CN111004123A - Preparation method of ethyl 3-ethoxypropionate - Google Patents
Preparation method of ethyl 3-ethoxypropionate Download PDFInfo
- Publication number
- CN111004123A CN111004123A CN201911349014.3A CN201911349014A CN111004123A CN 111004123 A CN111004123 A CN 111004123A CN 201911349014 A CN201911349014 A CN 201911349014A CN 111004123 A CN111004123 A CN 111004123A
- Authority
- CN
- China
- Prior art keywords
- fixed bed
- bed reactor
- ethyl
- ethyl acrylate
- acidity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 title claims description 12
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 18
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000007259 addition reaction Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 alkali metal alkoxide Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The embodiment of the invention discloses a preparation method of 3-ethoxy ethyl propionate, and relates to the technical field of chemical synthesis. The method uses low-acidity absolute ethyl alcohol and ethyl acrylate to perform addition reaction under the catalytic action of strong-basicity ion exchange resin to prepare the 3-ethoxy ethyl propionate, and because the acidity of reactants is within 10ppm, the catalyst is not influenced, so that the conversion rate of the catalyst is high, and high yield (the conversion rate and the yield of the method are both more than 98 percent) is obtained.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, and particularly relates to a preparation method of 3-ethoxy ethyl propionate.
Background
The 3-ethoxy ethyl propionate is an important organic solvent and an organic synthesis intermediate, and is widely applied to the coating industry, the electronic industry and the synthesis of medical intermediates.
U.S. Pat. No. 5,5081285 uses ethanol and ethyl acrylate to obtain ethyl 3-ethoxypropionate under the catalysis of methanesulfonic acid, the reaction temperature is 120-.
[ tetrahedron letters,46(19), 3279-.
Patent CN200810061996.1 adopts alkali metals such as metal sodium or alkali metal alkoxide as a catalyst, 3-ethoxy ethyl propionate is synthesized by absolute ethyl alcohol and ethyl acrylate, the reaction time is shortened to within 3 hours, the yield can reach 96% at most, but the catalyst is acid-sensitive, water is extremely sensitive, once the catalyst is damaged when meeting water or acid, the catalyst cannot be regenerated, and acid is needed to neutralize the system to be neutral or even acidic after the reaction is finished, so that the separation step is added, certain salt-containing wastewater is generated, the difficulty of product purification is increased by generating organic salt through the reaction, the side reaction is increased by highly releasing heat in the neutralization process, the purity of the product is within 99.8%, the product cannot be further processed into an electronic-grade product, and the product cannot be used in the photoelectric industry.
In addition, it has been reported that the 3-ethoxypropionic acid ethyl ester is obtained by catalyzing absolute ethyl alcohol and ethyl acrylate with a strongly basic ion exchange resin, however, since the trace acid content in the absolute ethyl alcohol and the ethyl acrylate is generally 200-500ppm, the strong-base ion exchange resin is neutralized, the catalytic effect is affected, the dosage of the strong-base ion exchange resin needs to be increased (generally about 20% of the mass of the ethyl acrylate is used), the strong-alkaline ion exchange resin has high price and short service life, generally loses the catalytic effect within 6 to 8 hours, needs to be regenerated, can be regenerated for only 7 times at most, and the strong-base ion exchange resin is easy to break and lose the purpose, the conversion rate is not high, generally between 70 and 90 percent, a large amount of waste water is generated by regenerating the strong-base ion exchange resin, the production cost is greatly increased, and large-scale continuous production cannot be realized.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a novel preparation method of ethyl 3-ethoxypropionate, which has the advantages of simple synthesis, mild conditions, less side reactions, good catalyst effect, simple separation process and convenience for continuous production.
In order to solve the above problems, the present invention proposes the following technical solutions:
a preparation method of ethyl 3-ethoxypropionate comprises the following steps:
a reaction step, carrying out addition reaction on absolute ethyl alcohol and ethyl acrylate according to a molar ratio of 3-100:1 under the action of a composite catalyst, wherein the reaction temperature is-5-35 ℃, and obtaining a mixture containing 3-ethoxy ethyl propionate;
a purification step, wherein the mixture containing the 3-ethoxy ethyl propionate is purified and separated to obtain high-purity 3-ethoxy ethyl propionate;
wherein the acidity of the absolute ethyl alcohol is less than or equal to 10 ppm; the acidity of the ethyl acrylate is less than or equal to 10 ppm;
the dosage of the composite catalyst is 0.1-15% of the weight of the ethyl acrylate;
the composite catalyst includes a strongly basic ion exchange resin.
