WO2016105111A1

WO2016105111A1 - Continuous reactor for simultaneously producing and distilling anhydrosugar alcohol, and method for preparing anhydrosugar alcohol by using same

Info

Publication number: WO2016105111A1
Application number: PCT/KR2015/014153
Authority: WO
Inventors: 최영보
Original assignee: 에스케이이노베이션 주식회사
Priority date: 2014-12-23
Filing date: 2015-12-23
Publication date: 2016-06-30
Also published as: KR20160076780A; KR102262949B1

Abstract

The present invention relates to a continuous reactor for simultaneously producing and distilling an anhydrosugar alcohol, and a method for preparing an anhydrosugar alcohol by using the same and, more specifically, to a reactor comprising an impeller blade, having a specific structure, for carrying out, in one reactor, the conversion of sorbitol into an anhydrosugar alcohol and the distillation and separation step of the produced anhydrosugar alcohol.

Description

Continuous reactor for simultaneously producing and distilling anhydrosugar alcohols and a method for producing anhydrosugar alcohols using the same

The present invention relates to a continuous reactor for simultaneously producing and distilling anhydrosugar alcohols and a method for producing anhydrosugar alcohols using the same. More particularly, the reaction for converting sugar alcohols such as sorbitol to anhydrosugar alcohols and The present invention relates to a reactor having an impeller blade having a specific structure for performing distillation and separation of a sugar alcohol in one reactor.

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

Anhydrosugar alcohols are prepared through dehydration reactions that remove one or more water molecules inside the sugar alcohol molecule, and have new bond structures that are completely different from sugar alcohols such as double bonds, ether bonds, cyclic bonds, and the like. For example, if 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 can be prepared. Such anhydrosugar alcohols are expected to be applied in many industries because the application of a variety of applications, such as cardiac and vascular treatments, adhesives, mouthwashes, emulsifiers, polymer additives, bioplastics.

Conventional methods for producing anhydrosugar alcohols are widely used to react under reduced pressure using sulfuric acid as a catalyst (Republic of Korea Patent Registration 10-1079518). However, if 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 since the decompression condition must be continuously achieved, a large amount of energy is consumed and the overall production cost increases. . In addition, it is not easy to manufacture a continuous vacuum reactor having high reliability, most of the processes are using a batch or semi-batch reactor.

On the other hand, anhydrosugar alcohols have a high boiling point, and since they are easily decomposed by high temperature heat, when using ordinary atmospheric distillation, it is difficult to separate them, so a vacuum distillation process is frequently used (US 6,639,067). However, the pressure reduction conditions must be maintained not only in the reaction process but also in the separation process, and the manufacturing cost increases rapidly because the yield ratio of the anhydrosugar alcohol is lowered every time the multi-step process is performed.

In order to solve the disadvantage of this multi-stage reactor, a reactor that simultaneously performs the reaction and distillation in one reactor has been developed. In this direct distillation method, since the production and distillation of isosorbide should be performed at the same time in the reactor, the apparatus for this needs to have both the characteristics of the reactor and the characteristics of the still. In particular, in order to rapidly evaporate the isosorbide formed in the reaction solution, the surface agitation (Surface Renewal) of the reaction solution is required.

Republic of Korea Patent 1376481 discloses a reactor for performing distillation at the same time as the reaction. Although the present invention has the advantage of distilling isosorbide generated at the same time as the reaction using a solid acid catalyst, it is easy to separate the catalyst and increase the yield and purity of the isosorbide. Distillation only on the surface has the disadvantage that the overall reaction rate is slow.

Accordingly, the present inventors endeavored to solve the above problems, and as a result, a reactor having a first impeller rotating vertically and a second impeller rotating horizontally to stir the reactant for surface renewal of the reaction solution. Using to develop a reactor that can perform the conversion of sugar alcohol to anhydrosugar alcohol and distillation of anhydrosugar alcohol at the same time in one reactor, by using this to produce anhydrosugar alcohol, generated inside the reaction solution As the evaporation rate of the anhydrous sugar alcohol is increased, the reaction efficiency is enhanced, and when an additional impeller blade for discharging high viscosity side reactions is installed, it is confirmed that the side reactions are also easily discharged, thereby completing the present invention. .

