TW200413308A - Process and apparatus for the acid-catalyzed hydrolysis of carboxylic esters from azeotropic mixtures - Google Patents

Abstract

The present invention relates to a process, and also to an apparatus, for hydrolytically cleaving carboxylic esters from chemical processes in which the carboxylic ester is obtained as an azeotropic mixture of carboxylic ester and the corresponding alcohol.

Description

200413308 V. Description of the invention (1) 1. [Technical field to which the invention belongs] In some chemical methods, the azeotropic mixing of acetic acid esters and corresponding alcohols may appear as a by-product. For example, the azeotrope can be: acid ester and methanol (the azeotrope contains 9% by weight of methanol, the boiling point is 5 ^ 0 C), ethyl acetate and ethanol (the azeotrope contains 31% by weight alcohol has a boiling point of 71.PC), propyl acetate and bupropanol (the azeotrope contains 49% / by weight bupropanol, the boiling point is 95 ° C), isopropyl acetate and 2- Propanol (^ Buddha contains 52% by weight of 2-propanol with a boiling point of 80.0, n-acetate, di and n-butanol (azeotrope contains 47% by weight of n-butanol, boiling point 2C) or copolymers of secondary-butyl acetate and secondary-butanol (the azeotrope contains 86% by weight of secondary-butanol, with a boiling point of 99.80c) and other copolymers. Examples In other words, if the methyl acetate obtained in the chemical method is relatively small, the direct marketing of such contaminated by-products or waste products is usually not carried out, or because it cannot be used in other processing methods. However, if Purification of the acetic acid (the purification work is costly and complicated), and adding the reactants acetic acid and methanol to obtain a value far higher than the contaminated acetic acid-Qiao itself The dissociation of carboxylic acid esters is best carried out by means of hydrolysis of acid S. The acidic hydrolysis is an equilibrium reaction which can be combined with a traditional distillation reactor or a separate reactive distillation column, as a batch or It is implemented in a continuous manner. [Prior art] US Patent No. 5,770,770 has disclosed a method in a reactive distillation column = hydrolyzed monoacetic acid formic acid mixture, which contains at least 50% by weight of acetic acid methyl acetate in methyl acetate. The hydrolysis of ester fluids

V. Description of the invention (2) The water system and water quality shall be alcoholic acid and methyl alcohol. The exchange of the above mentioned properties shall be performed in one step to deactivate the reaction zone of the continuous ion exchange packing. It mixes and flows through the ion exchange packing in the opposite direction. Methyl acetate without hydrazone 1 was recycled in the reaction zone. The hydrolysate is removed at the bottom of the column. Recycle back to the reaction zone. The sinus office of methyl acetate 丨 A _ _ is only a mixture of methyl acetate from polyethylene waste, which has, for example, an azeotropic composition of ethyl acetate and fermented yeast. The teaching of U.S. Patent No. 5,770,770 is to use a strongly acidic ionizer as a catalyst for the hydrolysis of carboxylic acid esters. Disadvantages of the method of US 5,770,770, which uses only a single reactive distillation column, are that the amyl ester is only partially hydrolyzed. Another disadvantage of this method is that the method has two feed points. The reason is that the separate feed is not good for energy consumption. The remote reactant fluid forces the use of at least one additional purification step. Another disadvantage is that metal ions from the feed of acetic acid acetate can catalyze the catalyst in the reactive distillation column, which results in shortening the operating time of these plants. In the published European patent specification EP 1 22 0 825 A2, a method and a method in which a feed flow system including a carboxylic acid ester is first introduced ~ a pre-reactor 'in the pre-reactor, the carboxylic acid ester is In contact with the first catalyst in the presence of water, the water partially dissociates the carboxylic acid ester into a hydrolysate. The reaction mixture from the pre-reactor is passed into a reactive distillation column to be contacted with a second catalyst in order to at least partially convert the resulting carboxylic acid ester into the corresponding carboxylic acid and alcohol. The advantage of the method described in European patent EP 1 2 2 0 8 2 5 is that the conversion rate of two-arbitrary scriptures is higher than that of the method just described. Moreover, using a pre-reactor can improve

