CN113461512B - Preparation method of 3-hydroxypropionic acid - Google Patents
Preparation method of 3-hydroxypropionic acid Download PDFInfo
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- CN113461512B CN113461512B CN202110900785.8A CN202110900785A CN113461512B CN 113461512 B CN113461512 B CN 113461512B CN 202110900785 A CN202110900785 A CN 202110900785A CN 113461512 B CN113461512 B CN 113461512B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
Abstract
The invention relates to a preparation method of 3-hydracrylic acid, which comprises the steps of taking a mixture of acrylic acid, water and a polymerization inhibitor containing a catalyst as a reaction raw material, and obtaining the main product of 3-hydracrylic acid through a hydration reaction process, wherein the catalyst is a saturated organic acid with the carbon number not more than 3. Compared with the prior art, the method has the advantages of simple components of reaction products, good catalyst performance, easy recovery, low operation cost and the like.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and relates to a preparation method of 3-hydroxypropionic acid, in particular to a method for preparing 3-hydroxypropionic acid by homogeneous catalysis of acrylic acid hydration.
Background
3-hydroxypropionic acid (3-HP for short), and has molecular formula of C 3 H 6 O 3 The molecular weight is 90.08, the chiral organic acid is an achiral organic acid with three carbon atoms, the acid dissociation constant (pKa) is 4.5, the liquid is colorless liquid at normal temperature (part of the product is light yellow), the liquid is almost odorless, and the chiral organic acid is soluble in water, ethanol and ether, has two functional groups, namely hydroxyl and carboxyl, and is a precursor of a plurality of optically active substances. 3-HP is involved in a variety of reactions: esterification reaction is carried out on the obtained product and alcohol to generate ester, malonic acid is generated through oxidation, acrylic acid is generated through dehydration, and 1, 3-propanediol is obtained through reduction; wherein 1, 3-propanediol is the main monomer of polytrimethylene terephthalate fiber (PTT), and can also be used for producing coatings, adhesives, water treatment chemicals and personal care products. The 3-HP monomer can be used as an additive and a preservative of food or feed and also can be used as a raw material of high-performance polyester. Compared with the mainstream degradable materials such as polylactic acid (PLA) and the like, the poly-3-hydroxypropionic acid (P3 HP) serving as the degradable thermoplastic material has more excellent physical properties, such as higher ductility and tensile property, stronger water vapor barrier property and wider application prospect, so that the P3HP becomes a hot spot for research and development in the field of degradable materials.
At present, the preparation method of 3-HP mainly adopts a chemical method and a microbial fermentation method. Wherein, the microbial method has low yield, high cost and complicated separation and purification process, and is not suitable for large-scale production. The chemical method mainly comprises 3-hydroxypropionitrile hydrolysis, 3-hydroxypropionaldehyde oxidation, reformatsky reaction and acrylic acid hydration, wherein the acrylic acid hydration method has the advantages of simple process conditions, low production cost, relatively high environmental friendliness and great industrial value.
The reaction for hydration of acrylic acid to produce 3-hydroxypropionic acid is represented as follows:
the reports of preparing 3-hydroxypropionic acid by hydrating acrylic acid are few, and the preparation process of only the patent in the literature is complex and difficult to realize industrial production.
Patent CN1753858A discloses a method for preparing 3-hydroxypropionic acid by using carbon dioxide, sulfur dioxide, nitrogen oxide and organic base or inorganic base with pKa more than 7 as catalysts and adopting an acrylic acid hydration method, wherein the 3-hydroxypropionic acid is obtained by reacting at 170 ℃ for 18h, the yield of the 3-hydroxypropionic acid is 68.7%, the yield of ether dimer is 13.1%, the product is 3-hydroxypropionate after the reaction, the steps of acidification, extraction and the like are required, and the recovery and the separation are complex.
Patent CN102746141A discloses that inorganic protonic acid, lewis acid or solid acid is used as catalyst, the reaction temperature is 90-250 ℃, the reaction time is 3-18 hours, the conversion rate of acrylic acid is 86.67%, and the selectivity of 3-hydroxypropionic acid is 80.45%.
Patent CN110981718A discloses that acrylic acid is continuously hydrated to prepare 3-hydroxypropionic acid by taking an acidic modified molecular sieve as a catalyst, the reaction is carried out in a fixed bed reactor, and the liquid hourly space velocity is 1h -1 The reaction temperature is 100 ℃, the conversion rate of acrylic acid is 97.26 percent, and the selectivity of 3-hydroxypropionic acid is 89.41 percent, the method realizes that the conversion rate and the selectivity of the reaction are improved under mild conditions, and the self-polymerization side reaction of the acrylic acid is inhibited, but the catalyst molecular sieve is inactivated due to dealumination, the regeneration is difficult, and the service life is short.
