Title of Invention: System and method for preparing ester-based composition
technical field
[One]
Cross-Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0039716 dated April 4, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
technical field
[4]
The present invention relates to a system and method for producing an ester-based composition, characterized in that a plurality of batch reactors are sequentially operated.
background
[5]
Phthalate-based plasticizers accounted for 92% of the global plasticizer market by the 20th century (Mustafizur Rahman and Christopher S. Brazel "The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges" Progress in Polymer Science 2004, 29, 1223-1248), mainly used to give flexibility, durability, and cold resistance to polyvinyl chloride (hereinafter referred to as PVC) and to improve processability by lowering the viscosity during melting. From hard products such as pipes to soft products that are soft and stretchable and can be used for food packaging, blood bags, flooring, etc. .
[6]
However, in spite of the compatibility with PVC of phthalate-based plasticizers and excellent softness imparting properties, recently, when PVC products containing phthalate-based plasticizers are used in real life, little by little leakage to the outside of the product causes endocrine disorders (environmental hormones) estimated substances and heavy metal levels. Controversy has arisen that it may act as a carcinogen (NR Janjua et al. "Systemic Uptake of Diethyl Phthalate, Dibutyl Phthalate, and Butyl Paraben Following Whole-body Topical Application and Reproductive and Thyroid Hormone Levels in Humans" Environmental Science and Technology 2008, 42, 7522-7527). In particular, in the 1960s, it was reported that di-(2-ethylhexyl) phthalate (DEHP), the most used phthalate-based plasticizer in the United States, leaked outside PVC products. Global environmental regulations, including various studies on the harmfulness of phthalate-based plasticizers to the human body, began to be implemented.
[7]
Accordingly, many researchers have developed a new non-phthalate-based plasticizer that excludes phthalic anhydride, which is used in manufacturing phthalate-based plasticizers, or suppressed the leakage of phthalate-based plasticizers to respond to environmental hormone problems and environmental regulations caused by the leakage of phthalate-based plasticizers. Research is underway to develop spill control technology that can significantly reduce risks and meet environmental standards.
[8]
On the other hand, as a non-phthalate-based plasticizer, the terephthalate-based plasticizer is not only at the same level in terms of physical properties as the phthalate-based plasticizer, but is also spotlighted as a material free from environmental problems, and various types of terephthalate-based plasticizers are being developed. In addition to research on developing terephthalate-based plasticizers with excellent physical properties, research on facilities for manufacturing such terephthalate-based plasticizers are also being actively carried out. is being requested
[9]
[10]
Prior art literature
[11]
(Patent Document 1) Republic of Korea Patent Publication No. 10-1354141
[12]
(Non-Patent Document 1) Mustafizur Rahman and Christopher S. Brazel "The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges" Progress in Polymer Science 2004, 29, 1223-1248
[13]
(Non-Patent Document 2) NR Janjua et al. "Systemic Uptake of Diethyl Phthalate, Dibutyl Phthalate, and Butyl Paraben Following Whole-body Topical Application and Reproductive and Thyroid Hormone Levels in Humans" Environmental Science and Technology 2008, 42, 7522-7527
[14]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[15]
The present invention is intended to provide an efficient method and system for producing an ester-based composition, employing a plurality of batch reactors mainly used for esterification reactions, connecting them in parallel, and sequentially operating them so that the entire process is semi- An object of the present invention is to provide a method and a system for producing an ester-based composition that secures both the stability of the batch reactor itself and the efficiency of the semi-continuous process by allowing it to run continuously.
means of solving the problem
[16]
In order to solve the above problems, the present invention provides a mixer in which a reaction mixture of a polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms is formed, N batch reactors connected in parallel in which the esterification reaction of the reaction mixture is performed, and the N A reaction unit equipped with an outlet line for discharging the reaction product from the batch reactor, a supply control unit for controlling the input amount and input path of the reaction mixture so that the reaction mixture is sequentially supplied from the mixer to the N batch reactors to sequentially complete the reaction; and a separation unit that receives the reaction product to remove unreacted alcohol and includes at least one separation column.