Page 5 200413308 V. Description of the invention (3) For the operating time of the reactive distillation column, the toxins (eg, metal ions) of the Gein catalyst remain mainly in the prereactor. The selection limit of the catalyst material used in the prereactor is less than that of the favorable catalytic packing used in the reactive distillation column. ~ The disadvantage of the method described in long European patent EP 1 220 82 5 is that if the entering fluid contains the corresponding alcohol, the acid-catalytic hydrolysis is chemically balanced from the pre-reactor and / or the reactive distillation column reaction device The product is removed. For a composition with a fermenting ratio, even if the method is used, the yield will not be satisfactory. According to the teachings of Zhizhi, European Patent Ep 1 220 825, before using these compositions in the method, it must be supplemented in an expensive and complicated manner. Before the processing procedure, the azeotropic mixture of ethyl acetate and methanol (by means of azeotropic distillation (extractive therapeutic distillation or pressure swing distillation) was used by expensive and complicated inconvenience methods (eg, From polyvinyl alcohol) is separated into ethyl acetate and methanol, which preferably have a concentration of 97% by weight. According to the prior art, it is only appropriate to use acetic acid acetate fluid as the entry fluid. [Brief of the Invention] [Inventive Content] ^ This hairy month is a method of hydrolyzing and dissociating carboxylic acid esters by chemical methods (where carboxylic acid esters can be prepared in the form of a mixture of carboxylic acid S and corresponding alcohols). And device. The object of the present invention is to provide a method and a device that allow an azeotropic mixture of weiwei acid and the corresponding alcohol to be fed to a one-hydrolysis reaction, eliminating expensive and complicated inconvenient purification.

Page 6 V. Description of the invention (4) IV. [Embodiment] Provide a method for contacting a carboxylic acid hydrolysis catalyst with a carboxylic acid ester method, the pre-carboxylic acid and alcohol, and then pre-reverse distillation In the tower, it is hydrolyzed and converted into acid and alcohol with the hydrolysis there, and the compound with higher homogeneity as the compound with lower homogeneity is used as the method. This method includes the use of renegade acid to enter the fluid. In the case of the rate of crystallization, any process of carboxylic acid to flow into the fluid in the processing procedure of the present invention --- step omitting azeotropic distillation and azeotropic mixing and refining processing, the distillation column can be omitted without replacing Can (the lid is not used for steaming or the azeotropy of the esters and alcohols is reduced to reduce the complexity of processing and control. This volume of documentation can achieve this goal. The present invention = the method of hydrolysis to carboxylic acids and alcohols. Where it enters the flow The first y: in the reaction n with the member, and the carboxylic acid s will be partially resolved, the hydrolysis mixture is brought into contact with a reactive plugging agent, and the at least part of the _ Divided into components, the distillate is removed from the top of the reactive distillation column, and the bottom fluid is removed from the bottom of the fractionation column. The azeotropic mixture formed with the corresponding alcohol is a surprising advantage of the present invention: The azeotropic mixture of alcohol can be fed directly. Another advantage is that the purification work (such as azeotropic distillation) containing the acid S is intended. Furthermore, the work of the museum greatly simplifies the azeotropic distillation of the carboxylic acid ester and the corresponding alcohol. At least two steaming equipment are required for the function. This can lead to an increase in the distillation tower of the plant, which can be used in other processing procedures), and // the hydrolysis of the mixture to refine the entire processing process. Significantly, azeotropic mixtures including carboxylic acid esters and oblique alcohol are related to the carboxylic acid The acid esters are mixed at least with water, and the mixture is passed into the pre-reaction vessel. Suitably, the molar ratio of carboxylic acid I to water is about 1: 1

200413308 V. Description of the invention (5) 1 ·· 15, but 1: 2 to 1: 1 0 is preferable, and 1: 4 to 1: 7 is more preferable. In order to achieve an appropriate conversion rate, for example, an azeotropic mixture of carboxylic acid esters and alcohols and a mixture of water are heated to 30 to 100 ° C, but preferably 40 to 90 ° C, especially 5 0 to 80 ° C is better. In a particularly suitable embodiment, the eutectic mixture of the ferulate and the alcohol is mixed with hot water (eg, cooled hot steam condensate). In this way, the expected inlet temperature of the incoming fluid consisting of azeotrope and water before entering the prereactor can be achieved.