Further, the composite catalyst also comprises a cocatalyst and a stabilizer; wherein the stabilizing agent is silica gel or a molecular sieve.
Further, before the reacting step, a deacidifying step is also included:
deacidifying the absolute ethyl alcohol and the ethyl acrylate to obtain the absolute ethyl alcohol with the acidity of less than or equal to 10ppm and the ethyl acrylate with the acidity of less than or equal to 10 ppm.
Further, the deacidification step is carried out in a first fixed bed reactor, and deacidified resin is arranged in the first fixed bed reactor; the dosage of the deacidification resin is 0.1 to 15 percent of the weight of the ethyl acrylate.
Further, the reaction step is carried out in a second fixed bed reactor, and the composite catalyst is arranged in the second fixed bed reactor.
Further, the first fixed bed reactor and the second fixed bed reactor are connected in series.
Further, the first fixed bed reactor is a tubular reactor or a tower reactor; the second fixed bed reactor is a tubular reactor or a tower reactor.
Further, the strongly basic ion exchange resin is a quaternary ammonium anion exchange resin.
Further, the purification step is performed in a rectification column.
Compared with the prior art, the invention can achieve the following technical effects:
the method uses low-acidity absolute ethyl alcohol and ethyl acrylate to perform addition reaction under the catalytic action of strong-basicity ion exchange resin to prepare the 3-ethoxy ethyl propionate, and because the acidity of reactants is within 10ppm, the catalyst is not influenced, so that the conversion rate of the catalyst is high, and high yield (the conversion rate and the yield of the method are both more than 98 percent) is obtained.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a process flow diagram of a preparation method of ethyl 3-ethoxypropionate provided by an embodiment of the present invention.
Reference numerals
The system comprises a dosing tank 10, a first fixed bed reactor 20, a second fixed bed reactor 30 and a rectifying tower 40.
Detailed Description
The technical solutions in the embodiments will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, wherein like reference numerals represent like elements in the drawings. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Referring to fig. 1, an embodiment of the present invention provides a preparation method of ethyl 3-ethoxypropionate, including the following steps:
a reaction step, carrying out addition reaction on absolute ethyl alcohol and ethyl acrylate according to a molar ratio of 3-100:1 under the action of a composite catalyst, wherein the reaction temperature is-5-35 ℃, and obtaining a mixture containing 3-ethoxy ethyl propionate;
a purification step, wherein the mixture containing the 3-ethoxy ethyl propionate is purified and separated to obtain high-purity 3-ethoxy ethyl propionate;
wherein the acidity of the absolute ethyl alcohol is less than or equal to 10 ppm; the acidity of the ethyl acrylate is less than or equal to 10 ppm;
the dosage of the composite catalyst is 0.1-15% of the weight of the ethyl acrylate;
the composite catalyst includes a strongly basic ion exchange resin.
In a specific embodiment, the composite catalyst further comprises a cocatalyst and a stabilizer; wherein the stabilizing agent is silica gel or a molecular sieve.
It is understood that the cocatalyst is a substance which has no activity or little activity, but can change partial properties of the catalyst, such as chemical composition, ionic valence, acidity and alkalinity, surface structure, grain size and the like, so that the activity, selectivity, antitoxicity or stability of the catalyst is improved.
In the embodiment of the present invention, a common promoter may be selected to improve the catalytic activity and stability of the strongly basic ion exchange resin, and the type of the promoter may be determined by a person skilled in the art according to the need, which is not specifically limited by the present invention.
In a specific embodiment, the strongly basic ion exchange resin is a quaternary ammonium anion exchange resin.
It is understood that the composite catalyst used in this embodiment is composed of three components, i.e., strongly basic ion exchange resin, catalyst and stabilizer, to improve the conversion rate and service life of the catalyst.
In one embodiment, before the reacting step, a deacidifying step is further included:
deacidifying the absolute ethyl alcohol and the ethyl acrylate to obtain the absolute ethyl alcohol with the acidity of less than or equal to 10ppm and the ethyl acrylate with the acidity of less than or equal to 10 ppm.