[17]
In addition, the present invention is a step of forming a reaction mixture by adding a polycarboxylic acid and an alcohol having an alkyl carbon number of 3 to 10 into a mixer (S1), and sequentially introducing the reaction mixture into N batch reactors connected in parallel to perform the reaction By doing so, the reaction is sequentially completed in N batch reactors to produce a reaction product semi-continuously (S2), and the reaction product is semi-continuously transferred to a separation unit to remove unreacted alcohol (S3) Including, wherein N is an integer of 3 or more provides a method for producing an ester-based composition.
Effects of the Invention
[18]
The manufacturing method and manufacturing system of the present invention can sequentially operate a plurality of parallel-connected batch reactors so that the entire reaction process operates semi-continuously, thereby securing both the stability of the batch reactor and the efficiency of the semi-continuous process. can do.
Brief description of the drawing
[19]
1 is a process flow diagram illustrating a system for preparing an ester-based composition including a mixer, a supply control unit, a reaction unit, and a separation unit according to an embodiment of the present invention.
[20]
2 is a process flow diagram illustrating a system for manufacturing an ester-based composition including a mixer, a supply control unit, a reaction unit, and a separation unit, wherein the supply control unit is provided inside the mixer according to an embodiment of the present invention.
[21]
3 to 5 are process flow diagrams illustrating a system for producing an ester-based composition in which a route through which a catalyst can be added is respectively indicated in an embodiment of the present invention.
[22]
6 is a process flow diagram illustrating a system for preparing an ester-based composition including a mixer, a feed control unit, a reaction unit, a separation unit, and a trans reaction unit according to an embodiment of the present invention.
Modes for carrying out the invention
[23]
Hereinafter, the present invention will be described in more detail.
[24]
The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[25]
[26]
In the manufacturing method and manufacturing system of the present invention, polycarboxylic acid refers to a compound having two or more carboxylic acid groups, and may mean, for example, dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid. The polycarboxylic acid used in the present invention may have 2 to 5 carboxylic acid groups, 2 to 4 carboxylic acid groups, or 2 to 3 carboxylic acid groups. When the polycarboxylic acid has an excessively large number of carboxylic acid groups, it may not be smoothly applied to the production method or production system of the present invention due to the high molecular weight of the polycarboxylic acid itself. The polycarboxylic acid is particularly preferably dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid. In the case of dicarboxylic acid, one selected from the group consisting of linear dicarboxylic acid having 2 to 10 carbon atoms, terephthalic acid, phthalic acid, isophthalic acid, and cyclohexane dicarboxylic acid. In the case of tricarboxylic acid, it may be at least one selected from the group consisting of citric acid, trimellitate acid and cyclohexane tricarboxylic acid, and in the case of tetracarboxylic acid, benzenetetracarboxylic acid, furantetracarboxylic acid, cyclohexane tetracarboxylic acid, and tetrahydro It may be at least one selected from the group consisting of furan tetracarboxylic acid. In addition, the polycarboxylic acid may include an anhydride or derivative thereof as well as itself.
[27]
In the production method and production system of the present invention, the alcohol having 3 to 10 alkyl carbon atoms is linear or branched from the group consisting of propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol and decanol. It is preferable that it is 1 or more types selected. In addition, the alcohol may be a single type of alcohol or a mixture containing isomers having the same carbon number. For example, when the alcohol is an alcohol having 3 alkyl carbon atoms, the alcohol may be one type of 1-propanol or 2-propanol, or a mixture containing 1-propanol and 2-propanol in a certain ratio. When the alcohol is in the form of a mixture containing isomers having the same carbon number, the relative amount between the isomers is not particularly limited.
[28]
[29]
Ester-based composition manufacturing system
[30]
The present invention provides a mixer in which a reaction mixture of polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms is formed, N batch reactors connected in parallel in which the esterification reaction of the reaction mixture is performed, an inlet line receiving the reaction mixture from the mixer, and a reaction unit equipped with an outlet line for discharging reaction products from the N batch reactors, and the reaction mixture is sequentially supplied from the mixer to the N batch reactors to sequentially complete the reaction. It provides a system for producing an ester-based composition comprising a supply control unit, and a separation unit that receives the reaction product through the outlet line of the reaction unit to remove unreacted alcohol.
