TWI282746B - Method and apparatus for esterification - Google Patents

Abstract

This invention provides an improved reactive distillation method and apparatus for acetic esterification, especially for producing esters of medium and low carbon numbers such as ethyl acetate or isopropyl acetate from alcohol through reactive distillation process of acetate esterification. The method is capable of increasing the conversion ratio of the esterification significantly and producing esters of very high purity of industrial grades.

Description

1282746 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a manufacturing method and a method thereof, and more particularly to a manufacturing method and apparatus for high purity _ which can be industrial grade or higher. [Prior Art] Ethyl acetate and isopropyl acetate are important solvents in the industry, and can be used for plastics, oils, inks, etc., and can also be used as raw materials for synthetic fragrances. At present, the process of Jl for ethyl benzoate can be roughly divided into the following ways: (i) First use the pre-reactant to carry out the acetic acid esterification reaction, and then use multiple recovery towers and phase separation tanks to carry out the esters. Purification and recovery of the product, this procedure should be proposed by Keyes (l932) at the earliest; however, the process involves more units and is slightly more complicated, and is not conducive to operation and maintenance. (ii) The design of a single reactive distillation column, which is a general reactive Luohe tower design, which mainly divides the steaming tower into three sections: the reaction section, the Jinggu section and the stripping section; A homogeneous or heterogeneous catalyst promotes the reaction. There is considerable research in the literature for such a single reactive distillation column. The earliest & ethyl acetate single reactive steaming tower process may be proposed by Suzuki et al. in 1972, (v〇 Ra and 仏—this, 2001), the operation and control of the reactive distillation column in this ethyl acetate process, but the purity of the ester product at the top of the column is still not high, and the bottom product still contains four components. Further processing. According to the data in the literature, the reaction of such a steamed tower is not high enough for the ethyl acetate product, so it is impossible to find the industry. In general, this form of reactive steaming 1 product is limited to the azeotrope of the three components of the acid humiliation ester, while the bottom of the tower is limited to screaming and screaming 'and therefore must be reprocessed or 1 out of the necessary product' For example, the United States specializes in the township 6693213, the top of the tower is divided into: after the discharge of impure is difficult, and the high-purity acid reactants at the bottom of the tower, both in the process and H Xiao is a disadvantage. (4) The process of using two steaming towers as the main process, this design mainly uses a reactive tower and a recovery tower (such as Bock, 1997), although this design can obtain high purity in the bottom of the second recovery tower. The ethyl acetate product, however, the mixture of the sub-components and the H-components needs to be sent back to the first steaming %' and the first-root reaction steaming tower bottom water-transfer mixture also needs to be treated. In view of this, the applicant has carefully tested and researched, and has not proposed the "_manufacturing method and equipment" of the case, which provides a kind of reaction steaming for improving the knowledge and manufacturing process. The method for producing esters and the equipment thereof are designed to have different thermodynamic properties for the esterification reaction, and the design of the g-reaction is based on the g of the present invention. High-purity esters of industrial grade or higher can be obtained by the method and equipment. SUMMARY OF THE INVENTION The present invention is to provide a _fine manufacturing method comprising the following steps: (8) mixing-acid feed with-alcohol feed in-reactive steaming soil to produce a reaction-- a gaseous mixture; (b) deriving the first gaseous mixture to the reactive column, and cooling the first money mixture to produce a liquid mixture; (e)_ liquid-liquid phase separation tank separating the liquid mixture 1282746, Dividing it into a first liquid mixture and a second liquid mixture; (d) introducing a first portion of the first liquid mixture into the reactive distillation column; (e) purifying and separating the first liquid mixture a second portion to produce a high purity ester product and a second gaseous mixture; and (f) cooling the second gaseous mixture to form a third liquid mixture; and (g) the third liquid mixture The liquid-liquid phase separation tank is introduced to perform separation again.