In one embodiment, the deacidification step is performed in a first fixed bed reactor 20, wherein the deacidification resin is disposed in the first fixed bed reactor 20; the dosage of the deacidification resin is 0.1 to 15 percent of the weight of the ethyl acrylate.
When the anhydrous ethanol and the ethyl acrylate are deacidified, in order to facilitate the operation, the anhydrous ethanol and the ethyl acrylate are uniformly mixed according to a proportion, the mixed solution is deacidified by a first fixed bed reactor, and the mixed solution of the anhydrous ethanol and the ethyl acrylate which is discharged from the first fixed bed reactor can be directly used as a reactant of an addition reaction.
In one embodiment, the reaction step is performed in a second fixed bed reactor 30, and the composite catalyst is disposed in the second fixed bed reactor 30.
In one embodiment, the first fixed bed reactor 20 is in series with the second fixed bed reactor 30.
It can be understood that the first fixed bed reactor and the second fixed bed reactor are connected in series, so that the operation can be greatly simplified, and the absolute ethyl alcohol and the ethyl acrylate which are subjected to acid removal by the first fixed bed reactor can directly enter the second fixed bed reactor for addition reaction.
Before the reactor is used, the catalyst in the first fixed bed reactor and the catalyst in the second fixed bed reactor are cleaned by absolute ethyl alcohol, and then nitrogen is used for purging, so that the moisture in the reactor is taken away, and impurities are prevented from being mixed.
In a specific embodiment, the first fixed bed reactor is a tubular reactor or a tower reactor; the second fixed bed reactor is a tubular reactor or a tower reactor.
In one embodiment, the purification step is performed in a rectification column. After the addition reaction is finished, the materials discharged from the second fixed bed reactor comprise 3-ethoxy ethyl propionate, excessive absolute ethyl alcohol and a small amount of unreacted ethyl acrylate. 3-ethoxy ethyl propionate can be easily separated and purified by a rectification mode to obtain high-purity 3-ethoxy ethyl propionate (more than 99.8 percent); excess absolute ethyl alcohol and a small amount of unreacted ethyl acrylate can be fed into the first fixed bed reactor again for recycling.
The reaction is substantially homogeneous, and may be continuous or semi-continuous. The product is separated from the reacted materials, the excessive absolute ethyl alcohol is recycled, and the strong-base ion exchange resin can be continuously operated for more than 6 months and then regenerated for use.
The reaction can be carried out under vacuum, atmospheric pressure or under pressure.
The reaction time depends on the residence time of the reactor.
Compared with the other methods, the technical scheme provided by the embodiment of the invention has the following advantages:
1. the combined fixed bed reaction device (the first fixed bed reactor and the second fixed bed reactor are connected in series) combining deacidified resin and the composite catalyst can be used for more than 6 months continuously, and the catalyst has long service life, can be used for 1 to 2 years and does not need to be regenerated frequently;
2. the conversion per pass is high, the conversion rate is more than 98%, the product separation is simple, the catalyst is not required to be damaged and then the separation is carried out, the quality is good, and the purity is more than 99.8%;
3. basically no three wastes are generated, and the environmental protection requirement is met.
With continued reference to fig. 1, the embodiment will be described in detail below using the schematic diagram of the apparatus of fig. 1.
In examples 1 to 4, the first fixed bed reactor 20 was charged with deacidified resin, the second fixed bed reactor 30 was charged with composite catalyst, the influence of the life and temperature of the catalyst was examined by changing the ethyl acrylate concentration and also the dilution ratio (volume flow per hour divided by reactor volume) in the dosing tank 10, and when the ethyl acrylate concentration in the effluent exceeded 1% it was indicated that the catalyst had reached the end of use and required regeneration.
Example 1
The first fixed bed reactor 20 has a radius of 2.5 cm and a height of 25 cm and is filled with deacidified resin; the second fixed bed reactor 30 has a radius of 2.5 cm and a height of 75 cm, is filled with a composite catalyst (composed of strongly basic ion exchange resin, a cocatalyst and a stabilizer), and the first fixed bed reactor 20 and the second fixed bed reactor 30 are firstly cleaned by absolute ethyl alcohol to take away the components in the first fixed bed reactor and the second fixed bed reactor 30 until the water content of the obtained absolute ethyl alcohol is lower than 0.5%.