The above information described in this Background section is only for improving the understanding of the background of the present invention, and therefore does not include information that forms a prior art known to those of ordinary skill in the art. You may not.

발명의 요약Summary of the Invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a continuous reactor for simultaneously producing and distilling anhydrosugar alcohol and a method for producing anhydrosugar alcohol using the same.

In order to achieve the above object, the present invention is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohols, including a raw material supply unit for supplying raw materials, gas outlet, liquid outlet and the stirring means, the stirring means (i Impeller shaft rotated by the drive means; (ii) a first impeller installed in the middle of the impeller shaft and rotating in a vertical direction according to the rotation of the impeller; And (iii) a second impeller positioned at the lower end of the impeller shaft and rotating in a horizontal direction according to the rotation of the impeller.

The present invention also provides a method for producing anhydrosugar alcohols by simultaneously performing a continuous reaction and distillation, in the method of producing anhydrosugar alcohols by dehydrating sugar alcohols in the presence of a catalyst. do.

Figure 1 shows the overall configuration of the reactor and the direction of rotation of the impeller according to the present invention.

Figure 2 shows a detailed view of the first impeller.

3 shows a cut plane of the first impeller.

Figure 4 shows a state of the anhydrosugar alcohol reactor provided with a screen plate according to the present invention.

Figure 5 shows the gear used in the connection of the first impeller used in the present invention (a) worm gear (b) straight bevel gear (c) spiral bevel gear (d) helical bevel gear (e) arranged horizontally The combination of two gears and two gears arranged perpendicularly is shown, respectively.

Figure 6 shows a state of the anhydrosugar alcohol reactor having a means for scraping off the heavy reactants according to the present invention.

7 shows the means for scraping off side reactions and the outlet of the reactor bottom.

8 shows a state of anhydrosugar alcohol reactor with means for scraping off side reactions extending to the wall of the reactor according to the invention.

Figure 9 shows a state of the anhydrosugar alcohol reactor having a second supply according to the present invention.

발명의 상세한 설명 및 구체적인 Detailed description and specifics of the invention 구현예Embodiment

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 well known and commonly used in the art.

In the present invention, in the production of anhydrosugar alcohols using a continuous reaction and distillation apparatus of anhydrosugar alcohols, using a reactor having a first impeller rotating vertically and a second impeller rotating horizontally and a reactor in which a still distillation unit is integrated. When the product is distilled at high speed, it was to confirm that the continuous operation is possible.

In the present invention, using the anhydrosugar alcohol continuous reactor having a first impeller rotating in the vertical direction in accordance with the rotation of the stirring means and a 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 anhydrosugar alcohol was the same as that of the reduced pressure reaction using the conventional sulfuric acid as a catalyst, and the distillation rate of the anhydrosugar alcohol produced by the first impeller was agitated. It confirmed that it improves more.

Therefore, in one aspect, the present invention is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohols, including a raw material supply unit, a gas outlet, a liquid outlet and a stirring means for supplying raw materials, the stirring means is (i) An impeller shaft rotated by a rotating motor; (ii) a first impeller installed in the middle of the impeller shaft and rotating in a vertical direction according to 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 according to the rotation of the impeller.

In the present invention, the gas outlet may be characterized in that the water and anhydrosugar alcohol generated through the reaction is evaporated and discharged to the gas phase. In addition, the liquid discharge port is mainly discharged (Heavy Residues) is discharged, unreacted sugar alcohol and anhydrous sugar alcohol and water that are not completely vaporized may be discharged together.

In the present invention, the first impeller 220 may be characterized in that a plurality of grooves 221 is formed on the surface. The first impeller 220 is preferably located in the upper layer of the raw material filled in the reactor, but is not limited thereto. The first impeller 220 is rotated about the axis orthogonal to the impeller shaft 210, and thus the upper layer of the raw material is continuously stirred (Surface Renewal) so that anhydrous sugar alcohol produced by the reaction of the raw material is easily vaporized. To help. In this case, 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 may be increased to more rapidly vaporize the anhydrosugar alcohol.

