Cross-Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0039717 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 manufacturing method and manufacturing system in which the manufacturing efficiency of an ester-based composition is increased by optimizing process parameters of a plurality of series-connected reactors.
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
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[14]
The present invention is to provide an efficient method and system for producing an ester-based composition, and a method for efficiently and continuously producing an ester-based composition by arranging a plurality of reactors in series and optimizing the process parameters of each reactor, and a method for the same We want to provide a manufacturing system.
means of solving the problem
[15]
In order to solve the above problems, a polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms are added to a mixer to form a reaction mixture (S1), a total of N reactors are connected in series from the first reactor to the Nth reactor A step of continuously introducing the reaction mixture into a reaction unit to continuously prepare a reaction product (S2), a step of continuously moving the reaction product to a separation unit to remove unreacted alcohol (S3), and removing from the separation unit Including the step (S4) of introducing the unreacted alcohol back into one or more reactors selected from among the reactors of the reaction unit, wherein N is an integer of 3 or more, and the step S2 satisfies the following Relations 1) and 2) A method for preparing a phosphorus ester-based composition is provided:
[16]
1) T n1-1 ≤T n1
[17]
2) E n2-1 ≥E n2 ≥E 1
[18]
In the formula, n1 is an integer from 2 to N, n2 is an integer from 3 to N,
[19]
T x = temperature of the xth reactor
[20]
E x = {(number of moles of alcohol input to the xth reactor - c*number of moles of polycarboxylic acid injected into the xth reactor/c*number of moles of polycarboxylic acid injected into the first reactor)*100%}
[21]
c = the number of carboxylic acid groups included in one molecule of polycarboxylic acid.
[22]
In addition, the present invention is 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 in which N reactors in which an esterification reaction of the reaction mixture is performed is connected in series, and the reaction product is delivered A separation unit including one or more separation columns from which unreacted alcohol is received, a recovery unit for introducing the unreacted alcohol removed from the separation unit back into the reactor in the reaction unit, and the temperature of each reactor and the alcohol introduced into the reactor Provided is a system for preparing an ester-based composition comprising a variable control for controlling an amount.
Effects of the Invention
[23]
The manufacturing method and manufacturing system of the present invention can efficiently manufacture an ester-based composition by designing a process to continuously use a plurality of reactors arranged in series, and optimizing the process parameters of each reactor arranged in series.
Best mode for carrying out the invention
[24]
Example
[25]
Hereinafter, preferred examples are presented to help the understanding of the present invention. The following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention.
[26]
[27]
As the polycarboxylic acid, high-purity terephthalic acid (PTA) as a dicarboxylic acid, 2-ethylhexanol as the alcohol, and tetra(2-ethylhexyl) titanate were used as the catalyst. The energy consumption used in the process of 5 and Comparative Examples 1-4 was calculated. The reaction unit consisted of three reactors connected in series. On the other hand, in Tables 1 to 4, the final reaction conversion rate of the examples described as 99.9% is based on the actual completion of the reaction, and the conversion rate in the present invention can be set to 99.99% or more in order to minimize the loss of the reaction raw material. it is self-evident The following conversion rates are calculated based on the number of reaction products, and an acid value (KOH mg/g) of the reactant of 0.1 was used as a criterion for completion of the reaction.