Therefore, the prior art has the problems of low yield, difficult catalyst separation and short service life.
Disclosure of Invention
Aiming at the problems of complex reaction product components, poor catalyst performance, difficult subsequent separation and particularly difficult catalyst circulation in the prior art, the invention provides the method for preparing the 3-hydroxypropionic acid with high efficiency and low cost, and the method has very high selectivity, simple subsequent separation measures and easy establishment of material circulation and is suitable for industrial production.
The technical scheme of the invention is as follows:
a preparation method of 3-hydracrylic acid takes acrylic acid and water as reaction raw materials, under the action of a catalyst, the acrylic acid is subjected to hydration reaction to generate the 3-hydracrylic acid, and the catalyst is a saturated organic acid with carbon number not more than 3 so as to overcome the defect of an inorganic acid catalyst;
preferably, the catalyst is selected from saturated organic acids having a pKa <2.2 and a boiling point of less than 200 ℃, more preferably, the saturated organic acids include, but are not limited to, mixtures of one or more of difluoroacetic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, pentafluoropropionic acid, trifluoromethanesulfonic acid, so that the catalyst has a strong acidity comparable to that of the inorganic acid and a boiling point of less than 3-hydroxypropionic acid, simplifying the separation process;
preferably, the reaction raw material further comprises a polymerization inhibitor to reduce self-polymerization of acrylic acid, which affects normal operation, and the polymerization inhibitor comprises but is not limited to a mixture of one or more of hydroquinone, p-hydroxyanisole and phenothiazine.
Preferably, the purity of the acrylic acid is greater than 99.0%, and the water is one of distilled water, double distilled water, deionized water and ultrapure water.
Besides 3-hydroxypropionic acid, the reaction product also has a small amount of byproducts, and the reaction byproducts are one or a mixture of 3-hydroxypropionic acid dimer etherification products, poly-3-hydroxypropionic acid and polyacrylic acid.
The preparation method specifically comprises the following steps:
(1) Preparing a reaction raw material mixture: fresh acrylic acid and water pass through pipelines, fresh polymerization inhibitor passes through pipelines, and the mixture of acrylic acid, water and catalyst which is recycled passes through pipelines, and then the mixture of acrylic acid, water and catalyst which is supplemented passes through pipelines and enters a raw material preparation tank to be mixed, so that a reaction raw material mixture with a certain composition is prepared;
(2) Preheating reaction raw materials: conveying the reaction raw material mixture to a preheater by a raw material conveying pump through a pipeline, and heating to a preset reaction temperature by adopting steam;
(3) Carrying out hydration reaction: the high-temperature reaction raw material mixture obtained from the preheating step enters a hydration reactor, and hydration reaction is carried out under the action of a catalyst to generate 3-hydroxypropionic acid, so as to obtain a mixed product containing the 3-hydroxypropionic acid, the residual acrylic acid, water, the catalyst and a polymerization inhibitor in the reaction, and a byproduct;
(4) Rectifying and recovering saturated organic acid, water and acrylic acid: feeding the mixed product obtained in the step (A) into a rectifying tower through a pipeline, rectifying the mixed product under a reduced pressure state, obtaining the recovered catalyst, unreacted acrylic acid and water at the top of the rectifying tower, returning the recovered catalyst, unreacted acrylic acid and unreacted water to a raw material preparation tank through the pipeline for recycling, and obtaining a 3-HP product at the bottom of the tower;
preferably, in the step (1), the molar ratio of water to acrylic acid in the reaction raw material mixture is (1.
Preferably, in the step (1), the molar ratio of the catalyst to the acrylic acid is (1.
More preferably, in the step (1), the molar ratio of the catalyst to the acrylic acid is (1.
Preferably, in the step (1), the molar ratio of the polymerization inhibitor to the acrylic acid is (1.
In the above technical solution, in the step (3), the reaction conditions of the hydration reaction are as follows: the reaction temperature is 100-200 ℃, the reaction residence time is 3-10 h, preferably, the reaction temperature is 120-180 ℃, and the reaction residence time is 3-8 h.