According to a first aspect of the invention, the reactive distillation column contains a solid catalyst. According to a first aspect of the invention, the solid catalyst is an ion exchange resin. According to a first aspect of the present invention, the reactive distillation column further comprises a plurality of rectification plates and a plurality of reaction plates. According to a first aspect of the present invention, wherein the number of plates of the rectifying plates is 5 to 15 〇

According to a first aspect of the present invention, wherein the number of plates of the reaction plates is 8 to 20, according to the first concept of the present invention, wherein the acid feed and the alcohol feed are reacted at the bottom of the reactive distillation column. . According to a first aspect of the invention, the molar ratio of the feed of the acid feed to the alcohol feed is between 1 〇·· u to 1·〇: 1.0. According to a first aspect of the invention, the acid feed is acetic acid. According to a first aspect of the invention, the alcohol feed is selected from the group consisting of ethanol, isopropanol and butanol. According to a first aspect of the invention, the pressure operating range 7 of the method is 1 to 2 atmospheres. According to the first concept of the present invention, it is 70 to 125 °C. Temperature Operating Range of 乂i(a) According to the first concept of the present invention, it is ambient temperature of ~50 °C. The temperature operating mode of ^i(c), according to the first concept of the present invention, is in the step of a system-rich mixture and a mixture of the first and second aqueous phases. - Liquid city compound - 畐 type 八 According to the invention of the first concept, in _), the first liquid mixture is hydrolyzed by -T guangguan. According to the first aspect of the present invention, in the step (e), the two portions of the first liquid-smelling mixture are introduced into a recovery column for purification and separation. According to a first aspect of the present invention, the step-temperature operating range is 75 to 95 °C. A second concept of the present invention is to provide an ester production apparatus comprising a reactive distillation column having a first feed port and a second feed port at the bottom and having a -first discharge at the top a mouth and a third feed port, wherein the acid feed and the alcohol feed are respectively reacted by the first feed port and the second feed port into the reactive steamed towel to react with the wire. To produce a gas m mixture; a liquid-liquid phase separation tank having a fourth feed port, a fifth feed port, a second discharge port, and a third discharge port p, wherein the fourth feed port Is connected to the first discharge port of the reactive distillation column; a S-recovery column having a fourth discharge port and a sixth feed port, wherein the fourth discharge port is connected to the liquid The fifth feed port of the liquid phase separation tank is connected; and a T-type split pipe having a first end, a second end and a third end, wherein the first end is connected to the reactive distillation column The third feed port is connected, the second end is connected to the second discharge port of the liquid-liquid phase separation tank, and the third end is connected to the ester recovery tower. The sixth feed port is connected. According to the second concept of the present invention, the gaseous mixture of the towel is cooled and converted into a liquid mixture, and the liquid phase separation tank is introduced to separate the non-high purity organic phase liquid mixture, the non-high purity. The first portion of the organic phase-rich liquid mixture is returned to the top of the anti-ship distillate via the third feed port, and the second portion of the non-high purity rich organic phase liquid mixture is verified by the split type When the tube enters the ester with the sixth feed port, the tray is subjected to a purification separation procedure to obtain a high-purity self-purpose product from the four discharge ports of the bottom of the recovery column. According to a second aspect of the present invention, the reactive distillation column further comprises: a reaction plate disposed in the bottom portion of the reactive steamed baffle; and a plurality of fine II plates disposed in the The top of the tower of the reactive tower is to the middle section; and it is filled between the middle section of the counter-neutral steaming scale to the bottom section or between the upper section and the bottom section of the towel. According to the above concept, the number of plates of the rectifying plates is 5 to 15. According to the above concept, the number of plates of the reaction plates is 8 to 20. According to the above concept, the solid catalyst is an ion exchange resin. According to the above concept, the ratio of the amount of the bottom plate filling of the solid catalyst to the amount of filling of the tray is 1 to 100. σ 1282746 According to the second concept described above, the ratio of the amount of the bottom plate filling of the solid catalyst to the filling amount of the tray is 〗 〇 〇. /, According to a second aspect of the invention, wherein the acid feed to the alcohol feed dose ratio is between U:u and 1.0:1.0. A second concept of the invention wherein the acid feed is acetic acid. According to the original H, I shot isopropyl alcohol and butanol. Ding 卞 k k k 酉 、, Φ According to the second structure of the present invention, 1 operating range is 1 to 2 atmospheres. ~〃~曰痛4 The pressure of making equipment: County: Ming's second concept, more includes - ::::: It is connected to the reaction one operation (4) The second concept of the temperature invention of the tower 'where the Φ is the range It is normal temperature ~125 °c. The degree of the 祁 日 日 刼 according to the second phase of the invention, the range is ~ 95. Temperature operation of the meso recovery column According to the second concept of the present invention, an ester-water azeotrope. , Hi-compound according to the second trick of the present invention. ^5, ^ Wei. Xin Xin, the S-type manufacturing equipment further includes a first cold-deficient and a second two condenser, ... 3 brother 〆 discharging Π and the fourth feeding; - 广 如 如 is connected to the fourth discharge Π and the fifth inlet ～ and the second condensing 11 is connected to 10 according to the second concept of the present invention, wherein The ester recovery column further includes a - fifth discharge port to derive the high purity ester product. A. According to a second aspect of the invention, the ester manufacturing apparatus further comprises an ester storage port attached to the fifth discharge port at the bottom of the ester recovery column to collect the resulting high purity product. According to the second concept of the present invention, the ester preparation device further comprises a water bead storage tank connected to the third discharge port at the bottom of the liquid-liquid phase separation tank for collecting from the liquid-liquid phase separation tank. The separated - rich water phase material. The present invention can be further understood by the following drawings and detailed descriptions. [Embodiment] The ester of the present invention is designed to meet the reactivity of the g-reaction reaction. The reaction can be simply written as the following formula:

