CN114773188B - Continuous recovery method of methyl cardiac acid raffinate - Google Patents
Continuous recovery method of methyl cardiac acid raffinate Download PDFInfo
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- CN114773188B CN114773188B CN202210371446.XA CN202210371446A CN114773188B CN 114773188 B CN114773188 B CN 114773188B CN 202210371446 A CN202210371446 A CN 202210371446A CN 114773188 B CN114773188 B CN 114773188B
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C07C67/00—Preparation of carboxylic acid esters
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- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
The invention discloses a continuous recovery method of methyl cardiac acid raffinate, which comprises the steps of continuously allowing methyl cardiac acid raffinate containing isopentenyl cardiac acid and methanol to pass through at least one group of fixed bed reactors filled with catalysts in series in sequence for reaction to obtain methyl cardiac acid, and controlling the temperature from the first fixed bed reactor to the last fixed bed reactor in the fixed bed reactors to be reduced in sequence. The invention adopts a program cooling mode, can shorten the reaction time and improve the conversion rate of the isopentenyl cardiac acid ester.
Description
Technical Field
The invention relates to a continuous recovery method of methyl cardiac acid residual liquid.
Background
Methyl cardiac acid is known as methyl 3, 3-dimethyl-4-pentenoate and is typically prepared by reacting isopentenol with trimethyl orthoacetate. The reaction process involves claisen rearrangement with side reactions, by-products being high boiling isopentenyl cardiac esters. In the rectification and purification process of the crude methyl cardiac acid, the byproduct, namely the isopentenyl cardiac acid ester, exists in the residual liquid in the tower kettle.
CN112479872a discloses that the methyl cardiac acid isoamylene ester in the methyl cardiac acid ester rectification raffinate and methanol are subjected to transesterification reaction in the presence of sodium methoxide as a catalyst, the temperature is controlled at 70-75 ℃ to obtain methyl cardiac acid ester with higher mass fraction, but the reaction is performed under the constant temperature condition, the reaction time is longer, the conversion rate of the methyl cardiac acid isoamylene ester is not high enough, sodium methoxide is a homogeneous catalyst, the subsequent recovery is difficult, and the post-treatment is complex.
CN1896044a discloses that the reaction of isopentenyl cardiac acid ester with methanol in the presence of sodium methoxide as catalyst at 140 ℃ for 6 hours, the conversion of isopentenyl cardiac acid ester is 79.6%, which is lower; the patent also discloses that the reaction of isopentenyl cardiac acid ester with methanol in the presence of tetraisopropyl titanate as catalyst at 152 deg.c for 7.5 hr, with isopentenyl cardiac acid ester conversion of 94.2%, but at high temperature, the reaction tends to discolor methyl cardiac acid ester product.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides an improved continuous recovery method of methyl cardiac acid residual liquid, which can shorten the reaction time and improve the conversion rate of the isopentenyl cardiac acid ester.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a continuous recovery method of methyl cardiac acid raffinate comprises the steps of continuously allowing methyl cardiac acid raffinate containing isopentenyl cardiac acid and methanol to pass through at least one group of fixed bed reactors filled with catalysts in series in sequence for reaction to obtain methyl cardiac acid, and controlling the temperature from the first fixed bed reactor to the last fixed bed reactor in the fixed bed reactors to be reduced in sequence.
In some embodiments of the invention, the temperature of the plurality of fixed bed reactors is 50 to 130 ℃, and the temperature difference between two adjacent fixed bed reactors is 15 to 30 ℃.
In some embodiments of the invention, the temperature of the first fixed bed reactor is 100 to 130 ℃; the temperature of a second fixed bed reactor in the plurality of fixed bed reactors is 80-100 ℃; the temperature of the third fixed bed reactor in the plurality of fixed bed reactors is 50-80 ℃.
Preferably, the temperature of the first fixed bed reactor is 100-110 ℃; the temperature of the second fixed bed reactor is 80-90 ℃; the temperature of the third fixed bed reactor is 60-70 ℃.
In some embodiments of the invention, the methyl cardiac acid rectification raffinate comprises 65-70% by mass of isopentenyl cardiac acid esters.
In some embodiments of the invention, the molar ratio of isopentenyl cardiac acid ester to methanol is from 1:1 to 10.
In some embodiments of the invention, the catalyst is selected from one or a combination of two of a solid base catalyst selected from one or a combination of two of a single component metal oxide and a supported metal oxide and a strongly basic ion exchange resin.