Preferably, the hydration reactor is a stirred tank, a packed column, a plate column or an empty column, and any combination thereof is also possible.
Preferably, in the step (4), the bottom temperature of the rectifying tower is 100-180 ℃, and the rectifying pressure is 1-20 kPa, preferably 1-10 kPa.
Theoretically, the higher the vacuum degree (the lower the pressure), the lower the rectification temperature, which is beneficial to the efficient purification of the 3-hydroxypropionic acid at lower temperature and the reduction of side reactions, but the higher the vacuum degree, the higher the requirement on a vacuum pump, and the less beneficial to the industrial amplification.
The specific operation process of the invention is carried out according to the following steps:
(i) Freshly preparing an acrylic acid aqueous solution in a raw material preparation tank, adding a small amount of polymerization inhibitor, and adding a catalyst into a reaction solution in proportion;
(ii) The reaction liquid is conveyed to a preheater and is heated to a preset reaction temperature by adopting steam;
(iii) Purging the reactor with nitrogen for many times to discharge air, preheating to obtain a high-temperature reaction raw material mixture, feeding the high-temperature reaction raw material mixture into a hydration reactor, and reacting at normal pressure;
(iv) After the reaction is finished, fully cooling the reactor, slowly releasing the pressure to normal pressure, and sampling and analyzing;
(v) And transferring the reaction product to a rectifying tower for reduced pressure distillation, sampling and analyzing liquid at the top and the bottom of the tower, and returning the material at the top of the tower to the raw material preparation tank for recycling.
Compared with the prior art, the invention has the following advantages:
the method takes saturated organic acid such as trifluoroacetic acid and the like as the catalyst, not only provides a strong acid reaction environment, has high activity under mild conditions and low boiling point, but also adopts a reduced pressure rectification method to separate a reaction system with low boiling point and products with high boiling point, reduces side reactions in the separation process, is beneficial to the purification of reaction products and the circulation of the catalyst and raw materials, obtains better technical effect, and can be used in the industrial production of 3-hydroxypropionic acid. By adopting the technical scheme of the invention, the conversion rate of acrylic acid reaches 74.4%, the selectivity of 3-hydroxypropionic acid reaches 99.9%, and compared with the existing preparation method, the method has higher selectivity of 3-hydroxypropionic acid, and in addition, the method has no defects of catalyst deactivation (molecular sieve dealumination deactivation) and the like, and has the problems of short service life and difficult separation. The invention takes saturated organic acid such as trifluoroacetic acid and the like as the catalyst, the catalyst has good performance, is easy to separate and recover, can obviously reduce the cost, and has obvious progress.
Drawings
FIG. 1 is a flow diagram of a system for preparing 3-hydroxypropionic acid according to the present invention;
FIG. 2 selectivity and conversion of acrylic acid at different reaction times in example 1;
FIG. 3 NMR spectrum of the reaction product of step (3) in example 1;
FIG. 4 NMR spectra of isolated 3-hydroxypropionic acid and oligomers thereof of example 1;
FIG. 5 NMR spectrum of the mixed solution isolated in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
FIG. 1 is a flow chart of a preparation process system of 3-hydroxypropionic acid, and a preparation method of 3-hydroxypropionic acid comprises the following steps:
(1) Preparing a reaction raw material mixture: fresh acrylic acid passes through a pipeline 1 and water passes through a pipeline 2, fresh polymerization inhibitor passes through a pipeline 3, and the mixture of the acrylic acid, the water and the catalyst which are circulated back passes through a pipeline 5 and then passes through a pipeline 4 together with the supplemented catalyst enters a raw material preparation tank 101 to be prepared according to the proportion to obtain a reaction raw material mixture;
(2) Preheating reaction raw materials: the reaction feed mixture is conveyed by a feed transfer pump 102 through a line 6 to a preheater 103 and heated with steam to a predetermined reaction temperature;
(3) Carrying out hydration reaction: the high-temperature reaction raw material mixture obtained from the preheating in the step (2) enters a hydration reactor 104, and is subjected to hydration reaction under the action of a catalyst to generate 3-hydroxypropionic acid, so that a mixed product containing the 3-hydroxypropionic acid, the residual acrylic acid, water, the catalyst, a polymerization inhibitor and byproducts is obtained;
(4) Rectifying and recovering saturated organic acid, water and acrylic acid: and (4) feeding the mixed product obtained in the step (3) into a rectifying tower 105 through a pipeline 7, rectifying under a reduced pressure state, obtaining the recovered catalyst and unreacted acrylic acid and water at the top of the rectifying tower 105, returning the recovered catalyst and unreacted acrylic acid and water to the raw material preparation tank 101 through a pipeline 5 for recycling, obtaining a 3-HP product at the bottom of the tower, and outputting the 3-HP product through a pipeline 8.