[31]
The manufacturing system provided by the present invention can be used for carrying out the manufacturing method of the present invention, and includes a mixer 1 , a feed control unit 2 , a reaction unit 3 and a separation unit 4 .
[32]
1, the mixer 1 performs mixing of the polycarboxylic acid 11 and the alcohol 12 that are introduced into the mixer, and the reaction mixture generated from the mixer passes through the supply control unit 2 to the reaction unit ( 3) is sequentially introduced into each batch reactor (31 to 3N) included in. When the reaction in each reactor is completed, the reaction product moves to the separation unit 4, in which the unreacted alcohol 42 is removed, and the ester-based composition 41 is finally obtained.
[33]
In particular, the supply control unit 2 included in the manufacturing system of the present invention performs a role of determining the input start time, input amount and input completion time for each reactor when sequentially inputting the reaction mixture from the mixer to each reactor, It allows the sequential input of the reaction mixture to each reactor connected in parallel and the discharge of the reaction products.
[34]
The supply control unit may be a separate unit connected to the mixer as shown in FIG. 1 or may be a unit included in the mixer as shown in FIG. 2 . When the supply control unit is included in the mixer, the supply control unit may control the input path and the input amount of the reaction mixture directly discharged from the mixer.
[35]
In addition, as shown in FIGS. 3, 4 or 5 , the production system of the present invention may introduce the catalyst 13 into a polycarboxylic acid, an alcohol, or a reaction mixture thereof.
[36]
[37]
6, the production system provided by the present invention further includes a trans reaction unit 5 for trans-esterification reaction by adding an alcohol having 3 to 10 alkyl carbon atoms to the reaction product from which unreacted alcohol is removed. can The alcohol 52 input from the trans reaction unit is different from the alcohol input from the mixer, and the ester-based composition 51 including different ester-based compounds may be prepared through the trans reaction unit.
[38]
[39]
In addition, in the manufacturing system provided by the present invention, at least one of the N reactors is connected to the upper part of the reactor, and the alcohol and water discharged through the upper part of the reactor are separated from the gas-liquid separation column, and discharged through the upper line of the gas-liquid separation column. It may be provided with a decanter for recirculating alcohol to the reactor by layer-separating the liquid discharged through the lower line of the condenser and the gas-liquid separation column and the liquid condensed in the condenser for cooling the gas.
[40]
As described above, when the reactor is provided with a gas-liquid separation column, a condenser and a decanter, the efficiency and economic feasibility of the reaction can be increased by liquefying the alcohol, which is an opportunity during the reaction, and re-introducing it into the reactor, and at the same time, a by-product of the esterification reaction Phosphorus water can be removed to allow the reaction to proceed forward, i.e. to achieve a high conversion.
[41]
[42]
In addition, the supply control unit in the manufacturing system provided by the present invention may be to control one or more selected from the input path and the input flow rate of the reaction mixture to change according to a set time interval.
[43]
The supply control unit in the manufacturing system of the present invention must determine the input path and input flow rate of the reaction mixture so that the N reactors can function sequentially, and thus the reaction time, the total number of reactors, the desired production volume, etc. When a time interval is set and the input path and input flow rate of the reaction mixture are controlled by setting the set time interval as a period, after the reaction in each reactor is completed, the reaction is returned to the corresponding reactor when all or almost all of the reaction products are discharged. Since the mixture input is started, all reactors can be operated without gaps, and the efficiency of the process can be increased.
[44]
In addition, the time interval set in the supply control unit may be 50%, 60%, 70%, 80% or 90% or more of the value obtained by dividing the reaction time in one reactor by N, 150%, 140%, 130% , 120% or 110% or less. When the time interval is set in the above-mentioned range, it is possible to minimize the loss of not operating the reactor.
[45]
[46]
On the other hand, the above-mentioned reaction time is a value obtained by adding up the time consumed for the reaction and the time consumed for input of the reaction mixture and discharge of the reaction product. For example, when 30 minutes are consumed for the reaction and 15 minutes are consumed each for the input of the reaction mixture and the discharge of the reaction product, the reaction time is 60 minutes. If there are 4 reactors in this case, the dosing time interval for each reactor is 15 minutes, and the dosing of the reaction mixture to each reactor is started every 15 minutes.