• K acid + alcohol 〇acetate + water The reaction is a -reversible reaction, wherein the acetate (ac_) refers to ethyl acetate or erythric acid (IV), and the acid (add) in the reaction formula is acetic acid, and « (alcohol) is ethanol or isopropanol. The catalyst required for the reaction mainly has two kinds of catalysts and non-uniform contact; in the reaction evaporation designed by the present invention, the reaction is carried out by a heterogeneous catalyst. The Μ 媒 伽 伽 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她Recycling issues and other issues. Solid catalyst-like secret exchange resin, such as commonly used in the industry 1282746

Amberlyst 15 (Rohm and Hass) or Purolite CT179 (Purolite). In addition, the filler structure of the catalyst can be placed in the tray using the conventional Katapak-S method or by using a solid-state device (Dayy pr〇CeSS Technology). First, as far as the physical properties of the entire reaction system are concerned, the boiling point of each component of the ethyl acetate system can be obtained as follows. (1) Table (1) Boiling point of the substance type (QC) Et0H/EtAc/H?0 70.09 EtAc /H,〇70.37 EtOH/EtAc 71.81 EtAc 77.20 Et〇H/H2〇78.18 EtOH 78.31 H20 100.0 — HAc 118.01 Φ zyw Fucheng knife contains a mixture of _ ester_water three components azeotrope and vinegar _ water, It has a boiling point with three two components, such as alcohol_water, and the existence of the azeotrope will form a =_ boundary to be separated on the separation. Among them, the lowest point of the Buddha's point is that the lightness/knife is a mixture of the three components of L water. The boiling point is about -9C... The heavy component of the point is acetic acid. The point is about u8〇1C3c. From the design of the general ,, the top of the tower The product is distilled to be close to the three components and the bottom of the mixture is acetic acid, and the product of the acetic acid B is the boiling point of W ye; the position of the /U is 'this is a single-reaction test tower does not stomach to obtain high purity 12 1282746 The reason for the ester product. Similarly, in the case of isopropyl acetate, the order of (10) points can be obtained as shown in the following table (1)' and the domain can be understood that the isopropyl acetate is subject to the same conditions in the reaction process, resulting in the intermediate boiling point product on the steaming residue. Difficulties: Table (ii) Substance type '- Boiling point (°c) IPA/IPAc/H20 —---— 74.22 IPAc/H20 76.57 IPA/IPAc --- 78.54 ipa/h2o 80.06 IPA 82.35 IPAc 88.52 h2o ---- --- 100.0 HAc 118.01

The invention mainly comprises a reactive distillation system consisting of a reactive steaming tower, a liquid-liquid splitting tank and a vinegar recovery tower, and the reaction distillation tower is divided into two sections, a rectifying section and a reaction section. The section means that the tray has a packed solid: a catalyst section, and the reaction section is disposed in the upper middle section of the reactive distillation column to the bottom plate or the middle section to the bottom plate, and the upper end of the reaction section is a rectifying section, and the acetic acid and the alcohol reactant are the same At the bottom of the reactive distillation column or the reboiler feed, since a large amount of high-purity acid will be retained in the bottom portion of the column, the amount of catalyst in the bottom of a reactive distillation column is 10 to 100 times to facilitate the reaction of a large amount of alcohol. The amount of feed needs to be more than the amount of acetic acid, the ratio is roughly about the ratio of alcohol to acid 1··〇·94 to 1: 〇_96, 13 1282746 ff, after the phase separation of the material, the organic phase and the organic phase The principle that the aqueous phase is immiscible separates the organic phase from the aqueous phase. Branch