[28]
[Table 1]
Example 1 Example 2 Example 3
Reactor 1 Reactor 2 Reactor 3 Reactor 1 Reactor 2 Reactor 3 Reactor 1 Reactor 2 Reactor 3
Reaction time (hr) 2.5 2 2 2.5 2 2 2.5 2 2
Catalyst usage (wt% compared to PTA) 0.3 0.3 0.3
Raw material input mole (PTA, 2-EH) 100, 200 48, (96+80) 9, (18+80) 100, 200 48, (96+80) 10, (20+80) 100, 240 50, (140+40) 10, (60+40)
Conversion rate (%) 52 91 99.9 52 90 99.9 50 90 99.9
T(℃) 200 220 220 200 220 230 200 220 220
E(%) 0 40 40 0 40 40 20 40 40
Energy (KWh) 66 72 15 65 73 18 74 72 15
Total energy (Kwh) 153 156 161
[29]
[Table 2]
Example 4 Example 5
Reactor 1 Reactor 2 Reactor 3 Reactor 1 Reactor 2 Reactor 3
Reaction time (hr) 2.5 2 2 2.5 2 2
Catalyst usage (wt% compared to PTA) 0.3 0.3
Raw material input mole (PTA, 2-EH) 100, 140 60, (60+140) 7, (-46+140) 100, 200 49, (98+80) 10, (20+80+10)
Conversion rate (%) 25 93 99.9 0 40 35
T(℃) 200 220 220 200 219 220
E(%) -30 40 40 0 40 35
Energy (KWh) 60 79 13 66 72 14
Total energy (Kwh) 152 152
[30]
[Table 3]
Comparative Example 1 Comparative Example 2
batch reactor Reactor 1 Reactor 2 Reactor 3
Reaction time (hr) 6 2.5 2 2
Catalyst usage (wt% compared to PTA) 0.3 0.3
Raw material input mole (PTA, 2-EH) 100, 200 50, (100+80) 10, (20+80)
Conversion rate (%) 99.9 50 90 97.3 (unclosed)
T(℃) 220 200 220 210
E(%) 60 0 40 40
Energy (KWh) 198 65 71 13
Total energy (Kwh) 198 149
[31]
[Table 4]
Comparative Example 3 Comparative Example 4
Reactor 1 Reactor 2 Reactor 3 Reactor 1 Reactor 2 Reactor 3
Reaction time (hr) 2.5 2 2 2.5 2 2
Catalyst usage (wt% compared to PTA) 0.3 0.3
Raw material input mole (PTA, 2-EH) 100, 200 52, (104+80) 12, (28+80+40) 100, 200 52, (104+80) 124 (28+80+40)
Conversion rate (%) 48 88 99.9 48 86 99.9
T(℃) 200 218 220 200 215 216
E(%) 0 40 60 0 40 60
Energy (KWh) 64 71 70 63 69 51
Total energy (Kwh) 205 156
[32]
From the results of Tables 1 to 4, it was confirmed that the continuous process of the present invention can achieve energy savings of about 20% compared to the conventional batch process (Comparative Example 1). In addition, it was confirmed that when the process variable conditions (E and T conditions) in the present invention are satisfied, less energy is used or the reaction can be smoothly completed compared to the case where it is not (Comparative Example 2-4).
[33]
[34]
Specifically, in the case of Comparative Example 2, which did not satisfy the T condition by lowering the temperature in the final reactor, the conversion rate did not reach 99.9% even though the reaction was carried out for the same time as in Examples. It was confirmed that it was inefficient compared to the example because a lot of time was required. In addition, in the case of Comparative Examples 3-4, which did not satisfy the E condition by adding alcohol to the final reactor, unnecessary energy used for heating the alcohol that did not participate in the actual reaction among the added alcohols increased compared to Examples It was confirmed that the usage was large.
Modes for carrying out the invention
[35]
Hereinafter, the present invention will be described in more detail.
[36]
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.
[37]
[38]
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.
[39]
[40]
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.
[41]
[42]
Method for producing an ester-based composition
[43]
In the present invention, a polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms are added to a mixer to form a reaction mixture (S1), a total of N reactors from the first reactor to the Nth reactor are connected in series to the reaction unit. Step (S2) of continuously preparing the reaction product by continuously introducing the mixture, the step of continuously moving the reaction product to a separation unit to remove unreacted alcohol (S3); and a step (S4) of introducing the unreacted alcohol removed from the separation unit back into any one of the reaction units into a reactor, wherein N is an integer of 3 or more.
[44]
[45]
mixing step (S1)
[46]
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.