Perhaps'the reaction mixture is fed from the pre-reactor into a reactive distillation column system above or below the catalyst deposition zone. The feed from the pre-reactor is preferably above or above the catalyst zone and below the upper precision zone. The product flow of the reactive distillation column can always be fed to a further separation step (preferably a distillation column), during which the mixture can be further separated. It is more preferable to mix with the fluid before the distillate of another suitable embodiment is at least partially fed into the pre-reaction column. The reconstituted acetic acid acetate hydrolyzes the refined compounds, including the use of unrefined ethyl acetate, while omitting any previous method of the present invention, which is a reaction mixture formed by the beneficial mixture of a co-fossil alcohol and water. Self-steaming pagoda tower '

The reaction including the carboxylic acid ester to be converted is returned to the pre-reaction column. The advantage of including carboxylic acid esters of at least 35% carboxylic acid esters is that, for example, fluids derived from polyvinyl alcohol, except for azeotropic mixtures of methyl acetate and methanol, can be directly distilled. Implemented in a continuous manner, the carboxylic acid esters are continuously fed to the pre-reaction tower, the pre-reaction tower is removed and sent to the reaction unit, and the unreacted carboxylic acid ester is converted into hydrolysis

Page 8 200413308 V. Description of the invention (6) The hydrolysate is continuously removed as a distillate or as a bottom fluid, and (maybe) continuously fed to a further separation step in a further step. In a suitable embodiment, the distillate of the reactive retort column including the ferric acid ester to be converted may be at least partially fed back into the pre-reaction column. In particular, it is more suitable to continuously include at least 3 carboxylic acid esters, a carboxylic acid ester fluid and a distillate before feeding it into the pre-reaction column. The volume feed rate per unit catalyst volume is from 0.1 to 5 / hour, but preferably from 0.5 to 8 / hour, and more preferably from 1 to 4 / hour. The present invention further provides a device for causing the carboxylic acid S to perform acid-catalytic hydrolysis in the presence of water to generate a corresponding carboxylic acid and a corresponding alcohol. The device includes: a) a distillation column, a carboxylic acid ester and The azeotropic mixture of alcohol is taken from the top of the distillation column, b) a pre-reactor containing a hydrolysis catalyst, having at least one inlet to feed a fluid flow including a carboxylic acid ester and water, and at least one outlet to discharge the reaction mixture , C) at least one heater for heating into the fluid and / or the pre-reactor, d) a reactive distillation column containing a hydrolysis catalyst and having an inlet connected to the pre-reactor, the reactive distillation column having At least one catalyst zone and at least one rectification zone, e) a line connected to the top of the reactive distillation tower to discharge the distillate, f) a line connected to the bottom of the reactive distillation tower to take out the bottom fluid,

Page 9 200413308

V. Description of the invention (7) g) A distillation column 'A distillation column is formed from a distillate or a branch at the bottom of the tower. It is particularly suitable to take out a specific embodiment. People ~ t; IL ^ In ', the official website is in the steamed tower, the secret of the round jealous Θ ow S day, and the alcohol system is ^ π ... ^ ~~ The heater of the reactor body of the reactor is formed by hot water for feeding (for example, cooling heating steam). The azeotrope and hot water for mixing can be adjusted to an appropriate temperature. "It will enter the fluid. Perhaps, the reactive distillation column has a catalyst zone, an upper and lower rectification zone, the upper rectification zone is located above the catalyst zone, and the product distillation zone is located below the catalyst zone. The rectification zone It can include separation disc 22 = ring, structured mass transfer packing, etc. The advantageous configuration of the pre-reactor is a long tube with a first catalyst. Perhaps, the first and second catalysts are acid solid catalysts, the The particle size of the first catalyst is about 0.3 to 3 mm, and the particle size of the second catalyst is 0.5 to 5 mm, and more preferably 0.6 to 1.2 mm. The pre-reaction The first catalyst in the vessel is advantageously a random filler in the form of spheres, rings, extrudates, etc., and the second catalyst is advantageously packed in the reactive distillation & as a structured catalyst filler. For example, ' If the reactive distillation tower is a tray tower, the catalyst in the tower can be arranged on the trays or downcomers. In a more suitable embodiment, the pre-reactor can be formed by a stirrer. A figure is a schematic diagram of a specific embodiment, the specific embodiment A device for performing acid-catalytic hydrolysis of carboxylic acid esters using a pre-reactor and a reactive distillation column in accordance with existing technology, including two steaming surfaces for separating azeotropic mixtures of acid esters and corresponding alcohols tower.