, the main structure of the design of acetic acid ethyl acetate and isopropyl acetate complete reaction steaming - reactive steaming, liquid-liquid phase separation tank and one 酉曰 + recovery tower three units, the reactants from the reaction steam II The bottom of the tower is manned, and the part of the reaction steaming tower is divided into the fine touch and the reaction section, and the reaction section is partially filled with solid. The dividing woman separates the three components of the pre-tower alcohol Lu water mixture and then returns part of the organic phase to the reactive steaming hall. The top portion of the top plate is sent to an ester recovery column for purification of the high purity ester product, which can be used to make high purity esters at the bottom of the column. Referring to the first figure, which is based on the preferred embodiment of the present invention, is used to provide a configuration of the manufacturing equipment according to the present invention; the following is a description of the method for producing an ester of the present invention. According to the configuration diagram, the steps are as follows.

The ester production equipment of the present invention mainly comprises a reactive distillation column 1, a -S recycling column 2, a _ _ _ _ _ _ _ _ _ _ _ _ Further configured in the apparatus - a first condensing duct system comprising a first cold/heart 6 and a pipe for connecting the reactive steaming tower 1 and the liquid-liquid phase separation tank 3, the apparatus further comprising a second A condensing duct system comprising a second cold head 7 and a pipe for connecting the ester recovery tower 2 and the liquid-liquid phase separation tank 3. Further, a first reboiler 4 is placed at the bottom 4 of the reactive distillation column and a first reboiler 5 is placed at the bottom of the ester recovery column 2. Ester recovery The bottom of the soil mixture 2 is connected to a cool storage tank c; and the water phase side of the liquid-liquid phase separation tank 3 is connected to a water storage tank D. 14 (10) 2746 The turbulent reaction of the turret and the slab of the pagoda and the pipe 10 and their associated pipes. A second pump 9 is additionally provided to connect the vinegar benin to the Ca and the ester recovery tower 2. = The organic phase of the shunt tube, the lion channel 3, is partially split into the ester recovery column 2 via the reflux line. m a certain purity of the acid feed (4) and the alcohol feed (8) (for example, acetic acid = money, the acid is acetic acid, the alcohol is ethanol), respectively, using the bottom of the reactive vaporization as the feed position, that is, The acid feed enthalpy and the alcohol feed 6 are respectively introduced from the bottom feed ports II, 12 of the reactive steam column 1, to generate a - gaseous mixture (ie, unpurified alcohol I water); The gas, the mixture is discharged from the top discharge port 〇1 of the reactive vapor column, and after being liquefied by the first condensation II 6 , the liquid liquid phase separation tank 3 is introduced through the feed σ 14 to carry out the liquid liquid. Miscellaneous. Further, the unpurified alcohol-ester water gaseous mixture from the top discharge port 4 of the recovery column 2 is also liquefied by the second condenser 7, and is introduced into the liquid-liquid phase separation tank 3 through the feed port 15 for carry out. The liquid phase is separated from the liquid phase. After the liquid phase is separated by liquid phase, the water-rich phase of the mixture is discharged from the discharge port 3 of the lower layer of the liquid-liquid phase, and enters the water storage tank d; and is mixed, and the machine phase is separated from the liquid-liquid phase. The upper layer of the tank 3 is extracted by the discharge port 〇2: the second pump 8, and is further divided into two streams through the τ-type splitter 1,, and the larger number of organic phase streams will be driven by the pump 8 and the τ type. The shunt tube is diverted and enters the top plate of the reactive steaming tower via the feed port 13, and the remaining organic phase stream is also passed through the feed port 16 by the diversion of the pump 8 and the T-type shunt tube 10. Enter the top of the ester recovery tower 2. 15 1282746 匕 混合物 反应 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( In the manufacturing apparatus and method of the present invention, there is no production or subtraction or the material is discharged from the bottom of the reactive spinning tower 1. The reaction temperature of each of the raw materials of the hybrid therapy 1 is through the feed flow ratio and the bottom of the tower.

