CN108325560B - Catalyst, preparation method thereof and method for preparing 3-hydroxy propionaldehyde - Google Patents

Catalyst, preparation method thereof and method for preparing 3-hydroxy propionaldehyde Download PDF

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CN108325560B
CN108325560B CN201810242623.8A CN201810242623A CN108325560B CN 108325560 B CN108325560 B CN 108325560B CN 201810242623 A CN201810242623 A CN 201810242623A CN 108325560 B CN108325560 B CN 108325560B
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acrolein
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difluoro
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袁帅
黄少峰
王中华
赵聪
董龙跃
刘振峰
吕艳红
任亚鹏
许振成
黎源
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Wanhua Chemical Group Co Ltd
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    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
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    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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Abstract

The invention relates to a catalyst and a preparation method thereof, and a method for preparing 3-hydroxypropionaldehyde. The catalyst has excellent hydrophobicity, can be dissolved in a non-polar solvent, and is insoluble in water. Is suitable for catalyzing acrolein hydration reaction to prepare 3-hydroxy propionaldehyde. When the oil-water two-phase process is used for preparing the 3-hydroxypropionaldehyde, the recycling degree of the catalyst is effectively improved, the loss of the catalyst is reduced, the once-through conversion rate of the acrolein is high, the process is simple to control, and the problems that the acrolein hydration solid catalyst is unstable and volatile and the water-soluble catalyst is not easy to separate are effectively solved.

Description

Catalyst, preparation method thereof and method for preparing 3-hydroxy propionaldehyde
Technical Field
The invention relates to a catalyst, in particular to a catalyst for preparing 3-hydroxypropionaldehyde, a preparation method thereof and a method for preparing 3-hydroxypropionaldehyde by catalyzing acrolein hydration reaction by using the catalyst.
Background
3-hydroxypropanal (3-HPA) is an intermediate for producing 1, 3-propanediol, a high-performance polymer monomer, and the preparation method of 3-HPA mainly comprises two routes of acrolein hydration and Ethylene Oxide (EO) hydroformylation. The catalyst formula and the catalyst recovery process of the ethylene oxide hydroformylation method are very complicated, EO reacts with synthesis gas under high pressure, and the risk level and the equipment investment are higher (patents US5777182, CN1216034A, CN1201407A, CN1520420A and the like). The reaction condition of acrolein hydration method is mild, investment is small, but because the raw material acrolein and 3-HPA are easy to self-polymerize, cross-polymerize and decompose, etc., in order to ensure the selectivity of 3-HPA, on one hand, water is required to react with acrolein under the condition of large excess, namely, the concentration of acrolein aqueous solution is generally not more than 20 wt%, on the other hand, the acidity of catalyst must be strictly controlled.
Patent US2434110 uses protonic acid as catalyst (such as hydrochloric acid, hydrofluoric acid, phosphoric acid, oxalic acid, acetic acid, etc.) to carry out acrolein hydration reaction, and even if polymerization inhibitor is added, the selectivity of 3-HPA is low; the documents US5284979 and US5962745 use a buffer solution prepared from carboxylic acid, phosphoric acid and tertiary amine base or aromatic nitrogen heterocyclic compound as a catalyst to catalyze acrolein hydration, wherein the 3-HPA selectivity is 80% when the conversion rate of acrolein is 60%, and the 3-HPA selectivity is only 62% when the conversion rate is increased to 93%. The above catalyst has a problem that the catalyst is dissolved in a water phase and is difficult to separate after the reaction is finished, and when the catalyst enters a subsequent separation system together with acrolein and 3-HPA, the heating in a rectifying tower causes complicated reactions such as condensation, decomposition and the like of the raw materials acrolein and 3-HPA, and the successful industrialization of the process is not reported at present.
In order to reduce the separation difficulty of the catalyst, the patent US5093537 takes a molecular sieve as the catalyst to catalyze the hydration of acrolein, and the selectivity of 3-HPA can reach 86-95%, but the conversion rate is only 40-60%; patent US5276201 TiO loaded with phosphoric acid and sodium dihydrogen phosphate2、γ-Al2O3For the catalyst to catalyze acrolein hydration, the selectivity of 3-HPA can reach 81%, but the conversion rate is only 58%. The above catalyst cannot give consideration to both the conversion of acrolein and the selectivity of 3-HPA.