Preferably, the one-component metal oxide is selected from CaO, znO and Na 2 O, a combination of one or more of O.
Preferably, the supported metal oxide is selected from the group consisting of TiO 2 Loaded CaO, zrO 2 Loaded ZnO, al 2 O 3 Na of load 2 O and SiO 2 A combination of one or more of the loaded MgO.
Preferably, the strongly basic ion exchange resin is selected from the group consisting of AmberLite HPR 900OH, amberlyst a26OH, amberLite FPA40 Cl, and AmberLite FPA98 Cl.
The volume of the catalyst filling accounts for 1-30% of the volume of the fixed bed reactor, and the volume percentage of the catalyst filling of the adjacent subsequent fixed bed reactor is 0-15% lower than that of the catalyst filling of the adjacent preceding fixed bed reactor.
In some embodiments of the invention, the volume of catalyst packed in the first fixed bed reactor is 20 to 25% of the volume of the first fixed bed reactor.
In some embodiments of the invention, the volume of catalyst packed in the second fixed bed reactor of the plurality of fixed bed reactors is 10 to 20% of the volume of the second fixed bed reactor.
In some embodiments of the invention, the volume of catalyst packed in a third fixed bed reactor of the plurality of fixed bed reactors is from 5 to 10% of the volume of the third fixed bed reactor.
Methyl cardiac sulfonate raffinate refers to raffinate separated and purified during synthesis of methyl cardiac sulfonate, and in some embodiments of the invention, the methyl cardiac sulfonate raffinate is raffinate purified by rectifying methyl cardiac sulfonate.
In some embodiments of the present invention, the methyl cardiac acid rectification raffinate and methanol are mixed uniformly in a premixer to obtain a feed mixture, and the feed mixture is passed into the first fixed bed reactor.
In some embodiments of the invention, a buffer tank is disposed between two adjacent fixed bed reactors of the plurality of fixed bed reactors.
In some embodiments of the invention, the continuous recovery process further comprises performing a rectification separation using a rectification column.
In some embodiments of the invention, the plurality of fixed bed reactors is 3 to 7.
Further, the number of the fixed bed reactors is 3 to 5.
Further preferably, the number of the fixed bed reactors is 3.
In the invention, methyl cardiac acid isoamylene ester in methyl cardiac acid rectification residual liquid reacts with methanol to generate methyl cardiac acid and isoamylene alcohol, and the reaction formula is as follows:
the reaction is exothermic reversible reaction, and the reversible reaction can be moved towards the positive reaction direction by reducing the reaction temperature, so that the conversion rate of the isopentenyl cardiac acid ester is improved. While lowering the reaction temperature generally reduces the reaction rate. The inventor finds that by adopting a program cooling mode, the reaction is firstly carried out at a higher temperature, so that the reaction can reach an equilibrium state at the temperature faster, then the cooling reaction is carried out, the reaction is continued, and the equilibrium conversion rate at a lower temperature is reached, so that the reaction rate is faster and the conversion rate is higher, and further the technical effects of shortening the reaction time and improving the conversion rate of the cardiac acid isopentenyl ester are realized.
In some embodiments of the invention, the continuous recovery process comprises the steps of:
1) Uniformly mixing the methyl cardiac acid rectification residual liquid and methanol in a premixer to obtain a raw material mixed liquid, and introducing the raw material mixed liquid into the first fixed bed reactor for reaction to obtain a first reaction liquid;
2) Introducing the first reaction liquid into a second fixed bed reactor in the fixed bed reactors to react to obtain a second reaction liquid;
3) Introducing the second reaction liquid into a third fixed bed reactor in the fixed bed reactors to react to obtain a third reaction liquid;
4) And (3) introducing the third reaction liquid into a rectifying tower, rectifying and separating to obtain the methyl cardiac pavilion.
Further, the mass airspeed of the raw material mixed solution is 0.1-0.2 h -1 。
Further, the mass airspeed of the first reaction solution is 0.2 to 0.5h -1 。
Further, the mass airspeed of the second reaction solution is 0.2 to 0.5h -1 。
In some embodiments of the invention, the mass percentage of isopentenyl cardiac acid esters in the third reaction solution is less than 6%.
Preferably, the mass percentage of the isopentenyl cardiac acid ester in the third reaction solution is less than 4%.
