anhydrosugar alcohol according to claim 1, further comprising a means for separating unreacted raw materials and by-products recovered from the unreacted raw material and by-product separation/recovering means and re-injecting the unreacted raw material into the reactor. Reaction and distillation apparatus.
The apparatus for continuous reaction and distillation of anhydrosugar alcohol according to claim 1, further comprising a reactor rotating device to mix the raw materials flowing down along the inner wall of the reactor.
The continuous reaction and distillation apparatus for anhydrosugar alcohol according to claim 1, wherein the reactor further comprises a means for scraping the inner wall surface to move to the separation/recovery means.
A method for producing anhydrosugar alcohol by dehydrating sugar alcohol in the presence of an acid catalyst, wherein the continuous reaction and distillation apparatus according to any one of claims 1 to 4 and 6 to 10 is used. Method for producing anhydrosugar alcohol through reaction and distillation.
12. The method of claim 11,
Method for producing anhydrosugar alcohol through continuous reaction and distillation, characterized in that it comprises the following steps:
(i) introducing a sugar alcohol and an acid catalyst into the reactor;
(ii) reacting the introduced enteric alcohol and acid catalyst while flowing along the reactor wall, heating the reactor wall to evaporate the product at the same time as the reaction;
(iii) condensing the evaporated product in a condenser at the center of the reactor;
(iv) recovering the product flowing down the condenser; and
(v) recovering unreacted raw materials and reaction by-products in step (ii) to separate unreacted sugar alcohols and acid catalysts, and then reintroducing them into the reactor.
The method of claim 11, wherein the acid catalyst is naphthalenesulfonic acid (NAS).

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