200413308 V. Description of the invention (8) The to-be-refined mixture (line 1) consisting of a carboxylic acid ester, its corresponding alcohol, and any emerging water is divided into a carboxylic acid ester rich in acid and acid in the distillation column C 1 / Alcohol fractionation liquid (highest azeotropy) (line 2) and—corresponding alcohol / water crane liquid (line 1 2) 'rectified from the flow system of line 1 2 Gu Ba c β into alcohol and water (mobile body 13 and flow Body 14). ° The distilling liquid (line 2) from the fractional preparation C1 and C1 is separated in the distillate column C2 and the distilling column C 3 by means of co-fossile (such as extractive or pressure distilling distillation) and contains The distillate of carboxylic acid ester (line 3) is fed into prereactor R1. The reaction partner water was added via line 15. The product flow (line 4) of the pre-reactor r 1 is passed into the reactive distillation tower C4 above or in the reaction zone. The distilling crane liquid (line 5) of the reactive distillate C4 is preferably used for discharging low-boiling impurities or for flushing. The bottom of the reactive distillation column (4) is sent to the distillation column C 5 by means of line 6 and divided there into an alcohol fraction (line 7) and a fraction including liquid and carboxylic acid (line 8). The second figure is a schematic diagram of a specific embodiment of the present invention. This specific embodiment is a device for carrying out acid-catalytic hydrolysis of carboxylic acid esters. The device uses a pre-reactor and a reactive distillation column. And a distillation column to further separate the bottom distillation liquid of the reactive distillation column, which can eliminate the purification of the azeotropic mixture of the carboxylic acid ester and the corresponding alcohol. It is composed of the carboxylic acid ester and its corresponding alcohol, and any water present The mixture to be refined (line 1) is divided into a carboxylic acid ester-rich carboxylic acid ester / alcohol fraction (highest azeotropic) (line 2) and a corresponding alcohol / moisture fraction (line 1) in distillation column C 1 2), the flow system from line 12 is separated into alcohol and water (flowing body 13 and flowing body 14) by means of distillation column c6.

200413308 V. Description of the invention (9) The mixture of the acid and the alcohol (the steaming liquid of the steaming tower c 1) (line 2) is directly fed to the pre-reactor R1, and the reaction partner water system passes through the line 丨5Join. The pre-reacted product R1 (line 4) is fed into or above the reaction zone of the reactive distillation tower C4. The distillate (line 5) from the reactive distillation column is preferably used to discharge low boiling impurities or for flushing. The bottom fractionation liquid (line 6) of the reactive distillation column C4 is refined into the alcohol fractionation liquid (line 7) and a fender liquid (line 8) composed of water and carboxylic acid in the distillation column C5. A schematic diagram of another specific embodiment of the present invention is shown in the third figure. The specific embodiment is a device for performing carboxylic acid-catalytic hydrolysis. The device uses a prereactor, a reactive distillation column, and a The distillation column further separates the bottom fraction of the reactive distillation column. The difference between this equipment and the equipment shown in the second figure is that the distillate is at least partially recycled from the top of the reactive distillation column to the pre-reactor to improve the conversion rate of the carboxylic acid ester. Purification of azeotropic mixtures of acids S and their corresponding alcohols. For example, ‘from the feed to the pre-reaction is Θ’ The steaming liquid can also be mixed with a common mixture of carboxylic acid vinegar and alcohol ’and other processing waste fluids can also be used directly. The to-be-refined mixture (line 1) composed of carboxylic acid S, its corresponding alcohol, and any emerging water is divided into a carboxylic acid-rich weilic acid vinegar / alcoholic crane liquid (azeotropic property) in distillation column C1 Highest) (line 2) and a corresponding alcohol / water solution (official line 12). The flow system from line 12 is divided into alcohol and water (flowing body 13 and flowing body 1 4) by means of distillation column c6. '' The azeotropic mixture of carboxylic acid ester and alcohol (distillate of distillation column C1) (line 2) is fed directly to prereactor R1. To improve the pre-reactor R1 carboxylate