In some embodiments of the invention, the temperature of the first fixed bed reactor is 100 to 130 ℃ and the pressure is 0.35 to 0.83MPa; the temperature of the second fixed bed reactor is 80-100 ℃ and the pressure is 0.20-0.35 MPa; the temperature of the third fixed bed reactor is 50-80 ℃ and the pressure is 0.10-0.20 MPa.
Preferably, the temperature of the first fixed bed reactor is 100-110 ℃ and the pressure is 0.35-0.48 MPa; the temperature of the second fixed bed reactor is 80-90 ℃ and the pressure is 0.20-0.26 MPa; the temperature of the third fixed bed reactor is 60-70 ℃ and the pressure is 0.10-0.13 MPa.
The boiling point of the reaction mass is increased under pressure, which is advantageous for the use of higher reaction temperatures.
After the raw material mixed solution is introduced into the first fixed bed reactor, the same temperature as the first fixed bed reactor can be reached faster; after the first reaction liquid is introduced into the second fixed bed reactor, the same temperature as the second fixed bed reactor can be reached faster; after the second reaction liquid is introduced into the third fixed bed reactor, the same temperature as that of the third fixed bed reactor can be reached relatively quickly.
In some embodiments of the present invention, in the step 1), the methyl cardiac acid rectification raffinate and the methanol are mixed uniformly in a premixer and preheated to obtain the raw material mixed solution, wherein the preheating temperature is 30-50 ℃.
The invention further provides a production method of methyl cardiac pavilion, which takes isopentenol and trimethyl orthoacetate as raw materials, and carries out reaction in the presence of a catalyst to obtain a crude methyl cardiac pavilion product, wherein the crude methyl cardiac pavilion product is purified to obtain methyl cardiac pavilion residual liquid, and the production method further comprises the step of recovering the methyl cardiac pavilion residual liquid by adopting the continuous recovery method of the methyl cardiac pavilion residual liquid.
Compared with the prior art, the invention has the following advantages:
the invention adopts the reaction under the condition of program cooling, and can improve the reaction conversion rate while improving the reaction rate, shortening the reaction time.
The invention adopts at least one group of fixed bed reactors which are sequentially connected in series, can realize continuous reaction, is suitable for large-scale production, has large heat exchange area and is easy to control the reaction temperature.
According to the invention, the catalyst is filled in a plurality of fixed bed reactors, so that the catalyst does not need to be separated, the catalyst recovery cost is reduced, the catalyst stability is good, and the activity of the catalyst is basically unchanged after long-time operation.
The reaction temperature of the present invention does not cause discoloration of the final methyl cardiac product.
Detailed Description
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
ZrO (ZrO) 2 The supported ZnO catalyst is respectively filled into the first fixed bed reactor, the second fixed bed reactor and the third fixed bed reactor, the filling amount of the catalyst is respectively 20% of the total volume of the first fixed bed reactor, 10% of the total volume of the second fixed bed reactor and 5% of the total volume of the third fixed bed reactor.
And uniformly mixing methyl cardiac acid methyl ester rectification residual liquid containing the cardiac acid isoamylene ester (wherein the mass fraction of the cardiac acid isoamylene ester is 68%) and methanol in a premixer, and preheating to 40 ℃ to obtain a raw material mixed liquid, wherein the molar ratio of the cardiac acid isoamylene ester to the methanol is 1:5. And continuously introducing the raw material mixed solution from the upper end of the first fixed bed reactor to react to obtain a first reaction solution. The mass airspeed of the raw material mixed solution is 0.125h -1 The temperature of the first fixed bed reactor was 110℃and the pressure was 0.48MPa. The first reaction liquid flows out from a discharge hole of the first fixed bed reactor, passes through an intermediate storage tank, and is continuously introduced into the second fixed bed reactor from the upper end for reaction, so as to obtain the second reaction liquid. The mass space velocity of the first reaction solution is 0.2h -1 The temperature of the second fixed bed reactor was 90℃and the pressure was 0.26MPa. And the second reaction liquid flows out from a discharge hole of the second fixed bed reactor, passes through an intermediate storage tank, and is continuously introduced into the third fixed bed reactor from the upper end for reaction, so that the third reaction liquid is obtained. The mass space velocity of the second reaction solution is 0.25h -1 The temperature of the third fixed bed reactor was 60℃and the pressure was 0.1MPa. Collecting a third reaction liquid from a discharge port of the third fixed bed reactor, sampling and performing GC detection, wherein the third reaction liquid contains the weight percentage of the isopentenyl cardiac acid esterThe ratio was 4.07%, and the reaction was completed.