In the present invention, the first impeller 220 may be characterized in that the heating means 222 is installed therein. Since the inside of the reactor is maintained at a high temperature of more than 150 ℃ and low pressure of less than 200torr produced anhydrosugar alcohol naturally evaporates. However, in order to increase the efficiency of evaporation, it is preferable that the first impeller has a heating means 222 installed therein. At this time, the plurality of grooves to increase the surface area serves to increase the surface area of the impeller in contact with the anhydrosugar alcohol may play a role of making the evaporation by heat easier. In addition, the heating means is preferably electric heating means, but is not limited thereto.

In the present invention, the gas outlet 120 may be characterized in that it comprises a reaction solution blocking means for preventing the discharge of the reaction solution. When the sugar alcohol is reacted under reduced pressure, boiling water is generated while the anhydrous sugar alcohol and water are rapidly vaporized. Due to this boiling phenomenon, a portion of the reaction solution may be discharged through the gas outlet 310 to reduce the concentration of the product. In addition, due to the rotation of the first impeller, some liquid may be scattered 310 toward the gas outlet and 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 product steam at the gas outlet. At this time, the reaction solution blocking means may be used without limitation means for separating the gas and the liquid, but preferably may be used a screening plate 300 or a cyclone separator that can cover the gas outlet.

In the present invention, the first impeller 220 may be connected to the impeller shaft, worm gear, straight bevel gear, spiral bevel gear or helical bevel gear. Worm gears or bevel gears are commonly used to transfer rotation between two orthogonal axes. In particular, bevel gears are distinguished from linear bevel gears, spiral bevel gears, or helical bevel gears according to the type of engagement. It is preferable to use a gear. At this time, a pair of first impellers are installed on both sides, and a second impeller is connected to the lower side, and therefore, the first impeller is preferably composed of a combination of two gears arranged horizontally and two gears arranged vertically.

The impeller according to the present invention may be installed at the lower portion of the second impeller 230, and may further include a means 240 for scraping the high viscosity (Heavy Residues) of the reactor bottom surface. When the anhydrosugar alcohol is prepared by the pressure reduction reaction, a side reaction product such as a polymer having high viscosity or a carbohydrate is produced. This side reaction is discharged to the liquid outlet at the bottom of the reactor. However, since the side reactions are difficult to smoothly discharge due to low fluidity, it is preferable to discharge the side reactions by means of scraping the high side reactions having high viscosity at the bottom of the reactor. At this time, the means for scraping off the side reactants is preferably made of silicon or plastic 241 which is stable at high temperature at the lower end contacting the bottom of the reactor to prevent damage to the bottom of the reactor. Also, the means for scraping off the side reactants move along the curve of the bottom of the reactor, and it is desirable to minimize the gap with the bottom of the reactor.

In the present invention, the means for scraping off the side reactions may be characterized in that it extends along the reactor bottom to the reactor wall. The side reactions are mainly formed at the bottom of the reactor, but are also formed on the wall of the reactor, which impedes the rotation of the impeller, so that the means for scraping off the side reactions preferably extends along the bottom of the reactor to the reactor wall. In addition, the means for scraping off side reactions have protrusions on the bottom and wall of the reactor, so that they can be located closer to the inner surface of the reactor, and when the side reactions precipitate on the inner surface of the reactor, they can be more effectively scraped off by the protrusions. have.

The reactor according to the present invention may further include a second supply unit 140 for supplying a portion of steam or product to the reactor. The supplied steam assists in the evaporation of the anhydrosugar alcohol produced in the reactor and serves to maintain the temperature inside the reactor. Part of the product can also be recycled to increase the purity of the anhydrosugar alcohols produced. At this time, the sparger is mounted inside the reactor of the second supply unit, so that a part of the steam and the product to be supplied are uniformly supplied into the reactor using the sparger. In addition, it is preferable that the sparger is also mounted inside the reactor of the raw material supply unit to which the raw material is supplied.

In the present invention, the raw material may be characterized in that the sugar alcohol and acid catalyst. Acid catalysts are used in the conversion of sugar alcohols to anhydrosugar alcohols. In the conventional continuous reaction, a solid acid catalyst is used to prevent loss due to volatilization of the catalyst. However, in the present invention, a catalyst having a higher boiling point (BP) than the anhydrosugar alcohol evaporated simultaneously with the reaction is used for evaporation. Minimize losses. 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 preferably reacts in a homogeneous phase with the raw material.