The mass ratio of the absolute ethyl alcohol to the ethyl acrylate in the batching tank 10 is 85: 15; the amount of deacidified resin in the first fixed bed reactor 20 was about 10% of the ethyl acrylate amount, and the amount of composite catalyst in the second fixed bed reactor 30 was about 5% of the ethyl acrylate amount.
The acidity of the mixed material of the ethyl acrylate and the absolute ethyl alcohol after passing through the first fixed bed reactor 20 is 5-9ppm, and the mixed material is cooled to the temperature of 9-13 ℃; introducing the mixture into a second fixed bed reactor 30 according to the dilution rate of 2.1, controlling the reaction temperature to be 26 +/-2 ℃, introducing the material discharged from the second fixed bed reactor 30 into a receiving tank (not shown), and measuring the content of the ethyl acrylate in the receiving tank; rectifying the material in the receiving tank by a rectifying tower 40 to obtain 3-Ethoxy Ethyl Propionate (EEP) with the purity of more than 99.8%, collecting the EEP as a product, calculating the yield, pumping excessive ethanol, unreacted ethyl acrylate and a small amount of EEP carried out from the rectifying tower 40 back to a proportioning tank 10, and adding fresh absolute ethyl alcohol and ethyl acrylate to adjust to 85: and 15, entering a combined fixed bed reaction device for cyclic reaction. After 60 days of continuous operation, the ethyl acrylate discharged to the receiving tank was 0.5%, the EEP purity was 99.92%, and the EEP yield was 98.5%.
Example 2
The difference from the example 1 is that the mass ratio of the absolute ethyl alcohol and the ethyl acrylate in the batching tank 10 is 85: 15; the amount of deacidified resin in the first fixed bed reactor 20 was about 12% of ethyl acrylate and the amount of composite catalyst in the second fixed bed reactor 30 was about 7% of ethyl acrylate.
The acidity of the mixed material of ethyl acrylate and absolute ethyl alcohol after passing through the first fixed bed reactor 20 is 5-9ppm, the mixed material is cooled to the temperature of 19-20 ℃, the mixed material is introduced into the second fixed bed reactor 30 according to the dilution rate of 2.0, the temperature of the second fixed bed reactor 30 is controlled to be 28 +/-2 ℃, the material discharged from the second fixed bed reactor 30 enters a receiving tank, the content of ethyl acrylate in the receiving tank is measured, the material in the receiving tank is rectified by a rectifying tower 40, EEP with the purity of 99.8% is obtained and collected as a product, the yield is calculated, excessive ethyl alcohol discharged from the rectifying tower 40, unreacted ethyl acrylate and a small amount of EEP carried out are pumped back to a material mixing tank 10, and fresh absolute ethyl alcohol and ethyl acrylate are added to adjust to 85: and 15, entering a combined fixed bed reaction device for cyclic reaction. After 90 days of continuous operation, the ethyl acrylate discharged into the receiving tank was measured to be 0.3%, and the collected EEP had a purity of 99.94 and a yield of 98.6%.
Example 3
The difference from the example 1 is that the mass ratio of the absolute ethyl alcohol and the ethyl acrylate in the batching tank 10 is 85: 15; the amount of deacidified resin in the first fixed bed reactor 20 was about 13% of ethyl acrylate, and the amount of composite catalyst in the second fixed bed reactor 30 was about 8% of ethyl acrylate.
The acidity of the mixed material of ethyl acrylate and absolute ethyl alcohol after passing through the first fixed bed reactor 20 is 5-9ppm, the mixed material is cooled to the temperature of 13-15 ℃, the mixed material is introduced into the second fixed bed reactor 30 according to the dilution rate of 2.0, the temperature of the second fixed bed reactor 30 is controlled to be 28 +/-2 ℃, the material discharged from the second fixed bed reactor 30 enters a receiving tank, the content of ethyl acrylate in the receiving tank is measured, the material in the receiving tank is rectified by a rectifying tower 40, EEP with the purity of more than 99.8% is obtained and collected as a product, the yield is calculated, excessive ethyl alcohol discharged from the rectifying tower 40, unreacted ethyl acrylate and a small amount of EEP are returned to a proportioning tank 10, and fresh absolute ethyl alcohol and ethyl acrylate are added to adjust to 85: and 15, entering a combined fixed bed reaction device for cyclic reaction. The operation was continued for 130 days, and it was found that 0.8% of ethyl acrylate discharged to the receiving tank, the yield of collected EEP was 98.5%, and the purity was 99.91%.