In a preferred embodiment, in the step (1), the molar ratio of water to acrylic acid in the reaction raw material mixture is (1.
As a preferred embodiment, in step (1), the catalyst is selected from saturated organic acids with pKa <2.2, more preferably, the saturated organic acids include, but are not limited to, difluoroacetic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, pentafluoropropionic acid, mixtures of one or more of trifluoromethanesulfonic acid.
In a preferred embodiment, in the step (1), the molar ratio of the catalyst to the acrylic acid is (1; more preferably, in the step (1), the molar ratio of the catalyst to the acrylic acid is (1.
As a preferred embodiment, in step (1), the polymerization inhibitor includes, but is not limited to, one or more of hydroquinone, p-hydroxyanisole, and phenothiazine, and the molar ratio of the polymerization inhibitor to the acrylic acid is (1.
As a preferable embodiment, in the step (3), the reaction conditions of the hydration reaction are: the reaction temperature is 100-200 ℃, the reaction residence time is 3-10 h, preferably, the reaction temperature is 120-180 ℃, and the reaction residence time is 3-8 h. The hydration reactor is a stirred tank, a packed tower, a plate tower or an empty tower, and can also be a combination of the stirred tank, the packed tower, the plate tower and the empty tower.
In a preferred embodiment, in the step (4), the bottom temperature of the rectifying column 105 is 100 to 180 ℃ and the rectifying pressure is 1 to 20kPa, preferably 1 to 10kPa.
In the examples, the following test methods were used to test the properties of the products prepared according to the invention:
1. high Performance Liquid Chromatography (HPLC)
The product prepared by the invention is detected by adopting a quaternary low-pressure liquid chromatography LC-2030i of Shimadzu corporation, a MetaChem Inertsil ODS-2C18 polar column (5 mu m,250x 4.6 mm) is used as a chromatographic column, and a mobile phase is H 3 PO 4 /KH 2 PO 4 Buffer solution: methanol =9:1, the concentration of the buffer solution is 0.1mol/L, the pH =2, the flow rate is 1mL/min, the column temperature is 35 ℃, and the wavelength of the ultraviolet detector is 210nm.
2. Nuclear magnetic resonance hydrogen spectrum ( 1 H-NMR)
The product prepared by the invention and the separated liquid are detected by a DRX 400MHz nuclear magnetic resonance spectrometer of Bruker company under the test conditions of 9.2T magnetic field intensity, 400.15MHz working frequency, 8010.54Hz spectral width, 10 mu m pulse width, 2s pulse delay and 32 times sampling, the diameter of a nuclear magnetic tube is 5mm, and the product obtained in the step (3) is D 2 O is a solvent, the sampling amount is 5 mu L, and the solvent is dissolved in 0.5mL of deuterated solvent; and (4) dissolving the product of the step (4) in 0.5mL of deuterated solvent by taking deuterated acetone as a solvent and sampling the volume of 5 mu L.
The following are specific examples:
example 1
A method of preparing 3-hydroxypropionic acid, comprising the steps of:
(1) Preparing a reaction raw material mixture: freshly preparing 50mL of acrylic acid aqueous solution in a raw material preparation tank, wherein the molar ratio of acrylic acid to water is 1.
(2) Preheating reaction raw materials: the reaction feed mixture was transferred to a preheater using a feed transfer pump and heated to 160 ℃ using steam.
(3) Carrying out hydration reaction: and (3) feeding the high-temperature reaction raw material mixture obtained by preheating in the step (2) into a hydration reactor for reaction, wherein the reaction temperature is 160 ℃, and the reaction retention time is 5h.
(4) Rectifying to recover saturated organic acid, water and acrylic acid: the mixed product obtained by the reaction enters a rectifying tower through a pipeline and is rectified under a reduced pressure state. The rectification pressure is 2kPa, the temperature at the bottom of the tower is 125 ℃, the liquid at the top of the tower and the liquid at the bottom of the tower are sampled and analyzed, and the material at the top of the tower returns to the raw material preparation tank for recycling.