[47]
[48]
Method for producing an ester-based composition
[49]
The present invention is a step of forming a reaction mixture by adding a polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms into a mixer (S1), by sequentially introducing the reaction mixture into N batch reactors connected in parallel to perform the reaction, In the N batch reactors, the reaction is sequentially completed to prepare a reaction product semi-continuously (S2), and the reaction product is semi-continuously transferred to a separation unit to remove unreacted alcohol (S3) And, N is an integer of 3 or more provides a method for producing an ester-based composition.
[50]
[51]
mixing step (S1)
[52]
The manufacturing method of the present invention includes a step (S1) of forming a reaction mixture by adding a polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms into a mixer.
[53]
[54]
Specifically, the step (S1) of forming the reaction mixture is a step of uniformly mixing the polycarboxylic acid and the alcohol having 3 to 10 alkyl carbon atoms in a mixer. In this step, before inputting the polycarboxylic acid corresponding to the reaction raw material and the alcohol having 3 to 10 carbon atoms into the reactor, the polycarboxylic acid and the alcohol having 3 to 10 carbon atoms are uniformly mixed in advance in a mixer, so that the raw materials are directly introduced. It is possible to solve the non-uniform reaction in the reactor that may occur in this case. In particular, since the reactor used in the present invention is a batch reactor, if the reaction raw materials are not mixed in advance and put into the reactor, the non-uniformity of the raw materials may be greatly increased depending on the position inside the reactor, and the agitation inside the reactor may be If it is not good, in particular, some raw materials may accumulate, which may cause difficulties in ensuring a uniform reaction time and conversion rate. On the other hand, when the reaction raw materials are mixed and added in advance, a substantially uniform degree of reaction can be obtained over the entire region of the reactor, and the reaction rate of each reactor can be maintained substantially uniformly to ensure the stability of the entire process.
[55]
[56]
In the production method of the present invention, step S1 may further include heating the reaction mixture to 50 to 200 °C, preferably 60 to 190 °C, more preferably 70 to 180 °C. Since the reaction mixture is heated in step S2 after step S1 to perform the reaction, when the reaction mixture is heated in advance in step S1 and put into the reactor, it can be easily and quickly reacted in the reactor. However, when the temperature to be raised in step S1 is too low, the effect of raising the temperature in advance has little effect. vaporization, etc. may occur, which may prevent a uniform reaction from proceeding.
[57]
[58]
Reaction step (S2)
[59]
The method for preparing the ester-based composition of the present invention comprises sequentially introducing the reaction mixture into N batch reactors to perform the reaction, so that the reaction is sequentially completed in N batch reactors to produce a reaction product semi-continuously ( S2).
[60]
[61]
In the case of a reaction process using a conventional batch reactor, a large amount of reaction products could be stably produced at one time, but the reactor is not operated in the process in which the reaction raw material is input or the reaction product is discharged. There were some bad downsides. Accordingly, the inventor of the present invention invented a method for producing an ester-based composition in which a plurality of batch reactors are used sequentially, so that the reaction product can be semi-continuously produced while maintaining the stability of the batch reactor.
[62]
[63]
Specifically, in step S2 of the manufacturing method of the present invention, the reaction mixture is sequentially introduced into N batch reactors, and each batch reactor to which the reaction mixture is added is heated to complete the reaction, and each batch reactor in which the reaction is completed is also sequentially The reaction product is discharged.
[64]
Exemplarily, step S2 may be performed as follows:
[65]
1) The reaction mixture uniformly mixed in the mixer is introduced into the first reactor, and the input to the first reactor is stopped after a predetermined amount of the reaction mixture is inputted.
[66]
2) After the time when the input is stopped, the first reactor is heated to perform the reaction, and the mixer introduces the reaction mixture into the second reactor.