Example 4
The difference from the example 1 is that the mass ratio of the absolute ethyl alcohol and the ethyl acrylate in the batching tank 10 is 90: 10, the amount of deacidified resin in the first fixed bed reactor 20 is about 15% of ethyl acrylate, and the amount of composite catalyst in the second fixed bed reactor 30 is about 15% of ethyl acrylate.
The acidity of the mixed material of ethyl acrylate and absolute ethyl alcohol after passing through the first fixed bed reactor 20 is 5-9ppm, the mixed material is cooled to 21 ℃, the mixed material is introduced into the second fixed bed reactor 30 according to the dilution rate of 2.0, the temperature of the second fixed bed reactor 30 is controlled to be 29 +/-2 ℃, the reacted material enters a receiving tank, the content of the ethyl acrylate in the receiving tank is measured, the material in the receiving tank is rectified by a rectifying tower 40, EEP with the purity of 99.8% is obtained and collected as a product, the yield is calculated, the excessive ethyl alcohol, the unreacted ethyl acrylate and a small amount of EEP carried out from the rectifying tower 40 are pumped back to a proportioning tank 10, and then fresh absolute ethyl alcohol and ethyl acrylate are added to be adjusted to be 90: and 10, entering a fixed bed for cyclic reaction. The operation was continued for 180 days, and 0.4% ethyl acrylate discharged to the receiving tank was measured, and the yield of collected EEP was 98.6% with a purity of 99%.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A preparation method of 3-ethoxy ethyl propionate is characterized by comprising the following steps:
a reaction step, carrying out addition reaction on absolute ethyl alcohol and ethyl acrylate according to a molar ratio of 3-100:1 under the action of a composite catalyst, wherein the reaction temperature is-5-35 ℃, and obtaining a mixture containing 3-ethoxy ethyl propionate;
a purification step, wherein the mixture containing the 3-ethoxy ethyl propionate is purified and separated to obtain high-purity 3-ethoxy ethyl propionate;
wherein the acidity of the absolute ethyl alcohol is less than or equal to 10 ppm; the acidity of the ethyl acrylate is less than or equal to 10 ppm;
the dosage of the composite catalyst is 0.1-15% of the weight of the ethyl acrylate;
the composite catalyst includes a strongly basic ion exchange resin.
2. The method of preparing ethyl 3-ethoxypropionate according to claim 1, wherein the composite catalyst further comprises a co-catalyst and a stabilizer; wherein the stabilizing agent is silica gel or a molecular sieve.
3. A process for the preparation of ethyl 3-ethoxypropionate according to claim 1, further comprising, before said reacting step, a deacidification step of:
deacidifying the absolute ethyl alcohol and the ethyl acrylate to obtain the absolute ethyl alcohol with the acidity of less than or equal to 10ppm and the ethyl acrylate with the acidity of less than or equal to 10 ppm.
4. A process for the preparation of ethyl 3-ethoxypropionate according to claim 3, wherein said deacidification step is carried out in a first fixed bed reactor in which deacidification resin is disposed; the dosage of the deacidification resin is 0.1 to 15 percent of the weight of the ethyl acrylate.
5. The method of claim 4, wherein the reacting step is performed in a second fixed bed reactor, and the composite catalyst is disposed in the second fixed bed reactor.
6. The method of claim 5, wherein the first fixed bed reactor is connected in series with a second fixed bed reactor.
7. The method for preparing ethyl 3-ethoxypropionate according to claim 6, wherein the first fixed-bed reactor is a tubular reactor or a tower reactor; the second fixed bed reactor is a tubular reactor or a tower reactor.