The turf is controlled by the buddha; and the temperature of each plate of the ester recovery tower 2 is also controlled by the buddha disposed at the bottom of the soil. In order to save the investment cost, in the manufacturing method and apparatus of the present invention, the filling range of the reactive steaming tower 1 is in the range from the upper portion of the steamed towel to the bottom plate or the middle portion to the bottom plate, and the catalyst filling of the bottom plate The amount is 1 to 10 times, even i to 100 times from the board. In the present invention, the catalysts used are Amerlyst's and Amerlyst^5, which are commercially available from Röhm and HassTM, and Porulite CT 179 from Pomlite.

According to a preferred embodiment of the invention, the temperature operating range for the reactive distillation column is selected depending on the product system; for example, the ethyl acetate system is from 7 ° C to 125 ° C, the isopropyl acetate system Then it is to 125 °C. Further, the temperature operating range of the ester recovery column 2 is selected to be from 70 ° C to 90 ° C for the ethyl acetate system and from 1 ° C to the isopropyl acetate system. In general, the temperature operating range of the liquid-liquid phase separation tank 3 is operated in the range of normal temperature to 50 °C. According to a preferred embodiment of the present invention, the pressure distillation range of the reactive distillation column 1 and the ester recovery column 2 of the ethyl acetate system and the isopropyl acetate system are both 16 1282746 to 1 to 2 atm; and the liquid-liquid phase separation tank 3 Then operate under normal pressure. In the present invention, the chemical feed molar ratio of the acid and the alcohol is operated between 9·9 and 1.0 by adjusting the feed flow rate of the acid. * * In the present invention, the reaction takes place in the liquid phase, and the product vinegar and water are fed to the top of the reactive distillation column 1 and the ester recovery column 2. In order to increase the reaction conversion rate, the unreacted liquid alcohol is also refluxed with water to the top of the reactive distillation column 1 for further conversion.

In the present invention, the theoretical value of the residual plate required for the reactive steaming tower i is 5 to 15 plates' and the number of plates of the reaction plate is 8 to 2 plates; in addition, the number of theoretical plates required for the vinegar recovery column 2 It is 5 to 15 plates. [Examples]. Example (1) = The chemical dose of acetic acid and ethanol is the reaction treatment system of Q 9652. The reaction operating range of the steaming tower is Μ to (2)

c 'its, the operating temperature is 7 (rc; the vinegar recovery tower temperature operating range is 5c', and then (four) # for the temperature of 7 叱. The fine medium uses the Porulite CT 179. The results are shown in the following table (3). The ratio of the chemical acid dosage of the reservoir 2 acid to the symmetrical chemical dosage is _4, and the reaction temperature of the steaming tower is 80 to m = re-operating temperature is 74 sink; The operating temperature range is c', and the operating temperature of the Buddha is 74. The catalyst is Amerlyst 15 or the results are as follows (3). 17 1282746 Table (3) System ethyl acetate ginseng (apricot/fell, one曰百曰贝例(一λ) > Bellow Recovery Tower Reactive Distillation Column Ester Recovery Tower Total Theoretical Plate 20 10 24 8 Theoretical Stripping Plate 9 7 Theoretical Reaction Plate 11 14 Theoretical Distillation Plate 9 _ 10 Acetic Acid Feeding plate bottom plate ----- bottom of the bottom plate ^ Alcohol feed plate bottom plate --- acetic acid feed concentration (mole fraction) 0.95 0.95 alcohol feed concentration (ethanol / isopropanol) (mole Fraction rate) 0.87 0.6491 acetic acid / alcohol chemical dose molar feed ratio 0.9652 0.944 product ester concentration (Mole fraction) Liquid-liquid phase separation tank (.〇40 0.99000 —---- 0.99000 50 $ Therefore, the present invention is particularly directed to the thermal φ mechanical properties of different esterification reaction separation systems, and to the esterification reaction separation system. The process is designed to obtain high-purity vinegar products of industrial grade or higher through the present invention. _ In summary, the present invention is a novel, advanced and industrially useful invention, and has profound development value. The invention is modified by those skilled in the art without departing from the scope of the application. [Fig. Brief Description] The first figure is an ester production according to a preferred embodiment of the present invention. The equipment configuration is not intended to illustrate the ester manufacturing equipment and manufacturing method of the present invention. 18 1282746 References: ι·Tang Yongtang, Design and Control of Complete Ethyl Ethyl Reactor Distillation Procedure, PhD thesis, Institute of Chemical Engineering, National Taiwan University (2003)·2·Lai Yikuan's Reaction Distillation Program Design for Azeotropic Feed: Ethyl Acetate and Isopropyl Acetate, Master's thesis of Institute of Chemical Engineering, National Taiwan University ( 2005). 3. Tang5 YT; Chen, YW; Hung, S5 B.; Huang, Η. P.; Lee, MJ; Yu5 C· C·, “Design of Reactive Distillations for Acetic Acid Esterification with Different Alcohols,,, AIChE J., 51, 1683-1699, (2005).