Page 12 200413308 V. Description of the invention (10) f = yield of action. In addition, from the top of the reactive distillation column, a highly acid-rich distillate (line 6) is fed to the pre-reactor R1. The reaction partner water system, and two are added from line 15. The product flow (line 4) of the pre-reactor r 1 is fed to f; the reaction zone of the reactive distillation column C4 or above the reaction zone. A part of the steam distillation tower C4 (line 5) is preferably used to discharge low boiling point sloppyramine for flushing. The bottom of the reactive distillation column (line 6) is divided into an alcohol fraction (line 7) and a fraction composed of water and carboxylic acid (line 8) in distillation column C5. For example, the hydrolysis of azeotrope of acetic acid acetate and methanol by carboxylic esters and their corresponding alcohols is used as an example (eg: what happens when preparing polyvinyl alcohol) The hydrolysis of azeotropic mixtures of carboxylic acid esters and corresponding alcohols is described below. Other examples of azeotropic mixtures of carboxylic acid esters and corresponding alcohols include: 2 ethyl acetate and ethanol, propyl acetate and propyl alcohol, isopropyl acetate and propyl 2 n-butyl acid and n- Butanol or secondary-butyl acetate and secondary ~ butanol ether. Methyl acetate with a weight ratio of 81% by weight and methanol with a weight ratio of m by weight (after the distillate from the retort column C1 is taken out) are mixed with water which preferably exceeds the methyl acetate -f -mole times. Subsequently, it is better to mix the temperature of 50 to 80 ° C and cry at place g of the inverting box ^ ^, bamboo, and put into the pre-reaction box R1. To achieve this, it is better to use hot water (such as cooled heated steam condensate). This pre-reactor R1 is equipped with an acidic solid catalyst (e.g. a transformer). The particle diameter of the catalyst is preferably about 0.6 to 1.2 mm. Hui Luzhi, the catalyst material is commercially available (trademark η ^

Page 13 200413308 V. Description of Invention (11) Produced by Roma and Haas. For example, useful catalysts are: zeolite, alumina, silica, and the like. This mixture of methyl acetate and water flows through pre-reactor R1 and contacts the catalyst material. This results in partial hydrolysis of the ethyl acetate. The conversion of acetoacetate in the prereactor is from 20 to 100% of the equilibrium conversion, and more preferably from 50 to 80%. The resulting reaction mixture was sent into a reactive steamer tower C4 via a line. In the reactive distillation column C4, water and methyl acetate are contacted with a catalyst material which hydrolyzes methyl acetate to acetic acid and methanol. In this way, a mixture of acetic acid, water and methanol is formed into the bottom distillation liquid of the reactive distillation. The bottom separation liquid is divided into the downstream distillation tower C5-a fractionation liquid containing methanol (mobile body 7) And a liquid extract consisting of water and acetic acid (mobile body 8). Experimental example 1 (comparative example): The implementation of experimental example 1 is based on the method and shooting equipment according to the existing technology. The azeotropic mixture of methyl acetate and methanol is mixed with water and fed directly to the reactive distillation column C4. The molar composition of the methyl acetate / methanol azeotrope to be hydrolyzed is: acetic acid acetate · methanol is 1.94: 1, corresponding to 81% by weight of g of acetate and μ% by weight of methanol. Exhaust_Household distillation column: Inner diameter: 1 100 mm Distillation zone: 5 theoretical layers (TS)

Reaction zone: 3 TS

200413308 V. Description of the invention (12) π stripping "zone: feed flow: azeotrope: water: product flow: distillate: bottom flow: experimental conditions: top pressure: feed point: heating output : Heat exchanger temperature:

8 TS 6 8 5 kg / h 9 0 0 kg / h 2 2 kg / h 1 563 kg / h

Above the 9 mbar reaction zone 9 9 0 仟 W 5 2 ° C Result: Methyl acetate conversion: 79.4% (irrespective of flushing, line 5) Reactive distillation column bottom fraction fraction composition: methyl acetate : 7.3% by weight methanol: 19. 9% by weight water: 51.0% by weight acetic acid: 21.8% by weight