8. The method of claim 1, wherein the strongly basic ion exchange resin is a quaternary ammonium anion exchange resin.
9. The method of claim 1, wherein the purifying step is performed in a rectifying column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911349014.3A CN111004123A (en) | 2019-12-24 | 2019-12-24 | Preparation method of ethyl 3-ethoxypropionate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911349014.3A CN111004123A (en) | 2019-12-24 | 2019-12-24 | Preparation method of ethyl 3-ethoxypropionate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111004123A true CN111004123A (en) | 2020-04-14 |
Family
ID=70116251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911349014.3A Pending CN111004123A (en) | 2019-12-24 | 2019-12-24 | Preparation method of ethyl 3-ethoxypropionate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111004123A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661642A (en) * | 2020-12-09 | 2021-04-16 | 北京化学试剂研究所有限责任公司 | EEP solvent and impurity removal process and system thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4948915A (en) * | 1986-07-22 | 1990-08-14 | Union Carbide Chemicals And Plastics Company Inc. | Catalytic process for production of alkoxylated esters |
| JPH11279121A (en) * | 1998-03-27 | 1999-10-12 | Idemitsu Petrochem Co Ltd | Production of alkyl beta-alkoxypropionate |
| CN104016861A (en) * | 2014-05-30 | 2014-09-03 | 深圳市普利凯精细化工有限公司 | Preparation method for synthesis of ethyl 3-ethoxypropionate |
-
2019
- 2019-12-24 CN CN201911349014.3A patent/CN111004123A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4948915A (en) * | 1986-07-22 | 1990-08-14 | Union Carbide Chemicals And Plastics Company Inc. | Catalytic process for production of alkoxylated esters |
| JPH11279121A (en) * | 1998-03-27 | 1999-10-12 | Idemitsu Petrochem Co Ltd | Production of alkyl beta-alkoxypropionate |
| CN104016861A (en) * | 2014-05-30 | 2014-09-03 | 深圳市普利凯精细化工有限公司 | Preparation method for synthesis of ethyl 3-ethoxypropionate |
Non-Patent Citations (3)
| Title |
|---|
| LEI YANG ET AL.: "Highly efficient KF/Al2O3-catalyzed versatile hetero-Michael addition of nitrogen, oxygen, and sulfur nucleophiles to α,β-ethylenic compounds", 《TETRAHEDRON LETTERS》 * |
| 李韬等: "叠合醚化保护床催化剂的失活原因与再生方法研究", 《工业催化》 * |
| 王文兴编著: "《工业催化》", 31 December 1978, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661642A (en) * | 2020-12-09 | 2021-04-16 | 北京化学试剂研究所有限责任公司 | EEP solvent and impurity removal process and system thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2778131B2 (en) | Method for producing methyl methacrylate | |
| CN111004123A (en) | Preparation method of ethyl 3-ethoxypropionate | |
| CN111018707A (en) | Preparation method of methyl 3-methoxypropionate | |
| CN107935888B (en) | Method for preparing 3-aminopropionitrile under supercritical condition | |
| JPS61238745A (en) | Production of allyl alcohol | |
| CN114163331A (en) | Preparation method of ultra-pure photoresist reagent methyl 3-methoxypropionate | |
| IE42182B1 (en) | Process for the preparation of tetra-methylethylenediamine | |
| JP2955866B2 (en) | Method for producing dialkyl carbonate | |
| JP2623810B2 (en) | Method for producing α-hydroxyisobutyric amide | |
| JPS5929633A (en) | Method for recovering acetic acid from aqueous solution of acetate | |
| EP0127396A2 (en) | Process and catalyst for the production of aromatic amines | |
| JP3476226B2 (en) | Purification method of methacrylamide aqueous solution | |
| JPS5944305B2 (en) | Method for producing N-t-butylformamide | |
| JP2803198B2 (en) | Method for producing methyl methacrylate | |
| CN108569965A (en) | A method of preparing 3- ethoxyl ethyl propionates | |
| US7002043B2 (en) | Process for producing 1,1,1-trifluoroacetone | |
| JPH1072392A (en) | Production of oligoglycerol | |
| JP3476227B2 (en) | Method for producing methacrylamide | |
| JPH04282375A (en) | Production of high-purity 1-methylpiperazine | |
| JP3623618B2 (en) | Process for producing N- (1-alkoxyethyl) carboxylic acid amide | |
| JPH06172283A (en) | Production of alpha-hydroxyisobutyric acid amide | |
| JP3796785B2 (en) | Method for producing benzyl alcohol | |
| JP2613515B2 (en) | Method for producing sodioformylacetone | |
| KR820000822B1 (en) | Process for producing salts of pyruvic acid | |
| CN115433103A (en) | Synthesis method of isophorone nitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200414 |