[67]
3) After the predetermined amount of the reaction mixture is added to the second reactor, the input to the second reactor is stopped. After this point, the second reactor is heated to perform the reaction, and the mixer introduces the reaction mixture into the third reactor.
[68]
4) In this way, the N reactors sequentially prepare a reaction product, and after the reaction mixture into the Nth reactor is completed, the reaction mixture is again introduced into the first reactor. In addition, in the case of the reaction product prepared after the reaction is completed, it is sequentially discharged in the same manner.
[69]
[70]
In step S2, the time interval between the input to each reactor, that is, the time interval when sequentially input is 90 to 110%, preferably 100% of the total reaction time divided by the number of reactors. When the reaction mixture is introduced to each reactor at such an interval, after the reaction is completed in each reactor, the reaction mixture input to the corresponding reactor is started again when all or almost all of the reaction products are discharged, so that all reactors are empty. It can be operated without it, and the efficiency of the process can be increased.
[71]
The above-mentioned reaction time is the sum of the time consumed for the reaction and the time consumed for the input of the reaction mixture and the discharge of the reaction product. For example, when 30 minutes are consumed for the reaction and 15 minutes are consumed each for the input of the reaction mixture and the discharge of the reaction product, the reaction time is 60 minutes. If there are 4 reactors in this case, the dosing time interval for each reactor is 15 minutes, and the dosing of the reaction mixture to each reactor is started every 15 minutes.
[72]
[73]
In the manufacturing method of the present invention, in the step S2, since the introduction of the reaction mixture into the reactor, the temperature increase and the reaction, and the discharge of the reaction product are simultaneously performed, at least one of the plurality of reactors receives the reaction mixture, and at least another One reactor carries out the reaction, and at least one other reactor must discharge the reaction products. Accordingly, N is preferably an integer of 3 or more.
[74]
In particular, N may be an integer of 3 to 10, an integer of 3 to 7, or an integer of 3 to 5. When the number of reactors is too large, various additional devices are required, including a control unit for controlling that the reaction mixture is introduced into each reactor in order and the reaction product is discharged from each reactor, as well as a unit of one reactor. The reaction time may be shorter than the sum of the input time of the raw material input to the reactor and the discharge time of the reaction product, so that the reactor does not operate until the raw material is input, and as a result, the productivity may be adversely affected. . In addition, the space required for disposing each reactor may also be excessive, which may not be efficient in terms of the overall cost of the process.
[75]
[76]
In the step S2 of the production method of the present invention, an esterification reaction of a polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms is performed. The esterification reaction refers to a reaction in which a hydroxyl group of an alcohol and a carboxylic acid group of a polycarboxylic acid react to form an ester bond, and the esterification reaction in step S2 is 130 to 250° C., preferably 140 to 240° C., more preferably It may be carried out at a temperature of 150 to 230 °C. If the temperature raised in step S2 is lower than this, the energy required for the reaction is not sufficiently supplied and the reaction cannot proceed to a sufficient degree. Therefore, a sufficient amount of the reaction product may not be produced.
[77]
[78]
Separation step (S3)
[79]
The production method of the present invention also includes a step (S3) in which the reaction product is semi-continuously transferred to a separation unit to remove unreacted alcohol.
[80]
[81]
Specifically, the step S3 is a step in which the reaction products prepared in each of the N batch reactors are semi-continuously transferred to the separation unit, and then unreacted alcohol is removed from the separation unit. As described above, just as the input of the reaction mixture into the N batch reactors may be sequential, the discharge of the reaction products produced in each reactor may also be sequential or semi-continuous.
[82]
[83]
The separation unit used in step S3 may include one or more separation columns. According to the number of stages of the separation column included in the separation unit in the preparation method of the present invention, the composition ratio of the composition to be finally prepared may be changed, and those skilled in the art will know the separation unit according to the composition ratio or characteristics of the composition to be prepared. The number of stages of the separation column included in the can be appropriately adjusted. In addition, the separation unit may include a drum-type purification tank other than the separation column. The separation unit may remove the amount of unreacted alcohol contained in the reaction product to a level of 30% or less of the total, preferably 20% or less, more preferably 10% or less. By removing the unreacted alcohol in this way, the physical properties of the prepared ester-based composition may be uniform and excellent.