And pumping the third reaction liquid into a rectifying tower, rectifying and separating to obtain methyl cardiac pavilion, wherein the conversion rate of the isopentenyl cardiac pavilion is 90.7%, and the purity of the methyl cardiac pavilion is 99.81%.
Examples 2 to 8
Examples 2-8 are essentially the same as example 1, except that the reaction materials, catalyst types and loadings, and reaction process parameters are different, as shown in tables 1 and 2 below, where DPE means methyl cardiac pavilion and MBDP means isopentenyl cardiac pavilion.
TABLE 1 examples 2-8 reaction raw materials, catalyst types and loading
Table 2 examples 2-8 reaction parameters
Examples 2-8 the mass percent of isopentenyl cardiac acid ester, conversion and final methyl cardiac acid ester purity in the third reaction solution after reaction are shown in table 3 below:
TABLE 3 Table 3
Example 9
The recovery process of example 1 was run continuously, the reaction conditions were the same as in example 1, and the conversion and product purity at various run lengths were as shown in Table 4 below. The catalyst can stably and continuously run for more than 200 hours, and the activity of the catalyst is not obviously reduced.
TABLE 4 Table 4
| Run length/h | Conversion of isopentenyl cardiac acid ester/% | Purity/%of methyl cardiac |
| 10 | 92.1％ | 99.81％ |
| 50 | 92.0％ | 99.81％ |
| 100 | 91.8％ | 99.80％ |
| 200 | 91.7％ | 99.82％ |
Comparative example 1
Substantially the same as in example 1, the only difference is that: the temperature of the first, the second and the third fixed bed reactors is 70 ℃, and the mass space velocity of the first reaction liquid is 0.125h -1 The mass space velocity of the second reaction solution is 0.125h -1 . The result shows that the mass percentage of the isopentenyl cardiac acid ester in the third reaction liquid is 8.75%, the conversion rate of the isopentenyl cardiac acid ester is 80.7% after the rectification and separation in the rectifying tower, and the purity of the methyl cardiac acid ester product is 99.17%. Indicating that under isothermal reaction conditions, the conversion of the final isopentenyl cardiac ester was still reduced, even though the reaction time was longer in the second and third fixed bed reactors.
Comparative example 2
Substantially the same as in example 1, the only difference is that: the temperatures of the first, second and third fixed bed reactors were 110 ℃. The result shows that the mass percentage of the isopentenyl cardiac acid ester in the third reaction liquid is 11.51%, the conversion rate of the isopentenyl cardiac acid ester is 76.7% after the rectification and separation in the rectifying tower, and the purity of the methyl cardiac acid ester product is 99.23%.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (15)
1. A continuous recovery method of methyl cardiac pavilion residual liquid is characterized in that: continuously passing methyl cardiac acid raffinate containing isopentenyl cardiac acid ester and methanol through at least one group of fixed bed reactors filled with catalysts which are sequentially connected in series to react to obtain methyl cardiac acid ester, and controlling the temperature of the first fixed bed reactor to the last fixed bed reactor in the fixed bed reactors to be sequentially reduced; the temperature of the fixed bed reactors is 50-130 ℃, and the temperature difference between two adjacent fixed bed reactors is 15-30 ℃; the volume of the catalyst filling accounts for 1-30% of the volume of the fixed bed reactor, and the volume percentage of the catalyst filling of the adjacent subsequent fixed bed reactor is 0-15% lower than that of the catalyst filling of the adjacent preceding fixed bed reactor.
2. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 1, wherein: the number of the fixed bed reactors is 3-7.
3. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 1, wherein: the number of the fixed bed reactors is 3-5.
4. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 1, wherein: the number of the fixed bed reactors is 3.
5. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 1, wherein: the catalyst is selected from one or two of a solid base catalyst and a strong base ion exchange resin, and the solid base catalyst is selected from one or two of a single-component metal oxide and a supported metal oxide.
6. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 5, wherein: the one-component metal oxide is selected from CaO, znO and Na 2 A combination of one or more of O; and/or the supported metal oxide is selected from TiO 2 Loaded CaO, zrO 2 Loaded ZnO, al 2 O 3 Na of load 2 O and SiO 2 A combination of one or more of the loaded MgO; and/or the strongly basic ion exchange resin is selected from one or more of AmberLite HPR 900OH, amberlyst a26OH, amberLite FPA40 Cl, and AmberLite FPA98 Cl.
7. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 1, wherein: the mass percentage of the isopentenyl cardiac acid ester in the methyl cardiac acid raffinate is 65-70%; and/or the molar ratio of the isopentenyl cardiac acid ester to the methanol is 1:1-10.
8. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 1, wherein: the methyl cardiac acid raffinate is raffinate obtained by rectifying and purifying methyl cardiac acid; and/or mixing the methyl cardiac acid raffinate and the methanol uniformly in a premixer to obtain a raw material mixed solution, and introducing the raw material mixed solution into the first fixed bed reactor; and/or a buffer tank is arranged between two adjacent fixed bed reactors in the fixed bed reactors; and/or, the continuous recovery method further comprises rectifying separation by adopting a rectifying tower.
9. The continuous recovery method of methyl cardiac pavilion residual liquid according to any one of claims 1 to 8, wherein: the continuous recovery method comprises the following steps:
1) Uniformly mixing the methyl cardiac acid ester raffinate and methanol in a premixer to obtain a raw material mixed solution, and introducing the raw material mixed solution into the first fixed bed reactor for reaction to obtain a first reaction solution;
2) Introducing the first reaction liquid into a second fixed bed reactor in the fixed bed reactors to react to obtain a second reaction liquid;
3) Introducing the second reaction liquid into a third fixed bed reactor in the fixed bed reactors to react to obtain a third reaction liquid;
4) And (3) introducing the third reaction liquid into a rectifying tower, rectifying and separating to obtain the methyl cardiac pavilion.
10. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 9, wherein: the volume of the catalyst filled in the first fixed bed reactor accounts for 20-25% of the volume of the first fixed bed reactor; and/or the volume of the catalyst filled in the second fixed bed reactor in the plurality of fixed bed reactors accounts for 10-20% of the volume of the second fixed bed reactor; and/or, the volume of the catalyst filled in the third fixed bed reactor in the plurality of fixed bed reactors accounts for 5-10% of the volume of the third fixed bed reactor.
11. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 9, wherein: the mass airspeed of the raw material mixed solution is 0.1-0.2 h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the mass airspeed of the first reaction solution is 0.2-0.5 h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the mass airspeed of the second reaction solution is 0.2-0.5 h -1 。
12. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 9, wherein: the mass percentage of the isopentenyl cardiac acid ester in the third reaction solution is less than 6%.
13. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 9, wherein: the mass percentage of the isopentenyl cardiac acid ester in the third reaction solution is less than 4%.
14. The continuous recovery method of methyl cardiac pavilion residual liquid according to claim 9, wherein: the temperature of the first fixed bed reactor is 100-130 ℃, and the pressure is 0.35-0.83 MPa; the temperature of the second fixed bed reactor is 80-100 ℃ and the pressure is 0.20-0.35 MPa; the temperature of the third fixed bed reactor is 50-80 ℃ and the pressure is 0.10-0.20 MPa.
15. The production method of methyl cardiac pavilion adopts isopentenol and trimethyl orthoacetate as raw materials, and the raw materials react in the presence of a catalyst to obtain a crude methyl cardiac pavilion, and the crude methyl cardiac pavilion is purified to obtain methyl cardiac pavilion residual liquid, and the production method is characterized by comprising the following steps of: the production process further comprises recovering the methyl cardiac acid ester raffinate using the continuous recovery process of the methyl cardiac acid ester raffinate of any one of claims 1 to 14.
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| US4223159A (en) * | 1979-04-26 | 1980-09-16 | Fmc Corporation | By-product recycling process |
| CN1896044A (en) * | 2006-06-21 | 2007-01-17 | 湖北工业大学 | Penisopenteneester recovery method |
| CN103992206B (en) * | 2014-06-05 | 2016-09-07 | 南京工业大学 | Method and system for preparing isopentenol through ester exchange |
| CN109081779A (en) * | 2018-07-03 | 2018-12-25 | 沈阳化工大学 | A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester |
| CN112479872A (en) * | 2020-12-15 | 2021-03-12 | 安徽鑫泰新材料有限公司 | Recovery equipment and recovery method for rectification raffinate of methyl cardiate |
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