4. Hung, S·B·; Tang, Y·T.; Chen, Y·W·; Lai, I. K·; Hung, W. J·; Huang, Η·P·; Lee, M·J· ; Yu, C· C·, “Control of Different Reactive Distillation Configurations for Acetic Acid Esterification,'' (submitted to AIChE J.) (2005). 5· Tang, Y. T·; Huang, Η. P·; Chien , IL·, “Design of a Complete Ethyl Acetate Reactive Distillation System,” J. Chem. Eng. Japan, 36, 1352 (2003). 20

Claims (1)

I2_ —___ X. Patent application scope: »April 4th revised (more) Original 1. An ester manufacturing method comprising the following steps: (a) mixing a monoacid feed with a monol feed containing a solid a first gaseous mixture is reacted in the bottom of the reactive vaporization column; (b) the first gaseous mixture is led to the reactive distillation column, and the first gaseous mixture is cooled to produce a liquid mixture (c) separating the liquid mixture into a first φ-liquid mixture and a second liquid mixture by using a liquid-liquid phase separation tank; (d) introducing the first portion of the first liquid mixture into the liquid mixture In the reactive distillation column; (e) purifying and separating a second portion of the first liquid mixture to produce a high purity ester product and a second gaseous mixture; and (f) cooling the second gaseous mixture to Forming a third liquid mixture; and (g) introducing the third liquid mixture into the liquid-liquid phase separation tank for separation again. 2. The method of claim 1, wherein the solid catalyst is an ion exchange resin. 3. The method of claim 1, wherein the reactive distillation column further comprises a plurality of rectification plates and a plurality of reaction plates. 4. The method of claim 3, wherein the number of plates of the rectifying plates is 5 to 15. 5. The method of claim 3, wherein the number of the plates of the reaction plate is 8 to 20 〇 21 1282746. The method of claim 1, wherein the acid feed and the alcohol feed system are The reaction is carried out at the bottom of the reactive distillation column. 7. The method of claim 1, wherein the molar ratio of the acid feed to the alcohol feed is between 1 〇 ·· u to 1 (): 1 〇. 8. The method of claim 1, wherein the acid feed is acetic acid. 9. The method of claim 1, wherein the alcohol feed is selected from the group consisting of ethanol, isopropanol and butanol. 10. The method of claim 4, wherein the pressure operation of the method The range is 1 to 2 atmospheres. For example, the method of the first aspect of the patent scope, wherein the temperature of the step (8) falls within the range of 70 to 125 °C. 12. The method of claim 1, wherein the temperature operating range of step (c) is normal temperature ~ 50 QC. 13. The method of claim 1, wherein in the step (6), the first night mixture is a rich organic phase mixture, and the second liquid mixture is a water-rich phase mixture. The method of 14^1=^ the range of the method, wherein in the step (9), the first portion of the first liquid mixture is introduced into the reactive distillation column by a knife. 15. The method of claim 1 of the patent scope of the invention, wherein, in the step (8), the ^, , ., v^-4 wounds are introduced into the monoester recovery tower for purification and separation. . 16. The method of claim 1, wherein the temperature operation of the step (e) is 75 to 95 °C. 22 1282746 17. An ester manufacturing apparatus comprising: - a reactive refractory tower having a bottom - a feed inlet and a bottom: a second outlet having a first discharge port and a third feed The medium-acid feed and the alcohol feed are respectively produced by the first feed port and the second feed π 崎 domain anti-ship steamed towel & a solid catalyst which is filled between the bottom sections of the reaction column or between the upper section and the bottom section; a primary phase, a liquid phase separation tank having a fourth feed σ, a fifth feed port, a second discharge port and a third discharge port, wherein the fourth feed port is connected to the first discharge of the reactive distillation column, a vinegar recovery column, and has a fourth output sixth inlet Wherein the fourth discharge port is connected to the fifth feed port of the liquid-liquid phase separation tank; and the one-turn type branch pipe has a first end, a second end, and a first a third end 'where the first end is connected to the third feed port of the reactive distillation', the second end is connected to the second discharge port of the liquid-liquid splitting trough, and the a three-terminal system is connected to the sixth feed port of the ester recovery column; wherein the gas-stricken mixture is cooled to be converted into a liquid mixture, and the liquid liquid is introduced into the liquid phase to separate the non-high-purity rich machine Phase liquid mixture 'one of the non-high purity rich organic phase liquid mixture is refluxed into the top of the reactive steam scale via the third feed π, and the non-high purity rich organic phase liquid mixture The second portion of 23 1282746 is passed through the τ-type splitter and the sixth feed port into the ester recovery column for purification separation procedure to obtain a high purity at the fourth discharge port at the bottom of the ester recovery column. Ester product. 