Chelate resin catalysts such as polystyrene phosphoramidate and styrene aminocarboxylic acid resins can achieve acrolein conversion of 70% or more and 3-HPA selectivity of 80% or more (US5015789, CN1359363A, CN1616389A, etc.). The process has no problem of difficult separation of the catalyst, and realizes industrial production by the degussa. However, during the use of the chelate type resin catalyst, acrolein still inevitably undergoes trace condensation to generate some water-insoluble polymers which cannot flow with the aqueous solution of the acrolein, and the polymers are deposited on the pore channels and the surface of the catalyst, so that the activity of the catalyst is slowly reduced, the higher the conversion rate at the initial stage of the reaction, the faster the catalyst is deactivated, and the shorter the service life of the catalyst; therefore, it is necessary to control the reaction conversion rate at a low level in the early stage of the catalyst operation and to compensate for the loss of catalytic activity by gradually increasing the reaction temperature. The average conversion is only between 50-60% throughout the process, and large amounts of acrolein need to be recovered by subsequent rectification. And the reaction temperature must be frequently regulated, the reaction conversion rate is very sensitive to the change of the temperature, the conversion rate greatly exceeds the average level when the temperature is regulated slightly, the conversion rate is greatly reduced when the temperature is regulated slightly, and the composition fluctuation of the outlet of the reactor is very large (the research and development of the new technology of the process for synthesizing the 1, 3-propylene glycol by the hydration and hydrogenation of the acrolein-Thangyon and PhD university of east China doctor-thesis) so as to bring great challenges to the operation of the reaction process and the stable operation of a subsequent separation system.
Meanwhile, by adopting a chelate resin catalyst, a polymerization inhibitor needs to be added to slow down the inactivation of the catalyst caused by condensation and deposition of acrolein, so that on one hand, the cost is increased, on the other hand, most of the polymerization inhibitor is weak acid or weak alkaline, and some side reactions are caused by the temperature increase or the polymerization inhibitor concentration increase in the rectification process.
In summary, the prior art has difficulty in resolving the inter-operative relationship between acrolein conversion, 3-HPA selectivity, catalyst life and operational stability during the preparation of 3-HPA by hydration of acrolein.
Disclosure of Invention
The object of the present invention is to provide a catalyst which has hydrophobicity, can be dissolved in a nonpolar solvent, and is insoluble in water, and a method for producing the same. The catalyst can be used for catalyzing the acrolein hydration reaction to prepare 3-hydroxypropionaldehyde (3-HPA).
The invention also aims to provide a method for preparing HPA by acrolein hydration by using the catalyst, which can realize high conversion rate of the acrolein and high selectivity of 3-HPA on the one hand, and can realize stable operation of a device on the other hand, and has no problems that the catalyst in a homogeneous catalysis process is difficult to recover and the catalyst in a heterogeneous catalysis process is unstable, thereby improving the stability of the operation of the device and effectively reducing the energy consumption for separation and the production cost.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a catalyst for preparing 3-hydroxy propionaldehyde by acrolein hydration has a structural formula of formula I (2, 6-difluoro branched chain alkyl phenyl amino diacetic acid) and/or formula II (2, 6-difluoro branched chain alkyl phenyl amino methyl phosphoric acid),
Figure BDA0001605711480000031
wherein R is1And R2Is a fluorinated branched aliphatic radical, R1And R2The number of carbon atoms of (a) is 4 to 16, preferably 8 to 12.
Preferably, said R is1And R2Independently of each other, are selected from the following substituents:
Figure BDA0001605711480000041
preferably, the catalyst of the present invention is selected from one or more of the compounds of the following structural formula:
Figure BDA0001605711480000042
Figure BDA0001605711480000051
a process for preparing a catalyst of formula I according to the present invention, comprising the steps of:
(I-1) reacting 2, 6-difluoro-branched alkyl aniline with sodium chloroacetate to prepare 2, 6-difluoro-branched alkyl phenylamino diacetate sodium;
(I-2) then acidifying the sodium 2, 6-difluoro-branched alkyl phenylamino diacetate to obtain the catalyst 2, 6-difluoro-branched alkyl phenylamino diacetate in the formula I.
In the step (I-1) of the present invention, the molar ratio of 2, 6-difluorobranched alkyl aniline to sodium chloroacetate is 1 (2.1-2.5), preferably 1 (2.2-2.3).
In the step (I-1) of the present invention, the reaction is preferably carried out in the presence of a base comprising one or both of sodium hydroxide and potassium hydroxide; the molar ratio of the used amount of the alkali to the 2, 6-difluoro branched alkyl aniline is 1.1-1.3: 1, preferably 1.1-1.2: 1; the alkali is preferably used in the form of an aqueous solution having a concentration of 5 to 30 wt%, preferably 10 to 20 wt%.