Page 15 200413308 V. Explanation of the invention (13) Experimental example 2 (comparative example): The implementation of experimental example 2 is based on the method and shooting equipment according to the existing technology. An azeotropic mixture of ethyl acetate and ethyl alcohol is mixed with water and fed directly to the reactive distillation column C4. The processing feed of the azeotropic mixture is reduced to 500 kg / h, and the heating output is reduced to 700 watts. The molar composition of the methyl acetate / methanol azeotrope to be hydrolyzed is: acetic acid acetate: methanol is 1.94: 1, corresponding to 81% by weight of methyl acetate and 19% by weight of methanol. Reactive distillation column Inner diameter: Jingde zone · Reaction zone: π stripping "zone:

1 1 0 0 mm 5 Theoretical layer (TS) 3 TS 8 TS t Feed fluid azeotrope: Water: 500 kg / hour 6 500 kg / hour Product mobile fluid Distillate: Tower bottom fluid 1 6 kg / h 1 134 kg / h * Experimental conditions Tower pressure 28 mbar

Page 16 200413308 V. Description of the invention (14) Feed point: Heating output: Heat exchanger temperature above the reaction zone 7 0 0 仟 W 5 2 t: Result: Methyl acetate conversion: 9 6. 9% (flushing slightly Irrespective, the composition of the bottom distillation fraction of the reactive distillation column in line 5: methyl acetate, methanol, water: acetic acid: 1.1% by weight, 22.6% by weight, 49.3% by weight, 27.0% Weight ratio experimental example 3: Experimental example 3 uses the method of the present invention and the apparatus according to the second figure of the present invention. An azeotropic mixture of methyl acetate and methanol is mixed with water and fed to prereactor R1, and then The product of the pre-reactor R1 is sent to a reactive distillation column C4. The molar composition of the methyl acetate / methanol azeotrope to be hydrolyzed is: acetic acid acetate: methanol is 1.94: 1, corresponding to 81% by weight Than ethyl acetate and 19% by weight of methanol. T Inner diameter of reactive distillation column: Jinghe District · 1 1 0 0 mm 5 theoretical layer (TS)

Page 17 200413308 V. Description of the invention (15) Reaction zone: π stripping "zone:

3 TS 8 TS Feed azeotrope: Water: 700 kg / h 900 kg / h Distillate of product mobile body: Flow at the bottom of the tower 26 kg / h 15 74 kg / h Experimental conditions: Pressure at the top of the tower: Feed point: Heating output: Heat exchanger temperature 26 mbar above the reaction zone 7 0 0 Shiva 5 8 t 4 1. 8 ° / 〇9 8. 9% (irrespective of flushing, line 5) * Results: Conversion rate of acetic acid acetate-after pre-reactor-total reactive distillation column bottom fraction fraction composition: methyl acetate: 0.4% by weight

Page 18 200413308 V. Description of the invention (16) Methanol: Water: Acetic acid: 2 2.7% by weight 49.6% by weight 27.3% by weight Experimental Example 4: Experimental Example 4 uses the present invention Method and apparatus according to the invention according to the third figure. An azeotropic mixture of ethyl acetate and methanol is mixed with water and fed to prereactor R1, and the product of prereactor R1 is sent to reactive distillation column C4. The distillate of the reactive distillation column is at least partially recycled to the pre-reactor R1. The molar composition of the methyl acetate / methanol azeotrope to be hydrolyzed is: acetoacetate: methanol is 1.94: 1, corresponding to 81% by weight of methyl acetate and 19% by weight of methanol. Reactive distillation column Inner diameter: Intensive care zone · Reaction zone: " Stripping " Zone: Feed fluid: Azeotrope: Water:

1 1 0 0 mm 5 Theoretical layer (TS) 3 TS 8 TS * 6 8 5 kg / hour 9 30 kg / hour Product flow:

Page 19 200413308 1 5 kg / h 1 600 kg / h 5. Description of the invention (17) Distillate: Flow at the bottom of the experimental conditions: Pressure at the top of the tower: Feed point: Heating output: Recirculate to the pre-reactor Heat exchanger temperature: Result: 29 mbar above the reaction zone 4 9 0 仟 W 2 0 0 0 kg / h