Catalysts suitable for the present invention satisfy the following conditions.

(a) boiling point

A catalyst having a boiling point higher than isosorbide (160 ° C. at 10 mmHg) is selected to maintain catalyst activity without evaporation of the catalyst during the reaction. That is, the boiling point in 10 mmHg is 160 degreeC or more.

(b) acidity (pKa)

Catalysts having a suitable acidity are used to reduce the formation of side reactants such as polymers or coke at high temperature reaction conditions. The pKa range for increasing yield is -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

Catalysts are used that increase the contact efficiency between the catalyst and the feed, react in a homogeneous phase at reaction conditions, and maintain their activity without evaporation of the catalyst. To this end, the melting point may be 180 ° C or lower, preferably 160 ° C or lower, more preferably 140 ° C or lower, and even more preferably 120 ° C or lower.

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

In the present invention, the first impeller and the second impeller may be characterized in that each installed two to five. 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 up and down on one impeller shaft, it is also possible to install each of several impeller shaft.

In another aspect, the present invention provides a method for producing anhydrosugar alcohols by dehydrating sugar alcohols in the presence of a catalyst, wherein the continuous reactor is used to produce anhydrosugar alcohols simultaneously by continuous reaction and distillation. It is about.

Method for producing anhydrosugar alcohol according to the present invention comprises the steps of (a) adding a sugar alcohol and an acid catalyst to the reactor; (b) rotating the impeller shaft to rotate the first impeller and the second impeller to agitate the reactants; (c) recovering the product evaporated by the heated first impeller at the gas outlet; And (d) may be characterized in that it comprises the step of discharging the high viscosity side reactions from the liquid outlet.

In the present invention, the raw material may be characterized in that the sugar alcohol and acid catalyst.

In the present invention, the acid catalyst has a boiling point of 160 ° C or higher at 10 mmHg, pKa is -3.0 to 3.0, it can be characterized in that the reaction with the raw material homogeneous.

In the present invention, the acid catalyst may be characterized in that naphthalenesulfonic acid (NAphthalenesulfonic Acid, NAS).

In the present invention, it may be characterized in that it further comprises the step of recycling the product recovered in the step (c) to the reactor. When the resulting anhydrosugar alcohol is fed back into the reactor to increase the content of the anhydrosugar alcohol in the reactor, it is possible to produce high purity anhydrosugar alcohol. Therefore, it is preferable to recycle some of the product to increase the purity of the anhydrosugar alcohol, and at this time, it is more preferable to further supply steam to maintain the temperature inside the reactor, and to help evaporation of the anhydrosugar alcohol.

As described above in detail specific parts of the present invention, it will be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. will be. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Explanation of the sign

100: reactor 110: raw material supply unit

120: gas outlet 130: liquid outlet

140: second supply unit 200: driving means

210: impeller shaft 220: first impeller

221: first impeller groove 222: electrical heating means

230: second impeller

240: means of scraping side reactions

241: Silicone or plastic at the bottom of the means for scraping off side reactions

300: blanking plate 310: scattering reaction solution

The continuous reactor and the production method of the anhydrosugar alcohol using the same and the production and distillation of anhydrosugar alcohol according to the present invention using a reactor having both the characteristics of the reactor and the distillator, the production and distillation of anhydrosugar alcohol Anhydrous sugar alcohol produced by continuously stirring in one reactor and reacting the surface of the reaction solution by the first impeller vertically rotating, and stirring the reaction solution by the second impeller rotating horizontally. Its high distillation efficiency makes it useful for economical production of anhydrosugar alcohols.

Claims

In the continuous reactor for simultaneously performing the production and distillation of the anhydrosugar alcohol including a raw material supply unit, a gas discharge port, a liquid discharge port and a stirring means, the raw material is supplied,

The stirring means,

(i) an impeller shaft rotated by the drive means;

(ii) a first impeller installed in the middle of the impeller shaft and rotating in a vertical direction according to 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 according to the rotation of the impeller;

Continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohols characterized in that it comprises a.
The method of claim 1,

The first impeller is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohol, characterized in that a plurality of grooves are formed on the surface.
The method of claim 1,

The first impeller is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohols, characterized in that the heating means is installed therein.
The method of claim 1,