In the step (I-1), the reaction temperature is 30-80 ℃, preferably 50-70 ℃, and the reaction time is 0.5-2 h, preferably 1-1.5 h.
In the step (I-2) of the present invention, it is preferable to carry out acidification using hydrochloric acid and/or sulfuric acid. After acidification, the catalyst of formula I can be purified using well known prior art techniques, preferably by washing with water.
A process for preparing a catalyst of formula II according to the present invention, comprising the steps of:
(II-1) reacting 2, 6-difluorobranched alkyl aniline with chloromethyl phosphate to prepare 2, 6-difluorobranched alkyl phenyl phosphoramidate;
(II-2)2, 6-difluorobranched alkyl phenyl phosphoramidate by hydrolysis to obtain the catalyst 2, 6-difluorobranched alkyl phenyl aminomethyl phosphate of formula II.
Specific examples of chloromethyl phosphate esters described herein include, but are not limited to, chloromethyl dimethyl phosphate, chloromethyl diethyl phosphate, and chloromethyl diisopropyl phosphate.
In the step (II-1) of the present invention, the molar ratio of 2, 6-difluorobranched alkyl aniline to chloromethyl phosphate is 1 (1.1-1.5), preferably 1 (1.2-1.3).
In the step (II-1), the reaction temperature is 30-80 ℃, preferably 50-70 ℃; the reaction time is 0.5-2 h, preferably 1-1.5 h.
In step (II-2) of the present invention, after hydrolysis, the catalyst of formula II may be purified using known techniques of the prior art, preferably by washing with water.
The present invention also provides another method for preparing a catalyst of formula II, comprising the steps of: 2, 6-difluoro branched chain alkyl aniline reacts with chloromethyl phosphate to prepare 2, 6-difluoro branched chain alkyl phenyl amino phosphate, and the 2, 6-difluoro branched chain alkyl phenyl amino phosphate is acidified to obtain the catalyst 2, 6-difluoro branched chain alkyl phenyl amino methyl phosphoric acid shown in the formula II. Wherein the molar ratio of the 2, 6-difluoro branched alkyl aniline to the chloromethyl phosphate is 1 (1.1-1.5), preferably 1 (1.2-1.3); the reaction temperature is 30-80 ℃, and preferably 50-70 ℃; the reaction time is 0.5-2 h, preferably 1-1.5 h; preferably, hydrochloric acid and/or sulfuric acid are used for the acidification. After acidification, the catalyst of formula II can be purified using well known prior art techniques, preferably water washing.
The chloromethyl phosphate provided by the invention comprises but is not limited to chloromethyl sodium phosphate and chloromethyl potassium phosphate.
The preparation method of the 2, 6-difluoro branched chain alkyl aniline comprises the following steps: the 2, 6-difluoro branched chain alkyl aniline is prepared by alkylation reaction of aniline and fluoro olefin with 4-16 carbon atoms.
The fluoroolefin is selected from hexafluoropropylene oligomer, octafluoroisobutylene oligomer and octafluoroisobutylene; preferably, the fluoroolefin is selected from hexafluoropropylene dimer, hexafluoropropylene trimer, hexafluoropropylene tetramer, hexafluoropropylene pentamer, octafluoroisobutylene dimer, octafluoroisobutylene trimer, octafluoroisobutylene tetramer.
Preferably, the preparation method of the 2, 6-difluoro branched chain alkyl aniline comprises the following steps:
(1) reacting aniline, aluminum powder and aluminum trichloride;
(2) reacting the fluoroolefin with the product obtained in step (1).
In the step (1), the molar ratio of the aluminum powder to the aluminum trichloride is 3:1, and the molar ratio of the aluminum trichloride to the aniline is 0.05-0.2: 1, preferably 0.1-0.15: 1.
The reaction temperature in the step (1) is 150-230 ℃, preferably 180-210 ℃, and the reaction time is 0.5-5 h, preferably 1-3 h.
The reaction temperature in the step (2) is 250-350 ℃, and preferably 280-320 ℃; the molar ratio of the fluoroolefin to the aniline in the step (1) is 2.1-2.5: 1, preferably 2.2-2.3: 1.