[84]
[85]
It is advantageous in terms of production management that the separation column is typically continuously operated, and for this purpose, the reaction product discharged from each reactor may temporarily stay in a facility such as a tank before being introduced into the separation column. The reaction product including unreacted alcohol in the facility may be retained at a level of 0.1 to 10 hours, and there is no limitation on the size of the facility as long as it is within a range capable of stably and continuously supplying the reaction product to the separation column.
[86]
[87]
Catalyst addition step (S1-1 or S1-2)
[88]
The manufacturing method of the present invention includes the step of adding a catalyst to the reaction mixture between the steps S1 and S2 (S1-1) or, before the step S1, adding a catalyst to a polycarboxylic acid or an alcohol having 3 to 10 alkyl carbon atoms (S1-2) may be further included.
[89]
A catalyst can be used for the esterification reaction of an alcohol and a carboxylic acid, and when a catalyst is used, the reaction can be completed more quickly. The catalyst may be added to a mixture of polycarboxylic acid and alcohol, or to each polycarboxylic acid or alcohol prior to preparing the mixture. In particular, it is preferable in terms of overall efficiency of the process to add the catalyst directly to the alcohol.
[90]
[91]
The catalyst used in the production method of the present invention is an acid catalyst such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, para-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, alkyl sulfuric acid, aluminum lactate, lithium fluoride, potassium chloride , metal salts such as cesium chloride, calcium chloride, iron chloride, aluminum phosphate, metal oxides such as heteropolyacids, natural/synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate and organic metals such as polymers thereof It may be more than one species, and may preferably be a tetraalkyl titanate. As the tetraalkyl titanate, TiPT, TnBT, TEHT, etc. can be used, and it is preferable to use a tetraalkyl titanate having the same alkyl group as an alkyl group of an alcohol having 3 to 10 alkyl carbon atoms as a ligand. When a catalyst having the same alkyl group as a ligand is used as described above, it is preferable not to control or generate catalyst by-products that may be generated in a subsequent process.
[92]
The amount of the catalyst used may be different depending on the type of catalyst, for example, in the case of a homogeneous catalyst, 0.001 to 5% by weight, 0.001 to 4% by weight, 0.01 to 3% by weight, or 0.01 to 2 based on 100% by weight of the total reaction mixture % by weight, and in the case of a heterogeneous catalyst, from 5 to 200% by weight, from 5 to 150% by weight, from 10 to 150% by weight, or from 20 to 150% by weight of the total amount of the reaction mixture.
[93]
[94]
Trans reaction step (S4)
[95]
The manufacturing method of the present invention may further include a step (S4) of trans-esterification reaction by introducing an alcohol having 3 to 10 alkyl carbon atoms to the reaction product from which the unreacted alcohol is removed, and the alcohol added in the step is It is different from the alcohol input in step S1.
[96]
A composition including two or more types of ester compounds may be prepared through step S4, and a person skilled in the art may select an appropriate alcohol according to the type of ester compound to be included in the composition and perform trans-esterification reaction. The step S4 is preferably performed after the removal of the unreacted alcohol. If the step S4 is performed before the removal of the unreacted alcohol, the trans-esterification reaction with the newly added alcohol due to the remaining unreacted alcohol is not performed. It may not be easy, and even if a certain part of the reaction proceeds, the efficiency of the reaction may be reduced due to the large amount of alcohol. Therefore, it is preferable that the amount of unreacted alcohol included in the reaction product before the trans-esterification reaction is 10% or less.