Referring to FIGS. 2 to 5, which are graphs showing the changes of the selectivity and the conversion rate of acrylic acid at different reaction times, the NMR of the reaction product obtained in the step (3), the NMR of the separated 3-hydroxypropionic acid and the oligomer thereof, and the NMR of the separated mixed solution in example 1, respectively. It can be known that the reaction product obtained in step (3) mainly comprises 3-HP monomer, a small amount of etherification product of P3-HP and 3-hydroxypropionic acid dimer, and a very small amount of polyacrylic acid; after the rectification separation in the step (4), high-purity 3-hydroxypropionic acid, poly-3-hydroxypropionic acid and etherification products are obtained at the bottom of the tower, and all unreacted acrylic acid raw materials and catalysts are collected at the top of the tower.
Example 2
A process for preparing 3-hydroxypropionic acid comprising the steps of:
(1) Preparing a reaction raw material mixture: newly preparing 50mL of acrylic acid aqueous solution in a raw material preparation tank, wherein the molar ratio of acrylic acid to water is 1.
(2) Preheating reaction raw materials: the reaction feed mixture was transferred to a preheater using a feed transfer pump and heated to 150 ℃ using steam.
(3) Carrying out hydration reaction: and (3) feeding the high-temperature reaction raw material mixture obtained by preheating in the step (2) into a hydration reactor for reaction, wherein the reaction temperature is 150 ℃, and the reaction retention time is 5h.
(4) Rectifying to recover saturated organic acid, water and acrylic acid: the mixed product obtained by the reaction enters a rectifying tower through a pipeline and is rectified under a reduced pressure state. The rectification pressure is 2kPa, the temperature at the bottom of the tower is 125 ℃, the liquid at the top of the tower and the liquid at the bottom of the tower are sampled and analyzed, and the material at the top of the tower returns to the raw material preparation tank for recycling.
The reactor used is a packed tower reactor.
Example 3
A process for preparing 3-hydroxypropionic acid comprising the steps of:
(1) Preparing a reaction raw material mixture: newly preparing 50mL of acrylic acid aqueous solution in a raw material preparation tank, wherein the molar ratio of acrylic acid to water is 1.
(2) Preheating reaction raw materials: the reaction feed mixture was fed to a preheater by a feed transfer pump and heated to 140 ℃ with steam.
(3) Carrying out hydration reaction: and (3) feeding the high-temperature reaction raw material mixture obtained by preheating in the step (2) into a hydration reactor for reaction, wherein the reaction temperature is 140 ℃, and the reaction residence time is 6h.
(4) Rectifying to recover saturated organic acid, water and acrylic acid: the mixed product obtained by the reaction enters a rectifying tower through a pipeline and is rectified under a reduced pressure state. The rectification pressure is 2kPa, the temperature at the bottom of the tower is 135 ℃, the liquid at the top and the bottom of the tower is sampled and analyzed, and the material at the top of the tower returns to the raw material preparation tank for recycling.
The reactor used is an empty column reactor.
Example 4
A process for preparing 3-hydroxypropionic acid comprising the steps of:
(1) Preparing a reaction raw material mixture: newly preparing 50mL of acrylic acid aqueous solution in a raw material preparation tank, wherein the molar ratio of acrylic acid to water is 1.
(2) Preheating reaction raw materials: the reaction feed mixture was transferred to a preheater by a feed transfer pump and heated to 150 ℃ with steam.
(3) Carrying out hydration reaction: and (3) feeding the high-temperature reaction raw material mixture obtained by preheating in the step (2) into a hydration reactor for reaction, wherein the reaction temperature is 150 ℃, and the reaction residence time is 6h.
(4) Rectifying to recover saturated organic acid, water and acrylic acid: the mixed product obtained by the reaction enters a rectifying tower through a pipeline and is rectified under a reduced pressure state. The rectification pressure is 1.5kPa, the bottom temperature is 130 ℃, the liquid at the top and the bottom of the tower is sampled and analyzed, and the material at the top of the tower returns to the raw material preparation tank for recycling.
The reactor used is a sieve plate tower reactor.
Example 5
A method of preparing 3-hydroxypropionic acid, comprising the steps of:
(1) Preparing a reaction raw material mixture: freshly preparing 50mL of acrylic acid aqueous solution in a raw material preparation tank, wherein the molar ratio of acrylic acid to water is 1.
(2) Preheating reaction raw materials: the reaction feed mixture was fed to a preheater by a feed transfer pump and heated to 170 ℃ with steam.