5 8 ° C t Methyl acetate conversion after pre-reactor-total 8 9.7% 9 9 · 1% (flushing is ignored, line 5) Reactive distillation column bottoms fraction composition: methyl acetate: 0. 3% by weight methanolic water: acetic acid 2 2. 7% by weight 5 0. 0% by weight 2 7. 4% by weight i

Page 20 200413308 Brief description of the drawings Figure 1: A schematic diagram of a specific embodiment of the device of the present invention. FIG. 2 is a schematic diagram of another embodiment of the device of the present invention. The third diagram is a schematic diagram of another specific embodiment of the device of the present invention.

Page 21

Claims (1)

200413308 1. A method in which a hydrolytic catalyst is connected to a carboxylic acid and an alcohol, and then the distillation column is converted into a carboxylic acid with a higher chemical property and a lower chemical property. The method includes facilitating the flow into a fluid. 2 · If applying for special methyl ester and methanol 3 · If applying for special tower bottom flow components. 4. If the application of specialized carboxylic acid vinegar is applied, the reaction will be further transformed. 5 · If the application of special equipment enters the flow and is heated. 6. A kind of device method, in the presence of water hydrolysis hydrolysis reaction including acid reaction, the pre-treated water and alcohol, the compound as a compound using the acidic acid range azeotropic mixing range system profit range should be Sexual steaming effect. The scope of the system is borrowed, so that the pre-reaction reaction of the corresponding acid ester can be decomposed at the same time, and the steam is used as the purpose and the hydrolyzing agent that enters the reactor to the reactor is connected to the distillate from the bottom. In the method of converting alcohol into meta-acid and alcohol, the first part of the moving body and the prereactor is to partially dissolve the glutamic acid into a solution mixture and pass into a reactive vaporization reaction, and reduce the carboxylic acid to be converted. The part is divided into various components, and the top of the distillation tower is removed by volatilization, and the volatile body is removed from the bottom of the distillation tower. The azeotrope formed is used as the method of item 1, wherein the azeotrope is an acetate. The method of item 1 or 2, wherein the reactive distillation is given to a further separation step and is at least partially divided into the method of item 1, 2 or 3, which includes recycling the undistilled column distillate to the prereactor. The method of item 1, 2, 3 or 4, wherein the pre-reaction feed water is supplied to an azeotropic mixture of a carboxylic acid ester and an alcohol, which is one of the azeotropic mixture of a carboxylic acid ester and an alcohol. The ester implements acid to carboxylic acid and corresponding alcohol. The device includes: Page 22 200413308 VI. Application scope a) A distillation column, the azeotropic mixture of carboxylic acid and alcohol is taken out from the distillation column, a pre-reactor, which contains a hydrolysis catalyst, has at least one inlet for feeding includes Acid and water fluid flow, and at least ~ outlets to discharge the reaction mixture 'At least one such as a heater for heating into the flow and / or pre-reactor, a reactive distillation column containing a hydrolysis catalyst And has an inlet connected to the prereactor, the reactive distillation column has at least one catalyst zone and at least one rectification zone 'a pipeline connected to the top of the reactive distillation tower to discharge the distillate, a connected reactive distillation tower The bottom line is used to take out the bottom-closed fluid, a distillation column, and the line from the bottom of the reactive distillation column is used to form an inlet to the distillation column. Take out from the distillate or bottom fraction. For example, the device in the scope of patent application No. 6 wherein the unconverted ferric acid ester line 16 conveyed from the top of the reactive distillation column C 4 is connected to the pre-reaction R 1. 8 · The device according to item 6 or 7 of the scope of patent application, wherein the heating device used to heat the incoming fluid entering the pre-reactor is formed by hot water in the feed line 15. 9. For the device in the scope of claim 6, 7, or 8, the pre-reactor R1 is a stirrer. 10 · If the device in the scope of the patent application is 6, 7, 8 or 9, if the reaction b) c) d) e) f) g) 7 · Page 23 200413308 6. Scope of patent application The distillation column C4 is a tray column, and the hydrolysis catalyst is arranged on the trays or downcomers of the tray column.