18. The ester manufacturing apparatus of claim 17, wherein the reactive distillation column further comprises: a plurality of reaction plates disposed at a bottom portion of the reactive distillation column; A plurality of rectification plates are disposed at the top to the middle of the reactive distillation column. 19. The ester manufacturing apparatus of claim 18, wherein the number of the fine slabs is 5 to 15. 20. The ester manufacturing apparatus of claim 18, wherein the number of the plates of the reaction plates is 8 to 20. 21. The ester manufacturing apparatus of claim 18, wherein the solid catalyst is an ion exchange resin. 22. The apparatus for producing an ester according to claim 21, wherein the ratio of the amount of the bottom filler of the solid catalyst to the amount of the tray filled is 1 to 100. 23. The apparatus for producing an ester according to claim 22, wherein the ratio of the amount of the bottom filler of the solid catalyst to the amount of the tray filled is 1 to 10. 24. The ester manufacturing apparatus of claim 17, wherein the molar ratio of the acid feed to the alcohol feed is between 1.0: 1.1 and 1.0: 1.0. 25. The ester manufacturing apparatus of claim 17, wherein the acid feed is acetic acid. 24 Ί 282746 26 · The ester manufacturing equipment of claim 7 , wherein the alcohol feed is selected from the group consisting of ethanol, iso-alcohol and butanol. 27. Manufacture of vinegar according to claim 17 The pressure operation range of the vinegar manufacturing equipment is 1 to 2 atmospheres. 28. The vinegar manufacturing apparatus of claim 17, further comprising a reboiler and a second reboiler connected to the outside of the bottom of the reactive vaporization column and the ester recovery column, respectively. 29. The manufacturing equipment of the third aspect of the patent application, wherein the temperature range of the reactive steaming tower is 7〇~125〇c. 30. The ester manufacturing apparatus of claim 17, wherein the liquid liquid is a phase tank having a temperature operating range of from room temperature to 125 〇c. 31. The ester manufacturing apparatus of claim 17, wherein the ester recovery tower has a temperature operating range of 75 to 95 °C. 32. The ester manufacturing apparatus of claim 17, wherein the gaseous mixture is a mono-ester-water azeotrope. 33. The ester manufacturing apparatus of claim 17, further comprising a first condenser and a second condenser, wherein the first condenser is connected to the first discharge port and the fourth inlet The second condenser is connected between the fourth discharge port and the fifth feed port. 34. The ester manufacturing apparatus of claim 17, wherein the ester recovery column further comprises a fifth discharge port to derive the high purity ester product. 35. The ester manufacturing apparatus of claim 34, further comprising an ester storage tank connected to the fifth discharge port at the bottom of the ester recovery column to collect the obtained high purity ester product. CS > 25 1282746 36. The ester manufacturing apparatus of claim 17, further comprising a water storage tank connected to the third discharge port at the bottom of the liquid-liquid phase separation tank for collecting from the liquid The liquid phase separation tank separates one of the water-rich phase materials. 26 1282746 Year of the collection (〇月:ώ日修 (吏) is replacing page I VII. Designation of representative figure: Figure 0 (1) The representative figure of this case is: (1) (2) A brief description of the symbol of the representative figure : 1 Reactive distillation column 2 Ester recovery column 3 Liquid-liquid phase separation tank 4 Reboiler 5 Reboiler 6 Condenser 7 Condenser 8 Pump 9 Pump 10 T-type shunt tube A Acid feed B Alcohol feed C ester Storage tank D Water storage tank 11 ~ 16 Feed port 01 ~ 05 Discharge port 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: