Mutual citations and related applications
[2]
This application claims the benefit of priority based on the date of Korea Patent Application No. 10-2017-0114624 07 years 09 January 2017, and all information disclosed in the literature of the Korea patent application are included as part of the specification.
[3]
[4]
Art
[5]
The present invention relates to a process for preparing a composition using the ester prepared in the system utilizing an integrated reactor ester composition and do this.
[6]
BACKGROUND
[7]
Phthalate plasticizer accounts for 92% of global plasticizer market (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 reference), mainly poly is given to the vinyl chloride (hereinafter, such as PVC & quot;) in flexibility, durability, cold resistance, and introduced into a variety of content in an additive, PVC is used in order to improve the lowering workability viscosity upon melting, such as a solid pipe grow well, yet soft and hard products, from food packaging and blood bags, have a close relationship with the real world than any other material from the flexible product that can be used such as flooring have had direct contact with the human body as the inevitable widely used applications.
[8]
However phthalate PVC and compatibility and excellent plasticizer Despite the soft grant, and during recent phthalate plasticizer is used real-life of the contained PVC product is gradually seeps out products of endocrine disorders (environmental hormones) estimating materials and heavy metal levels there are hazards controversy that may act as a carcinogen is raised (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, page 42, 7522-7527). In particular, for environmental hormones since the introduction of the report that the phthalate-based plasticizers of the amount is the number of di-ethylhexyl phthalate (di- (2-ethylhexyl) phthalate, DEHP) is discharged to the outside of PVC in the United States in the 1960s, 1990s deohaejyeo interest in the study of the human body, including various hazards of phthalate plasticizers were starting to global environmental regulations are made.
[9]
In many researchers phthalate and to cope with environmental hormone problem, and environmental regulations due to plasticizer outlet, developing a phthalate-based plasticizer prepared when using the anhydride is a new non-phthalate alternative plasticizers excluded that or suppress the outflow of the phthalate-based plasticizer body to develop a spill suppression technology that can meet even significantly reduce the risks as well as environmental standards has proceeded out the research.
[10]
On the other hand, the non-phthalate as plasticizers, terephthalate-based plasticizers include phthalate as well as the same level in of plasticizer properties side, and the spotlight as a free substance from the environmental problems, a variety of terephthalate-based plasticizer, a situation which is being developed the physical properties are excellent terephthalate-based research to develop a plasticizer, as well as also has been actively carried out research on the plant for the production of such terephthalate-based plasticizer, more efficient and economical in terms of process design design of a simple process that is required.
[11]
[12]
Prior Art Document
[13]
Patent Documents
[14]
Patent Document 1: Republic of Korea Patent No. 10-1354141 No.
[15]
[16]
Non-Patent Document
[17]
(비특허문헌 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
[18]
(비특허문헌 2) N. R. 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
[19]
Detailed Description of the Invention
SUMMARY
[20]
The present invention is effective, as one to provide the economical and manufacturing of a simplified ester composition system, and separate alcohol integrated reactor and the mixing is carried out in the space reaction the reaction and ester compositions are ester compounds prepared is prepared column and the gas-liquid separation column introduced can be a facility space and reduction reaction facility is substantially removed through the can to provide a manufacturing method of the ester composition using the manufacturing system and this in a simplified ester composition capable of reducing the transfer time.
[21]
Problem solving means
[22]
In accordance with one embodiment of the present invention for solving the above problems, the present invention provides a product and a second alcohol, of carboxylic acid-based compound is a reaction wherein the direct ester react directly with the ester reaction comprising a first alcohol, and 2 or more carboxyl groups trans ester reaction the reaction is carried out within the reaction space, the integrated reactor equipped with a bottom outlet line to the outlet line and the top compartment and a liquid compartment which is associated with the gas phase, which; Said reaction product and a low boiling mixture of vapor vaporized from the integrated reactor is introduced through the top outlet line of the integrated reactor, the gas-liquid separation space, which gas-liquid separation is carried out, the low boiling point of the liquefied reaction product is recovered as an integrated reactor, the bottom return line and the gas phase an upper outlet line is provided with a gas-liquid mixture outlet separation column; Purification, the composition is the purified ester in the crude product discharge line and a second alcohol recovery line is the number of times that the alcohol comprises a bottom exit of the purifier unit that is ester composition and the second alcohol to the outlet line of the integrated reactor separation; The first alcohol and the alcohol storage tank 2 alcohol is stored inside the space is provided to be a mixture of alcohol of the first alcohol and a second alcohol storage is connected to the upper outlet line, and alcohol recovery line of the purification unit of the gas-liquid separation columns .; And alcohol separation space and the alcohol is provided with at least one recirculation line is recycled separate mixing alcohol separation column is a mixture of alcohol introduced is a mixture of alcohol separation along the alkyl carbon number of the alcohol from the alcohol tank, and including, the gas-liquid separation the reaction product of the column is a product of decomposition or reaction of the trans-ester directly ester reaction, the low boiling point mixture is provided with a manufacturing system comprises at least one of the first alcohol and a second alcohol.
[23]
Effects of the Invention
[24]
According to the invention, the equipment space can be reduced and the reaction equipment can be significantly removed and reducing transfer time, effective and may provide a method of producing ester composition economical, the manufacture of a simplified ester composition system and using the same. .
[25]
Brief Description of the Drawings
[26]
1 is a process flow diagram showing an example of a process for fabricating a conventional ester compositions.
[27]
Figure 2 is a process flow diagram which illustrates an example of a process for preparing ester compositions according to the manufacturing system of the present invention.
[28]
Mode for the Invention
[29]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[30]
The terms or words used in the description and claims of the present invention is general and not be construed as limited to the dictionary meanings are not, the inventor accordingly the concept of a term to describe his own invention in the best way on the basis of the principle that can be defined, which must be interpreted based on the meanings and concepts corresponding to technical aspects of the present invention.
[31]
[32]
The manufacturing system of the ester compositions
[33]
According to one embodiment of the invention, an integrated reactor; Gas-liquid separating column; Purification unit; Alcohol storage tank; And mixing the alcohol separation system; the production system is provided comprising a.
[34]
Specifically, the integrated reactor, the first alcohol and a carboxylic acid-based product of the compound is reacted ester reacts with the direct ester reaction directly to and the second within the reaction space transformer are ester reaction carried out for an alcohol reaction comprising a two or more carboxyl , it is provided with a bottom outlet line connected to the top outlet line and a liquid compartment is associated with the gas phase compartment.
[35]
Further, the vapor-liquid separating column, the low boiling point mixture in a direct ester reaction product and the vapor evaporated from the combined reactor flows through the top outlet line of the integrated reactor, the gas-liquid gas-liquid separation space is separated is carried out, the liquid directly ester reaction product the top outlet line is a low-boiling mixture of vapor phase containing a lower number of lines and the first alcohol is recovered as an integrated reactor outlet is provided.
[36]
It said top while being a low-boiling mixture of vapor that exits via the outlet line to the direct ester reaction is carried out with water and the first alcohol is included to reflux and the water and the first alcohol by decanting separated to recover a first alcohol to the reactor and direct the ester reaction ended and includes a first alcohol until the trans-ester reaction is carried out under reflux is first includes a first alcohol and a second alcohol of trace during which the alcohol can be removed, the trans ester reaction performed the via can be recovered in the first alcohol and a second alcohol to the reactor.
[37]
In addition, the integrated reactor may further comprise a stop line as the outlet line to the liquid phase in the reactor compartment, the stop outlet line is connected with the side of the gas-liquid separating column, one-half or more of the height direction of the gas-liquid separating column as specifically It can be connected to the side of the point.
[38]
The interruption to the outlet line may be material of the liquid to be that flows in a gas-liquid separation column, in particular flows a low-boiling mixture are not vaporized and the reaction product of a liquid, such as flowing the material of the gas phase to gas-liquid separation column to the top of the exit line have.
[39]
When provided with a stop outlet line as described above, advantages such as to maximize the removal level of the material to be removed with a speed of result process time of which may be gas-liquid separation efficiency is maximized The separation efficiency is improved by using the gas-liquid separating column the can get.
[40]
The purification unit, the purification, the alcohol is purified ester composition discharged purified product line and a first alcohol and the second being the lower end outlet of the line outlet in ester compositions, the first alcohol and the second alcohol in the combined reactor separation will the number of times that the alcohol recovery line provided that the alcohol storage tank is connected with the first alcohol and a top outlet line of the gas-liquid separating column and having an internal space in which two alcohol is stored, and an alcohol recovery line of the purification unit of claim 1 will be a mixture of alcohol and a second alcohol alcohol storage.
[41]
The purification unit using the facility, or the like at least one purification and the condenser, can be to perform the purification, a distillation column arranged in some cases, can, and to apply the appropriate number of facilities in accordance with the desired level of purity It may be. Each type of equipment can be applied to be used in tablets generally in the art and is not particularly limited.
[42]
The mixed alcohol separation column is provided with a separation space alcohol, recycled or more separate alcohol is a recycle line and one exhaust line which is a mixture of alcohol separated according to carbon number of the alkyl alcohol is a mixture of alcohol from the alcohol tank inlet.
[43]
In addition, at least one recycle line of the mixed alcohol separation column is preferably two recycled and the line may be provided, the first recycled to the first alcohol recycle line and the second alcohol is integrated reactor in which the alcohol is recycled into the integrated reactor the alcohol may be a second recirculation line and one exhaust line which may be a line in which the water is discharged.
[44]
Manufacturing system of ester compositions according to the invention by introducing the mixed alcohol separation column, can be reused by separating no longer disposed of the mixture of two or alcohol and water are mixed together, whereby the economic efficiency in the process operation It can be improved.
[45]
In addition, the manufacturing system may further comprise a product reservoir, the product reservoir may be connected with the crude product line of the purification unit.
[46]
According to one embodiment of the invention, processes such as the manufacturing system may be a batch type reaction system, the recovery of the alcohol may be performed after one cycle.
[47]
Further, it can preferably be directly carboxylic acid-based compound containing two or more carboxyl groups as a raw material for the reaction of terephthalic acid ester, first alcohol and a second alcohol may be a primary alcohol, -OH groups may be preferred that one individual . For example, because there is a fear proceed polymerization of a polyester can not match the process conditions applied in the manufacturing system of the present invention, can result in fouling polymers within the furnace due to the reactor 2 or more -OH groups, is beyond the object of the invention to be obtained a polyester composition, it is the first alcohol and the second alcohol is preferably -OH group, yet the primary alcohol applied to one individual.
[48]
In addition, the first alcohol and the second alcohol may be different in each of the alkyl carbon atoms, a has an alkyl carbon number of the first alcohol can be great be compared to the alkyl carbon atoms in the second alcohol, carbon atoms having an alkyl group of 1 to 12 there is an alcohol may be used. Preferably alkyl having a carbon number of the first alcohol may be from 6 to 12, carbon atoms, alkyl of the second alcohol may be from 1 to 5. More preferably alkyl having a carbon number of the first alcohol may be 7 to 10 days, alkyl having a carbon number of the second alcohol can be a 2 to 4.
[49]
The desired product in the manufacturing system in accordance with one embodiment of the present invention may be a composition containing the terephthalate may be containing the ester compound of the three and, preferably, three types of terephthalate as ester composition.
[50]
[51]
Reference to the accompanying drawings, will be described in detail one example of the present invention;
[52]
Figure 1 shows an example of a process flow diagram of a system for producing a conventional ester compositions. System for producing a conventional ester compositions can largely separated into two, which transformer for producing a polyester composition using the ester compound of the direct ester reaction step, a second step for preparing the ester compound of the first stage it is the ester process, and the two processes it is common to be performed separately.
[53]
Specifically, in the case of the direct ester reaction step of the first stage, when the first reactor (11a) in the carboxylic acid-based compound and the direct ester reaction of a first alcohol comprising groups of two or more carboxyl is performed, directly ester reaction was completed first gas-liquid separating column, removing the first alcohol and water using a (12a) and a first alcohol removal time is introduced to a first alcohol storage tank (14a), the first alcohol storage tank (14a) a first alcohol the stored dueotdaga supplies a first alcohol back to the first reactor (11a) when the entire process is completed one cycle.
[54]
The first is the flow outlet comprising with the by-product such as an ester compound and unreacted first alcohol produced by ester reaction directly in the reactor (11a) flows into the first buffer tank (16a), the first buffer tank (16a ) is the product and properly unreacted first unreacted first alcohol fed to the alcohol stripping column 17, the separation capacity, can control the by-product stream in accordance with the separation capacity of the unreacted first alcohol stripping column (17) remove.
[55]
The first buffer tank (16a) is the front end of the first reactor (11a) and reaction of the gas-liquid separation column (12a) is carried out in a batch reaction and a first alcohol stripping column 17 at the rear end is that the performed in a continuous manner in, can serve to connect the batch process and continuous process.
[56]
Subsequently, the product stream comprising unreacted first alcohol is removed the product flow, i.e., ester compounds, and again flows into the second buffer tank (16b), and serves to direct storage of the product, ester compounds of the ester reaction, trans claim the ester reaction and supplies the ester compound to the second reactor (11b). The unreacted alcohol is removed the first time is returned to the alcohol storage tank (14a).
[57]
A second buffer tank (16b) is also the second buffer is removed, the process of the alcohol at the front end is carried out continuously in a tank (16b), first the batch reaction of trans-esterification reaction from the rear end of the second buffer tank (16b) proceeds at the time the device for connecting the second reactor (11b) that is, that may be a device that connects to a continuous process and a batch process.
[58]
In the case of the trans-ester of the 2-stage reaction process, the directly proceeds ester In analogy to the reaction step, the ester in the composition in an ester reaction of trans-ester compound and the second alcohol in the second reactor (11b) is produced. After this time the reaction was complete, the direct esterification process, similar to the second gas-liquid separation column (12b) by removing the first alcohol, the second alcohol and trans-esterification product (by-product) in the reaction of the unreacted mixed alcohol tank through the It is recovered in (14b).
[59]
Furthermore, when the reaction is complete, the product stream is discharged from the reactor, the stream is introduced into the neutralizer 18 and the purification section 13 has a product can be purified via the equipment for purification. 1 Although the neutralizer 18 and the purification unit 13 is shown as a separate device, which may be integrated into a single plant.
[60]
The conventional ester composition production process, such is there are many equipment overlap, despite the similar process Fair, and did not apply to an integrated plant due to such a decrease mixed alcohol separated in the gas-liquid separation efficiency difficulty reason you that the alcohol is mixed.
[61]
However, ester integrated reaction system than the system is a step of preparing the ester composition using the process and the ester compound for preparing the ester compounds to an existing, which has been used in combination, the gas-liquid separating column and a mixture of alcohol separation efficiency a column of the composition of the present invention due to the application of, it is possible to significantly reduce the process equipment is duplicated plant can be reduced even more than half site, it is possible to secure the economical efficiency in manufacturing cost savings, reduced operating costs, such as processes and therefore, the process is simplified this efficiency can be maximized.
[62]
Figure 2 illustrates an example of a process flow diagram of a manufacturing system according to the present invention.
[63]
2, the integrated reactor 21 directly ester reacted with the trans ester in the reaction can be carried out in the same space in sequential order, and can reduce the equipment as compared to that used for two reactors, mixed alcohol separation column (25 ) through the introduction of two kinds of by-products of alcohol and other low boiling point of, it may be possible to properly recycled to the reactor in each reaction cycle, even if the separation of the first alcohol and a second alcohol introduced with the alcohol storage tank 24 of .
[64]
In the case of the conventional process, the reactor is present and is (equipment such as condenser, reflux tank, etc., including a separation column) separation processes exist separately separately and the side-by-side a continuous process and a batch process thus the buffer tank (16a, 16b) and continuous, but the process and included in the design a facility that connects the batch process are required, such as, is and the reactor is integrated separation process is integrated as in the present invention, if being able to separate the mixed alcohol has a buffer tank (16a, removing the plants, such as 16b) has the advantage that the process can be operated.
[65]
Specifically, carboxylic acid containing an at least first two carboxyl compound and the first alcohol is added to the integrated reactor 21 and the reaction can be initiated directly by the ester reaction ester compounds and unreacted first alcohol and 2 or more carboxyl groups carboxylic acid-based compound that contains, and can be a water generated as a by-product.
[66]
Removing the essentially made of the water is directly ester reaction that is generated as a by-product of the ester in the reaction, which can be carried through the gas-liquid separating column 22. Among specifically, the direct ester reaction may be There is a low-boiling compounds in the gas phase through the top outlet line 211 of the combined reactor 21 is to be released, low-boiling compounds at this point contains the water and the first alcohol, when water and the first alcohol is separated from the gas-liquid separation column 22 and a condenser (not shown) and a decanter (not shown) connected to the upper end of the column, the first alcohol is refluxed flows back to the reactor, the water is It can be removed. The first alcohol is recovered in the reflux may be returned through the inlet line, the line is the first alcohol is integrated reactor 21 through the lower return line 221 is connected to the bottom of the gas-liquid separation column 22, It may be recovered by.
[67]
When the direct ester reaction was completed, a second first alcohol a product order to the reaction proceeds toward the product from the equilibrium reaction of trans-ester reaction to, it applied previously may be added to the alcohol in the integrated reactor 21 to a transformer ester reaction need to be removed, and removal of the first alcohol can be performed through the gas-liquid separation column 22.
[68]
There is a direct ester reaction product and a low boiling mixture of vapor vaporized from the integrated reactor 21 flows out through the top outlet line 211 of integrated reactors can be introduced into the gas-liquid separation column 22, this time, by applying the pressure-gas-liquid It may be sent to the separation column (22). The material of the vapor flowing into the gas-liquid separating column 22 are able to be done by a gas-liquid separation using a boiling point difference and mass transfer in the gas-liquid separation space in the column, the vaporized directly ester reaction product is re-liquefying the gas-liquid separation column (22 ) flows back into the reactor through a lower return line 221, as the low boiling point mixture first alcohol may be stored is introduced into the alcohol storage tank 24 through the upper outlet line (222).
[69]
Because of the gas-liquid separation column 22 in the integrated reactor 21 within the pressure-sensitive material of the gas phase through the sending by the mass transfer area narrow and efficiency may be lower, so that preferably, connected to the liquid compartment of the integrated reactor 21 can be made to flow to an outlet line provided with a stop 213, a low boiling point liquid mixture and direct ester reaction product of a non-vaporized through, stops outlet line 213 is 1/2 of the height direction of the gas-liquid separation column 22, may be connected to the side portions of the above points, and the power unit (not shown) for sending the liquid materials of the reactor in the liquid phase divided by the gas-liquid separation column 22 may be provided in the stop outlet line, wherein the power unit is a wide variety of It may be a pump (not shown). In this way the gas-liquid separation column 22, when it comprises a break outlet line of the integrated reactor 21 so as to be introduced into There can maximize gas-liquid separation efficiency due to the increase in mass transfer area to the desired level in the reactor in a short period of time It can be removed first, unreacted alcohol.
[70]
The first alcohol removed from the gas-liquid separating column 22 was introduced into the alcohol storage tank 24 is then stored in a certain period of time or is directly introduced into the mixing alcohol separation column (25) for separating the first alcohol and a second alcohol this process can be carried out.
[71]
On the other hand, directly after the ester reaction is terminated and the unreacted within the integrated reactor 21, the first alcohol is removed, may be added to the second alcohol to the integrated reactor 21 for trans-ester reaction.
[72]
At this time, it may be present in an integrated reactor 21, the reaction product supply section (not shown), a reactant feed portion carboxylic acid-based compound, the first alcohol, the second all the reactants, such as alcohols comprising a two or more carboxyl are through parts of a supply of It may be injected, each supply unit may be provided, each injection. Further, the reaction after the advanced first cycle there is a mixture of alcohol separation in a mixed alcohol separation column (25) from the alcohol storage tank 24 alcohol recycle line (251a, 251b) the first alcohol and the second alcohol is injected into the reactor through the It may be.
[73]
Second and alcohol may be added directly ester is carried out in response trans ester reaction integrated reactor 21 with the ester compound in the product, the subsequent process can be similar to the direct ester reaction. Recovering the first alcohol and a second alcohol vaporized through the trans ester reaction medium to the direct gas-liquid separation as in the ester the reaction column (22) to the condenser (not shown) and decanter (not shown) as an integrated reactor 21 again can do.
[74]
When the trans ester reaction was completed, the product of the trans-ester reaction there is a purification step can be carried out for commercialization, the lyotropic liquid through the bottom outlet line (212) of an integrated reactor is introduced into the purification unit 23, purification unit (23 ) in the product it can be purified by using the facilities that include at least one purification and the condenser.
[75]
Purification unit 23 in may be to remove by-products or unreacted materials from the product, whereby the alcohol is a second alcohol, such as in the first alcohol by-product of unreacted separation through the alcohol recovery line 231, a storage tank (24 ) and to be introduced, after being introduced into the alcohol storage tank 24 is appropriately separated from the alcohol mixture separation column 25 may be recycled to the process integrated reactor 21 do.
[76]
Product such as unreacted substances are removed from the stream is able to flow to the crude product line 232. The product storage tank (not shown) through the product stored in the storage tank can be commercialized after the desired process.
[77]
The first alcohol and the second alcohol is an alcohol storage tank 24 and then flows into the saved period of time, or is directly introduced into the mixing alcohol separation column (25) a first alcohol and a second alcohol which is removed from the purification unit (23) a process in which separation can be performed, and the alcohol recycled to the well-integrated reactor 21 the reaction time of the line (251a, 251b) through which can be recycled, the columns of the discharge line at the top to remove with water present as a by-product , water may be removed through (251c).
[78]
Further, although not shown in the Figure 1 and 2, process design, in general apparatus it included in such a heat exchanger, a condenser, a reboiler and a pump may be any person skilled in the art and include in the design, properly arranged in accordance with the design.
[79]
[80]
Process for producing a polyester composition
[81]
According to another embodiment of the invention, steps a carboxylic acid-based compound and the ester compound and the water through the direct reaction of the ester in the first alcohol containing two or more carboxyl groups in an integrated reactor prepared (S1); Removing the low boiling point mixture containing the unreacted alcohol and water in the first reactor and the combined number of the first alcohol as the alcohol reservoir (S2); In the second step of the alcohol with the combined reactor produced composition of an ester through the reaction of the trans-ester ester compound and a second alcohol (S3); And a step (S4) for recovering the mixed alcohols to give the ester composition to the alcohol storage tank, a method of making a composition comprising an ester, is provided.
[82]
A method that applies the above production method in the above-described manufacturing system, a series of processes are also all identical to that described above, description of the reaction raw material, so also the same as that described above, and a description thereof will be omitted.
[83]
However, the in step S2 if the removal of the first alcohol, the unreacted include in the integrated reactor, the reactor is a first alcohol of the total, based on the weight of the unreacted substance, and preferably removed so that less than 2% by weight, this there removing a short time up to the level it may be desirable to utilize with the above-mentioned outlet line interruption.
[84]
The specific reaction conditions, direct reaction of ester and trans-ester reaction (temperature, pressure, time and the like), the reaction conditions applied in the art can be applied is not particularly limited.
[85]
[86]
Example
[87]
And to more specifically explain the present invention by the following examples. However, the Examples are not limited the scope of the invention to these are for illustrating the invention.
[88]
[89]
The following Examples 1 and 2 and Comparative Example 1 was simulation of a system, including the removal unit according to the present invention using a commercially available process simulation program ASPEN PLUS within BATCH MODELER.
[90]
[91]
Example 1
[92]
As a reaction raw material, terephthalic acid, 2-ethylhexanoic and then proceed to the introduction of the integrated reactor 21 the ester directly to the reaction ol, butanol introducing the integrated reactor 21 to complete the reaction proceeds and the reaction of trans ester 2 according to the process flow shown in the ester composition was carried out the manufacturing process, was carried out to directly react with the ester trans ester reaction medium to remove the 2-ethylhexanol via the outlet line stops and the top outlet line of the integrated reactor, the result shown in Table 1.
[93]
[94]
Example 2
[95]
But performs a process of manufacturing the polyester composition in the same manner as in Example 1, without applying ended outlet line of the integrated reactor, the reaction medium directly ester and trans-ester reaction, the 2-ethylhexanol was removed through the top outlet line the results are shown in Table 1.
[96]
[97]
Comparative Example 1
[98]
As a reaction raw material, terephthalic acid, 2-ethylhexanoic and then proceed with the ester reaction directly introduced into the first reactor (11a) ol, butanol in the simulation according to the process flow diagram, and the second reactor (11b) shown in Figure 1 introduced to the process simulation shown in Table 1. the results are carried out according to the process flow diagram shown in Figure 1, and to complete the reaction proceeds the trans ester reaction.
[99]
TABLE 1
Example 1 Example 2 Comparative Example 1
Material introduced amount (kg) Terephthalic acid 5.0 5.0 5.0
2-ethylhexanol 6.5 6.5 8.3
Butanol 1.2 1.2 2.3
Yield (kg) product 10.9 10.9 10.9
One cycle process execution time (hr) 18.7 19.2 19.8
Transfer step Duration (min) 40 40 110

[100]
, In the case of Examples 1 and 2, applying the integration process, it is possible to see that the process time is significantly shorter than in the comparative example 1 carried out as a separate step, the time, as can be seen in Table 1 are required for one cycle considering the fact that that time, can lead to significant delays look at the entire product supply and demand sides, and eventually it can be seen that to get the issue that productivity is lowered. That is, if applying the manufacturing system of the present invention using the integrated reactor, it was confirmed that can increase productivity.
[101]
In addition, it can be seen that the amount of 2-ethyl hexanol and butanol greatly reduced compared to the case of input Compared to raw material introduced amount, for example 1 and 2 to Comparative Example. Embodiment can be confirmed in Examples 1 and 2 in the case that it is possible to reduce the amount of raw material alcohol to be newly added because it introduces the mixed alcohol separation column which can be reused without having to discard the mixed alcohols.
[102]
And, that as a portion to be the increase in the efficient performance of the process operation, the transfer time in comparison to the comparative example, if the result of evaluating the time, Examples 1 and 2 required for the transfer can be reduced by about one-third It can be found. This allows, if applied to a manufacturing system of the ester composition according to the invention it can be confirmed that the process is operating efficiently is possible.
[103]
Further, in the case of Example 1 applied to stop the outlet line to the gas-liquid through the separation column in an integrated reactor, removal of the first alcohol, i.e. 2-ethylhexanol, shorter than the process time in comparison with the second embodiment to increase the gas-liquid separation efficiency It can also been confirmed.
[104]
[105]
Reference Numerals
[106]
11a: first reactor 11b: second reactor
[107]
12a: first gas-liquid separation column 12b: second gas-liquid separation column
[108]
13: purification
[109]
14a: an alcohol tank 14b: Mixed alcohol tank
[110]
16a: first buffer tank 16b: second buffer tank,
[111]
17: unreacted alcohol stripping column
[112]
18: heavy
[113]
21: Integrated reactor 22: a gas-liquid separation column
[114]
23: refining unit 24: storage tank alcohol
[115]
25: Mixing alcohol separation column
[116]
211: top of the outlet line 212: bottom of the exit line
[117]
213: stop exit line
[118]
221: lower recovery line 222: top outlet line
[119]
231: alcohol recovery line 232: purified product line
[120]
251a: first alcohol circulation line 251b: second alcohol circulation line

WE Claims

[Claim 1]
A first upper outlet line connected with the reaction space, vapor compartment and directly ester reaction of the carboxylic acid-based compound reaction including alcohols and two or more carboxyl groups which the trans ester reaction product and the second alcohol is reaction of the direct ester reaction performed and an integrated reactor equipped with a bottom outlet line connected to the liquid phase section; Said reaction product and a low boiling mixture of vapor vaporized from the integrated reactor is introduced through the top outlet line of the integrated reactor, the gas-liquid separation space, which gas-liquid separation is carried out, the low boiling point of the liquefied reaction product is recovered as an integrated reactor, the bottom return line and the gas phase an upper outlet line is provided with a gas-liquid mixture outlet separation column; Purification, the composition is the purified ester in the crude product discharge line and a second alcohol recovery line is the number of times that the alcohol comprises a bottom exit of the purifier unit that is ester composition and the second alcohol to the outlet line of the integrated reactor separation; The first alcohol and the alcohol storage tank 2 alcohol is stored inside the space is provided to be a mixture of alcohol of the first alcohol and a second alcohol storage is connected to the upper outlet line, and alcohol recovery line of the purification unit of the gas-liquid separation columns .; And alcohol separation space and the alcohol is provided with at least one recirculation line is recycled separate mixing alcohol separation column is a mixture of alcohol introduced is a mixture of alcohol separation along the alkyl carbon number of the alcohol from the alcohol tank, and including, the gas-liquid separation the manufacturing system of the reaction product from the column is a product of decomposition or reaction of the trans-ester directly ester reaction, the low boiling mixture comprising at least one of the first alcohol and a second alcohol.