[97]
[98]
Explanation of symbols
[99]
1: mixer
[100]
11: Injection route of polycarboxylic acid
[101]
12: the route of injection of alcohol
[102]
13: Catalyst input route
[103]
2: supply control
[104]
3: Reaction unit
[105]
31 to 3N: each batch reactor (N total)
[106]
4: Separation unit
[107]
41: Movement path of the ester-based composition from which unreacted alcohol is removed
[108]
42: movement path of the removed unreacted alcohol
[109]
5: trans reaction unit
[110]
51: 12 alcohol input and a different alcohol input route
[111]
52: Migration route of ester-based composition through trans-esterification reaction
[112]
Claims
[Claim 1]
a mixer in which a reaction mixture of a polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms is formed; a reaction unit provided with N batch reactors connected in parallel in which the esterification reaction of the reaction mixture is performed, an inlet line for receiving the reaction mixture from the mixer, and an outlet line for discharging reaction products from the N batch reactors; a supply control unit for controlling an input amount and an input path of the reaction mixture so that the reaction mixture is sequentially supplied from the mixer to the N batch reactors to sequentially complete the reaction; and a separation unit that receives the reaction product through the outlet line of the reaction unit and removes unreacted alcohol.
[Claim 2]
The method of claim 1, further comprising a trans reaction unit for trans-esterification reaction by adding an alcohol having 3 to 10 alkyl carbon atoms to the reaction product from which unreacted alcohol has been removed, wherein the alcohol input from the trans reaction unit is mixed with a mixer. A system for producing an ester-based composition that is different from the alcohol input in the.
[Claim 3]
The gas-liquid separation column according to claim 1, wherein at least one of the N reactors is connected to the upper part of the reactor, and the alcohol and water discharged through the upper part of the reactor are separated, and the gas discharged through the upper line of the gas-liquid separation column is cooled. A system for producing an ester-based composition comprising a decanter for recirculating alcohol to the reactor by layer-separating the liquid discharged through the lower line of the condenser and the gas-liquid separation column and the liquid condensed from the condenser.
[Claim 4]
The system for producing an ester-based composition according to claim 1, wherein the supply control unit controls at least one selected from the input path and the input flow rate of the reaction mixture to be changed according to a set time interval.
[Claim 5]
5. The system according to claim 4, wherein the time interval is 50% to 150% of a value obtained by dividing the reaction time in one reactor by N.
[Claim 6]
The system of claim 1, wherein the polycarboxylic acid is at least one selected from the group consisting of dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid.
[Claim 7]
The method according to claim 6, wherein the dicarboxylic acid is at least one selected from the group consisting of linear dicarboxylic acids having 2 to 10 carbon atoms, terephthalic acid, phthalic acid, isophthalic acid, cyclohexane dicarboxylic acid, anhydrides thereof, and derivatives thereof, The tricarboxylic acid is at least one selected from the group consisting of citric acid, trimellitate acid, cyclohexane tricarboxylic acid, anhydrides thereof, and derivatives thereof, and the tetracarboxylic acid is benzenetetracarboxylic acid, furantetracarboxylic acid, cyclohexane tetra A system for producing at least one ester-based composition selected from the group consisting of carboxylic acid, tetrahydrofuran, tetracarboxylic acid, anhydrides thereof, and derivatives thereof.
[Claim 8]
Forming a reaction mixture by adding a polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms into a mixer (S1); By sequentially introducing the reaction mixture into N batch reactors connected in parallel to carry out the reaction, the reaction is sequentially completed in the N batch reactors to produce a reaction product semi-continuously (S2); and a step (S3) in which the reaction product is semi-continuously moved to a separation unit to remove unreacted alcohol, wherein N is an integer of 3 or more.
[Claim 9]
The method of claim 8, further comprising: adding a catalyst to the reaction mixture between steps S1 and S2 (S1-1); Or, before the step S1, adding a catalyst to the polycarboxylic acid or alcohol having 3 to 10 alkyl carbon atoms (S1-2); Method for producing an ester-based composition further comprising a.
[Claim 10]
The method of claim 9, wherein the catalyst is a tetraalkyl titanate.
[Claim 11]
The method of claim 8, wherein step S1 further comprises heating the reaction mixture to 50 to 200°C.
[Claim 12]
The method of claim 8, wherein the temperature at which the reaction of step S2 is performed is 130 to 250°C.
[Claim 13]
The method of claim 8, further comprising the step (S4) of trans-esterification reaction by adding an alcohol having 3 to 10 alkyl carbon atoms to the reaction product from which unreacted alcohol has been removed, wherein the alcohol added in step S4 is A method for producing an ester-based composition that is different from the alcohol input in step S1.