[47]
[48]
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 not mixed in advance. It is possible to solve problems that may occur in the case of direct input into the reactor, for example, the non-uniform reaction problem such as the conversion rate varies depending on the position inside the reactor.
[49]
[50]
In the manufacturing method of the present invention, the step S1 is a step of raising the temperature of the reaction mixture to 50 to 200 ℃, preferably 60 to 190 ℃, more preferably 70 to 180 ℃ in addition to mixing the polycarboxylic acid and alcohol may include more. In order for the reaction mixture to perform the reaction, it is necessary to supply energy to the reaction mixture, and when the reaction mixture is heated in advance and put into the reactor before the reaction mixture is heated in step S2 and the full-scale reaction is carried out, it is more in the reactor. Efficient and quick to respond. However, if the temperature at which the temperature is raised in step S1 is too low, it may be rather uneconomical because the effect of raising the temperature in advance is small, and when the temperature is raised to an excessively high temperature and input into the reactor, the reaction raw material polycarboxylic acid and alcohol are vaporized etc. may occur, so that a uniform reaction may not proceed, or a loss of reaction raw materials may occur.
[51]
[52]
Reaction step (S2)
[53]
The method for preparing the ester-based composition of the present invention includes a step (S2) of continuously preparing a reaction product from the reaction unit by continuously introducing the reaction mixture into a reaction unit in which N reactors are connected in series to perform the reaction.
[54]
[55]
In the present invention, the esterification reaction is performed using a plurality of series-connected reactors. When a reaction unit in which a plurality of reactors are connected in series instead of a single reactor is used, the space design of the process is easier by using a reactor having a smaller size than when using a single reactor, thereby reducing the design cost and reducing the cost of the reaction material. Since a plurality of reactors connected in series are continuously passed, process variables for each reactor can be independently controlled to optimize the entire process, thereby maximizing the efficiency of the manufacturing process.
[56]
[57]
In particular, the process variable of step S2 in the manufacturing method of the present invention may satisfy the following relational expressions 1) and 2):
[58]
1) T n1-1 ≤T n1
[59]
2) E n2-1 ≥E n2 ≥E 1
[60]
In the formula, n1 is an integer from 2 to N, n2 is an integer from 3 to N,
[61]
T x = temperature of the xth reactor
[62]
E x = {(number of moles of alcohol input to the xth reactor - c*number of moles of polycarboxylic acid injected into the xth reactor/c*number of moles of polycarboxylic acid injected into the first reactor)*100%}
[63]
c = the number of carboxylic acid groups included in one molecule of polycarboxylic acid.
[64]
[65]
The E value is based on “the amount of alcohol required to react 100% of the polycarboxylic acid initially introduced in the first reactor”, compared with “the amount of alcohol required to react 100% of the polycarboxylic acid introduced into each reactor” It means the ratio of “amount of alcohol added”. The above amounts refer to amounts based on moles. For example, if the polycarboxylic acid is a dicarboxylic acid, 100 moles of the dicarboxylic acid are added to the reactor, and 300 moles of alcohol is added, the alcohol for 100% reaction of the dicarboxylic acid is 200 moles, so 100 moles of additionally added alcohol is , the ratio of E value corresponds to 50% in the ratio of 100 moles to 200 moles. The E value may be controlled through step S4 to be described later, or a method of removing or additionally adding alcohol between reactors connected in series.
[66]
[67]
The inventor of the present invention has found that the continuous optimization of the ester-based composition manufacturing process is possible by adjusting the temperature of each reactor and the E value in each reactor in the step S2 as in Relations 1 and 2 above. It was confirmed that, when the relational expression is satisfied, the amount of the ester-based composition produced can be maximized while the wasted reaction raw material is minimized, and the amount of the composition produced per unit time can also be maximized.