After reacting for 6-12 h in the step (2), cooling a reaction system to room temperature, adding one or more quenching catalysts of methanol, ethanol, propanol and isopropanol which are 10-30 times of the molar weight of aluminum elements contained in the aluminum powder and the aluminum trichloride in the step (1) and layering reaction liquid, wherein the oil phase is 2, 6-difluoro branched chain alkyl aniline and unreacted fluoro olefin, and rectifying to obtain the 2, 6-difluoro branched chain alkyl aniline.
The hexafluoropropylene oligomer or octafluoroisobutylene oligomer of the present invention may be prepared through known process. The preferred method comprises the steps of: introducing hexafluoropropylene or octafluoroisobutylene into a container containing 1-5 wt% KHF at a pressure of 2-10 MPaG and a temperature of 80-150 deg.C2In DMF solution, reacting for 1-10 h. After the reaction is finished, adding water into the reaction product to promote layering, and rectifying and separating the oil phase.
The catalyst of the invention can be used for preparing 3-hydroxypropionaldehyde by acrolein hydration.
The invention also provides a method for preparing 3-hydroxypropanal by acrolein hydration, which comprises the following steps: acrolein and water are subjected to hydration reaction in the presence of a catalyst and a nonpolar solvent, the obtained oil phase and the water phase are separated, wherein the oil phase containing the catalyst is recycled to the hydration reaction, and the water phase contains 3-hydroxypropionaldehyde. The aqueous phase enters a subsequent separation system.
The hydration reaction of the present invention is carried out in the absence of polymerization inhibitors.
The non-polar solvent of the present invention includes, but is not limited to, alkanes, alkenes, cycloalkanes, aromatics, substituted aromatics, and mixtures thereof, preferably one or more of isooctane, isononane, isododecane, and isohexadecane.
The volume ratio of the nonpolar solvent to water in the method for preparing 3-hydroxypropionaldehyde is 1: 9-9: 1, preferably 2: 8-8: 2, and the molar ratio of the catalyst to acrolein is 1: 50-1: 5, preferably 1: 20-1: 10; the mass ratio of the acrolein to the water is 5: 95-30: 70, preferably 10: 90-20: 80; the reaction temperature of the hydration reaction is 35-100 ℃, and preferably 50-70 ℃; the reaction pressure is 0-1 MPaG, preferably 0-0.2 MPaG; the reaction residence time is 0.2-8 h, preferably 0.5-4 h.
The reactor for the hydration reaction is a kettle type, tubular type or jet reactor, and the Reynolds number of liquid in the reactor is 4000-5000000, preferably 10000-1000000. When the tank reactor is adopted, a high-shear paddle is preferably adopted, when the tubular reactor is adopted, a static mixer is preferably added in the reactor to ensure that the oil phase containing the catalyst is dispersed into the water phase in a small-droplet form or the water phase is dispersed into the oil phase in a small-droplet form, the higher the turbulence intensity is, the higher the shearing speed is, the larger the specific surface area of the oil phase and the water phase is, and the higher the reaction efficiency is.
In the process for producing 3-hydroxypropanal of the present invention, the separation may be carried out by a method known in the art, and preferably, a coalescer and a water separator are used. The operation temperature of the coalescer is 10-80 ℃, and preferably 30-50 ℃; the operating pressure is 0 to 1MPaG, preferably 0 to 0.2 MPaG. The operating temperature of the oil-water separator is 10-80 ℃, and preferably 30-50 ℃; the operating pressure is 0 to 1MPaG, preferably 0 to 0.2 MPaG.
The catalyst of the invention has the following characteristics:
(1) the catalyst is dissolved in the non-polar solvent, and the acrolein is dissolved in the water, so that the catalytic reaction basically and completely occurs at an oil-water interface, and the generated 3-HPA has better water solubility and can quickly diffuse into the water phase. In this process, even if the acrolein condensate is generated, since the catalyst itself does not have a problem of clogging of the cell channels, there is no problem of deactivation of the catalyst, and therefore, it is not necessary to add an additional polymerization inhibitor to prevent the catalyst from being deactivated. Even if a small amount of catalyst molecules are wrapped by the condensation compound at the oil-water interface and lose the catalytic action, the catalyst with sufficient oil phase can still ensure the smooth reaction, and the reaction temperature does not need to be adjusted to ensure the conversion rate. When the loss of the catalyst reaches a certain degree, the loss can be compensated by adding a small amount of catalyst at the inlet of the reactor. When a small amount of solid acrolein condensate is formed in the reaction system, it may be continuously or intermittently removed from the reaction system through a filter.