[Claim 2]
The method of claim 1, will the stop outlet line is further provided within the liquid compartment the integrated reactor, the stop outlet line is connected to the interruption of the gas-liquid separation column break in the vapor-liquid separating column in the height direction of the column 1 / not less than two points in the manufacturing system.
[Claim 3]
The method of claim 2, wherein the manufacturing system of the stop outlet line of the integrated reactor, that is a low boiling point mixture containing the first alcohol is not vaporized and directly ester reaction product of a liquid spill.
[Claim 4]
A manufacturing system according to claim 1, wherein the recirculation line of the mixed alcohol separation column may comprise a first alcohol and a second alcohol recycle line recirculation line.
[Claim 5]
The method of claim 1, wherein the manufacturing system is a manufacturing system that includes a product storage tank, and further, which is connected to the purified product line of the purification unit.
[Claim 6]
The method of claim 1, wherein the manufacturing system is a manufacturing system of a batch reactor system.
[Claim 7]
According to claim 1, wherein the manufacturing systems carboxylic acid compound is terephthalic acid, which comprises a least two carboxyl.
[Claim 8]
The method of claim 1, wherein the first alcohol and the second alcohol is a manufacturing system and a primary alcohol, having a carbon number of the first alcohol is one greater than the number of carbon atoms in the second alcohol.
[Claim 9]
The method of claim 1 wherein said first alcohol and a second alcohol produced in the system of the alkyl group having 1 to 12 carbon atoms.
[Claim 10]
According to claim 1, wherein the manufacturing system wherein the ester composition is a mixture of the ester compound of the three.
[Claim 11]
Step in which the ester compound and the water produced through a carboxylic acid ester compound and direct reaction of a first alcohol containing two or more carboxyl groups in an integrated reactor (S1); Removing the low boiling point mixture containing the unreacted alcohol and water in the first reactor and the combined number of the first alcohol as the alcohol reservoir (S2); In the second step of the alcohol with the combined reactor produced composition of an ester through the reaction of the trans-ester ester compound and a second alcohol (S3); And a step (S4) for recovering the mixed alcohols to give the ester composition to the alcohol storage tank, process for producing a polyester composition comprising a.
[Claim 12]
The method of claim 11, wherein the manufacturing method in the step S2 is removed such that the total material below 2% by weight, based on the weight of the unreacted in the first alcohol is integrated reactor.
[Claim 13]
The method of claim 11, wherein the removal of the low boiling point mixture in the step S2 is carried out through a gas-liquid separating column, the line to the liquid compartment in the low boiling mixture is the low boiling point mixture in the gas phase by reducing the pressure and flows into the gas-liquid separating column integrated reactor the method of producing a low-boiling mixture of the liquid that is introduced into the gas-liquid separation by the column.
[Claim 14]
12. The method of claim 11, to separate the mixed alcohol of the alcohol storage tank in accordance with the number of carbon atoms and recycled to the first alcohol in the step S1, the second step (S5) for recycling the second alcohol in the step S3; further comprises a the method of manufacture.