[68]
In particular, the lower limit of T 1 in step S2 may be 100°C, 120°C, 140°C, 160°C or 180°C, and the upper limit of T 1 may be 220°C or 200°C. In addition, the lower limit of T N may be 140 ℃, 160 ℃, 180 ℃, 200 ℃ or 220 ℃, the upper limit of T N may be 220 ℃, 230 ℃, 240 ℃ or 250 ℃. If T 1 and T N are too low, sufficient heat may not be supplied for the reaction and thus a sufficient conversion rate may not be obtained.
[69]
Further, the lower limit of E 1 may be -30%, -20%, -10%, 0% or 10%, and the upper limit of E 1 may be 80%, 70%, 60%, 50% or 40%. . The lower limit of E N may be a value higher than the lower limit of E 1 , specifically 0%, 10%, or 20%, and the upper limit of E N may be the same as or lower than the upper limit of E 1 , and specifically may be 80%, 70%, 60%, 50% or 40%. When E 1 and E N are too few or too many, the two reaction raw materials are out of balance, and some of the reaction raw materials are wasted, and the composition in the maximum amount may not be prepared. In particular, when the E value of the first reactor is too high, the amount of alcohol that is excessively added from the beginning may be large, and a large amount of alcohol that does not participate in the actual reaction may be generated. In this case, the desired degree of conversion may not be achieved, or the actual reaction Too much energy is consumed to heat even the alcohol that cannot participate in the reaction, which may cause a problem in which the efficiency of the overall reaction process decreases.
[70]
[71]
In the manufacturing method of the present invention, N is preferably an integer of 3 or more, and more preferably an integer of 3 to 10. When the number of reactors is less than this, the technical advantage of arranging a plurality of reactors in series does not appear sufficiently. This may be rather large and may not be efficient in terms of the overall cost of the process.
[72]
[73]
Separation step (S3)
[74]
The production method of the present invention also includes a step (S3) in which the reaction product is continuously transferred to a separation unit to remove unreacted alcohol.
[75]
[76]
Specifically, step S3 is a step in which the reaction product prepared from the Nth reactor, which is the last reactor among the plurality of reactors, is continuously moved to the separation unit, and then unreacted alcohol is removed from the separation unit.
[77]
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.
[78]
[79]
Re-insertion step (S4)
[80]
The manufacturing method of the present invention includes a step (S4) of introducing the unreacted alcohol removed from the separation unit into one or more reactors selected among the reactors of the reaction unit again.
[81]
Specifically, step S4 is a step of adjusting the E value of each reactor by reintroducing unreacted alcohol removed in the separation unit from the first reactor of the reaction unit to one or more of the Nth reactors. By increasing the amount of alcohol input in this step S4, the E value of the reactor can be increased, and the E value of the reactor can be lowered by reducing the amount of alcohol input.
[82]
[83]
Catalyst addition (S1-1 or S1-2)
[84]
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.
[85]
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 dicarboxylic acid and alcohol, or to polycarboxylic acid or alcohol, respectively, 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.
[86]
[87]
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.
[88]
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.
[89]
[90]
Trans reaction step (S5)
[91]
The manufacturing method of the present invention may further include a step (S5) 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.
[92]
A composition including two or more types of ester compounds may be prepared through step S5, 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 the trans-esterification reaction. The step S5 is preferably performed after the removal of the unreacted alcohol, and if step S5 is performed before the removal of the unreacted alcohol, the trans-esterification reaction with the newly added alcohol due to the residual unreacted alcohol is not performed. It may not be easy, and even if a partial reaction proceeds, the efficiency of the reaction may be lowered due to the high content of alcohol. Therefore, the amount of unreacted alcohol included in the reaction product before the trans-esterification reaction is preferably 10% or less.
[93]
[94]
Ester-based composition manufacturing system
[95]
The present invention relates to a mixer in which a reaction mixture of polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms is formed, a reaction unit in which N reactors in which the esterification reaction of the reaction mixture is performed is connected in series, and the reaction product is received A separation unit from which the reaction alcohol is removed and including one or more separation columns, a recovery unit for introducing unreacted alcohol removed from the separation unit back to the reactor in the reaction unit, and the temperature of each reactor and the amount of alcohol introduced into the reactor Provided is a system for preparing an ester-based composition comprising a variable control to control.