The gas outlet is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohols, characterized in that it comprises a reaction solution blocking means for preventing the discharge of the reaction solution.
The method of claim 4, wherein

The reaction solution blocking means is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohol, characterized in that the screening plate or cyclone.
The method of claim 1,

The first impeller is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohol, characterized in that connected to the impeller shaft and worm gear, straight bevel gear, spiral bevel gear or helical bevel gear.
The method of claim 6,

The straight bevel gear, spiral bevel gear or helical bevel gear is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohols, characterized in that consisting of a combination of two gears arranged horizontally and two gears arranged vertically.
The method of claim 1,

A continuous reactor installed at the bottom of the second impeller, further comprising a means for scraping off the high viscosity side reactions on the bottom of the reactor to continuously produce and distill the anhydrosugar alcohol.
The method of claim 8,

The means for scraping off the side reactions is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohols, characterized in that the bottom portion in contact with the bottom of the reactor is made of silicon or plastic.
The method of claim 8,

The means for scraping off the side reactions is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohols, characterized in that extending along the reactor bottom surface to the reactor wall.
The method of claim 10,

The means for scraping off the side reactions is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohols, characterized in that it has a plurality of protrusions in the vicinity of the bottom and wall surface of the reactor.
The method of claim 1,

The reactor is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohol further comprising a second supply for supplying a portion of steam or product to the reactor on the other side of the lower end.
The method of claim 1,

A continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohol, characterized in that the sparger is mounted inside the reactor of the raw material supply unit.
The method of claim 12,

A continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohol, characterized in that the sparger is mounted inside the reactor of the second supply unit.
The method of claim 1,

The raw material is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohol, characterized in that the sugar alcohol and acid catalyst.
The method of claim 15,

The acid catalyst is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohol, characterized in that the boiling point at 10mmHg or more at 160 ℃, pKa is -3.0 ~ 3.0, and reacts in the same phase with the raw material.
The method of claim 15,

The acid catalyst is a continuous reactor for simultaneously performing the production and distillation of anhydrosugar alcohols, characterized in that naphthalenesulfonic acid (Naphthalenesulfonic Acid, NAS).
The method according to claim 1 or 15,

The raw material supply unit is a continuous reactor for simultaneously performing the production and distillation of the anhydrosugar alcohol, characterized in that the sugar alcohol supply and the catalyst supply is installed as one, or the sugar alcohol supply and the catalyst supply is installed separately.
A method for producing anhydrosugar alcohols by dehydrating sugar alcohols in the presence of a catalyst, characterized by using a continuous reactor for simultaneously producing and distilling the anhydrosugar alcohols of any one of claims 1 to 18. Process for producing anhydrosugar alcohols through simultaneous reaction and distillation.
The method of claim 19,

Method for producing anhydrosugar alcohols through simultaneous reaction and distillation, characterized in that it comprises the following steps:

(a) introducing the raw material into the reactor;

(b) rotating the impeller shaft to rotate the first impeller and the second impeller to agitate the reactants;

(c) recovering the product to be evaporated at the gas outlet; And

(d) discharging the high viscosity side reactions from the liquid outlet.
The method of claim 20,

The raw material is a sugar alcohol and an acid catalyst, characterized in that the production of anhydrosugar alcohol through the simultaneous execution of the continuous reaction and distillation.
The method of claim 21,

The acid catalyst has a boiling point of at least 160 ℃ at 10mmHg, pKa is -3.0 ~ 3.0, and the method of producing anhydrosugar alcohols through the simultaneous execution of the continuous reaction and distillation, characterized in that the reaction with the raw material and the same phase.
The method of claim 21,

The acid catalyst is a naphthalenesulfonic acid (Naphthalenesulfonic Acid, NAS) characterized in that the production of anhydrosugar alcohol through the simultaneous execution of the continuous reaction and distillation.
The method of claim 20,

A method for producing anhydrosugar alcohols by simultaneously performing a continuous reaction and distillation further comprising the step of recycling a portion of the product recovered in step (c) to the reactor.
The method of claim 24,

The method of producing anhydrosugar alcohols through the simultaneous reaction of the continuous reaction and distillation, characterized in that further supply of steam in the recycle step.