(3) Carrying out hydration reaction: and (3) feeding the high-temperature reaction raw material mixture obtained by preheating in the step (2) into a hydration reactor for reaction, wherein the reaction temperature is 170 ℃, and the reaction retention time is 5h.
(4) Rectifying to recover saturated organic acid, water and acrylic acid: the mixed product obtained by the reaction enters a rectifying tower through a pipeline and is rectified under a reduced pressure state. The rectification pressure is 2kPa, the temperature at the bottom of the tower is 125 ℃, the liquid at the top of the tower and the liquid at the bottom of the tower are sampled and analyzed, and the material at the top of the tower returns to the raw material preparation tank for recycling.
The adopted reactor is a reactor with 4 stirred tanks connected in series.
Example 6
A method of preparing 3-hydroxypropionic acid, comprising the steps of:
(1) Preparing a reaction raw material mixture: newly preparing 50mL of acrylic acid aqueous solution in a raw material preparation tank, wherein the molar ratio of acrylic acid to water is 1.
(2) Preheating reaction raw materials: the reaction feed mixture was fed to a preheater by a feed transfer pump and heated to 130 ℃ with steam.
(3) Carrying out hydration reaction: and (3) feeding the high-temperature reaction raw material mixture obtained by preheating in the step (2) into a hydration reactor for reaction, wherein the reaction temperature is 130 ℃, and the reaction residence time is 7h.
(4) Rectifying and recovering saturated organic acid, water and acrylic acid: the mixed product obtained by the reaction enters a rectifying tower through a pipeline and is rectified under a decompression state. The rectification pressure is 2kPa, the temperature at the bottom of the tower is 130 ℃, the liquid at the top and the bottom of the tower is sampled and analyzed, and the material at the top of the tower returns to the raw material preparation tank for recycling.
The reactor used is a reactor with 2 stirred tanks connected in series.
TABLE 1 analysis results of the product compositions in the examples
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A preparation method of 3-hydracrylic acid is characterized in that acrylic acid and water are used as reaction raw materials, under the action of a catalyst, the acrylic acid is subjected to hydration reaction to generate the 3-hydracrylic acid, and the catalyst is a saturated organic acid with the carbon number not more than 3; the boiling point of the saturated organic acid is less than 200 ℃, and the pKa value is less than 2.2;
the method specifically comprises the following steps:
(1) Preparing reaction raw materials: mixing fresh raw materials containing acrylic acid, water and polymerization inhibitor, incompletely reacted circulating materials and supplemented catalyst to prepare reaction raw materials with a certain composition;
(2) Preheating reaction raw materials: the reaction raw materials are conveyed to a preheater through a raw material conveying pump and preheated to a certain temperature;
(3) Hydration reaction: the reaction raw material from the preheater enters a hydration reactor, and hydration reaction is carried out under the catalysis of a catalyst to obtain a reaction product containing 3-hydroxypropionic acid;
(4) And (3) product separation: and (2) feeding the reaction product from the hydration reactor into a rectifying tower, rectifying under a reduced pressure state, wherein the pressure at the top of the rectifying tower is 1-10kPa, obtaining the recovered catalyst, unreacted acrylic acid and water at the top of the rectifying tower, returning the recovered catalyst, unreacted acrylic acid and water to the raw material preparation step, and obtaining a product containing 3-hydroxypropionic acid at the bottom of the rectifying tower.
2. The method of claim 1, wherein the saturated organic acid comprises one or more of difluoroacetic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, pentafluoropropionic acid, and trifluoromethanesulfonic acid.
3. The method for preparing 3-hydroxypropionic acid according to claim 1, wherein the reaction raw material further comprises a polymerization inhibitor, and the polymerization inhibitor is one or a mixture of hydroquinone, p-hydroxyanisole and phenothiazine.
4. The method according to claim 1, wherein the molar ratio of the water to the acrylic acid in the reaction raw materials is (1.
5. The method according to claim 1, wherein the molar ratio of the polymerization inhibitor to the acrylic acid in the reaction raw materials is (1.
6. The method of claim 1, wherein the hydration reactor is a stirred tank, a packed column, a tray column, or an empty column, or any combination thereof.
7. The method for preparing 3-hydroxypropionic acid as claimed in claim 1, wherein the reaction temperature of the hydration reactor is 100 to 200 ℃, and the reaction residence time is 3 to 10hr.
8. The method for preparing 3-hydroxypropionic acid as claimed in claim 1, wherein the temperature of the bottom of the rectifying tower is in the range of 100 to 180 ℃.
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