[96]
The manufacturing system provided by the present invention can be used to implement the manufacturing method of the present invention, and the components of each system are the same as those described above, and a detailed description thereof will be omitted.
[97]
In particular, the variable control unit included in the production system of the present invention determines the amount of alcohol to be added to each reactor among the total amount of recovered unreacted alcohol or the amount of alcohol that moves between each reactor and at the same time controls the temperature of each reactor. It satisfies the above relational expressions 1) and 2), thereby optimizing the reaction in the reactor.
Claims
[Claim 1]
Forming a reaction mixture by adding a polycarboxylic acid and an alcohol having 3 to 10 alkyl carbon atoms into a mixer (S1); a step of continuously preparing the reaction product by continuously introducing the reaction mixture into a reaction unit in which a total of N reactors are connected in series from the first reactor to the Nth reactor (S2); The reaction product is continuously moved to a separation unit to remove unreacted alcohol (S3); and injecting the unreacted alcohol removed from the separation unit into one or more reactors selected from among the reactors of the reaction unit again (S4); wherein N is an integer of 3 or more, and the following Relations 1) and 2) production method of satisfying the ester-based composition is to: 1) T n1-1 ≤T n1 2) E n2-1 ≥E n2 ≥E 1 in formula, n1 is an integer from 2 to N, n2 is from 3 to N is an integer, and T x = temperature of the x-th reactor E x = {(number of moles of alcohol input to the x-th reactor - c*number of moles of polycarboxylic acid input to the x-th reactor/ c*poly input to the first reactor number of moles of carboxylic acid)*100%} c = the number of carboxylic acid groups included in one molecule of polycarboxylic acid, wherein T x and E xwhere x is an integer from 1 to N.
[Claim 2]
The method according to claim 1, wherein the separation unit comprises one or more separation columns or a purification tank in the form of a drum.
[Claim 3]
The method of claim 1, further comprising: adding a catalyst to the reaction mixture between steps S1 and S2 (S1-1); Or, adding a catalyst to the polycarboxylic acid or alcohol before the step S1 (S1-2); the method for producing an ester-based composition further comprising a.
[Claim 4]
The method of claim 3, wherein the catalyst is a tetraalkyl titanate.
[Claim 5]
The method of claim 1, wherein step S1 further comprises heating the reaction mixture to 50 to 200°C.
[Claim 6]
The method of claim 1, wherein T 1 is 100 to 220°C, and T N is 200 to 250°C.
[Claim 7]
The method of claim 1, wherein E 1 is -30 to 80%, and E N is 0 to 80%.
[Claim 8]
According to claim 1, wherein the reaction product from which the unreacted alcohol has been removed, adding an alcohol having 3 to 10 alkyl carbon atoms to the trans-esterification reaction (S5) further comprising; the alcohol added in step S5 is A method for producing an ester-based composition that is different from the alcohol input in step S1.
[Claim 9]
The method 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 10]
10. The method of claim 9, wherein the dicarboxylic acid is at least one selected from the group consisting of a linear dicarboxylic acid 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 method for producing an ester-based composition of at least one selected from the group consisting of carboxylic acid, tetrahydrofuran, tetracarboxylic acid, anhydrides thereof, and derivatives thereof.
[Claim 11]
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 in which N reactors in which the esterification reaction of the reaction mixture is performed are connected in series; a separation unit receiving the reaction product to remove unreacted alcohol and including one or more separation columns; a recovery unit for introducing the unreacted alcohol removed from the separation unit back into the reactor in the reaction unit; and a variable control unit for controlling the temperature of each reactor and the amount of alcohol introduced into the reactor, wherein N is an integer of 3 or more.
[Claim 12]
12. The method of claim 11, 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