(2) The ortho-position of the benzene ring connected with the nitrogen atom is substituted by alkyl, so that a strong steric hindrance effect can be formed, the branched alkyl has strong rigidity, the strong steric hindrance effect can be formed at the adjacent position of the active group of the catalyst, acrolein with small molecular size and water can easily react in an included angle formed by the two branched alkyl, but the collision probability of the increased molecules and the active group of the catalyst is greatly reduced, and thus the high polymerization of the acrolein is effectively inhibited.
(3) The fluorination of the branched alkyl in the catalyst further improves the hydrophobicity of the hydrophobic end, the polarity of the 3-HPA product after the acrolein hydration is enhanced, the lipophilicity is reduced, and the hydrophobicity of the adjacent fluorinated group of the active group of the catalyst can reduce the adsorption probability of the 3-HPA and the active group of the catalyst, and inhibit the continuous self-condensation or the condensation with the acrolein to generate a byproduct. In addition, the fluoroalkyl group can also reduce the solubility of the catalyst in acrolein or 3-HPA aqueous solutions, on the one hand to reduce catalyst loss and on the other hand to avoid the catalyst entering subsequent processes to affect the recovery of the raw materials and the separation of the products.
The invention can realize 80 percent of acrolein single-pass conversion rate and more than 93 percent of 3-HPA selectivity under continuous and stable operation conditions, does not need to frequently adjust operation parameters such as reaction temperature and the like, is easy to separate the catalyst from reactants, and does not influence the subsequent product separation.
The invention has the positive effects that:
the method of the invention prepares 3-HPA by acrolein hydration, effectively solves the problems that solid catalyst is easy to inactivate and water-soluble homogeneous catalyst is difficult to separate, can realize high acrolein conversion rate and high 3-HPA selectivity on the premise of not using polymerization inhibitor, has extremely low catalyst consumption, small operation difficulty, does not need frequent operation temperature adjustment, has good operation stability, simple flow, small investment and low cost.
Detailed Description
The method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims of the invention.
Nuclear magnetism: Varian-NMR 300, chemical shifts are indicated in ppm.
High resolution Mass Spectrometry (HR-MS) APEX IV 7T FTICR.
Gas chromatograph: agilent-7820, the chromatographic conditions were as follows: DB-5 capillary chromatographic column with the diameter of 30m multiplied by 0.3mm, an FID detector, the temperature of a gasification chamber of 280 ℃, the temperature of a column box of 50-300 ℃, the temperature of the detector of 280 ℃, the flow rate of argon carrier gas of 20ml/min, the flow rate of hydrogen of 30ml/min, the flow rate of air of 300ml/min, the sample injection amount of 1 microliter and the split ratio of 10: 1.
Comparative example 1
Aminodiacetic acid chelate resin (Shanghai Kaiping resin Co., Ltd., D401) is used as a catalyst, and is stirred together with an acrolein aqueous solution to catalyze the acrolein hydration reaction (the concentration of the acrolein aqueous solution is 15 wt%), the mass ratio of the catalyst to the acrolein is 1:5, the reaction temperature is 65 ℃, the reaction time is 6h, and the change of the reaction conversion rate and the selectivity along with the use times of the catalyst is shown in the following table. The activity of the catalyst rapidly decreases with the increase of the number of times of use, and the thermogravimetric analysis shows that the organic matter deposition accounts for about 4 wt% of the weight of the catalyst and the specific surface area decreases by 9%.
Number of times of useNumber of 1 2 3 4 5
Acrolein conversion rate,% 82 66 51 40 34
3-HPA selectivity% 86 88 90 91 92
Comparative example 2
The following table shows the changes of conversion and selectivity of the reaction with the use times of the catalyst, wherein the reaction is carried out by stirring the phosphoramidate resin (D405, Anhui tree chemical industry sales Co., Ltd.) and an acrolein aqueous solution to catalyze the acrolein hydration reaction (the concentration of the acrolein aqueous solution is 15 wt%), the mass ratio of the catalyst to the acrolein is 1:5, the reaction temperature is 65 ℃, the reaction time is 6 h. The activity of the catalyst is rapidly reduced along with the increase of the using times, and the thermogravimetric analysis shows that the organic matter deposition accounts for about 5 wt% of the weight of the catalyst, and the specific surface area is reduced by 11%.
Number of times of use 1 2 3 4 5
Acrolein conversion rate,% 86 72 60 52 45
3-HPA selectivity% 83 85 87 89 90
Example 1
The structural formula of the catalyst 1 is
Figure BDA0001605711480000121
The preparation method comprises the following steps:
1) adding KHF with the content of 5 wt% into a reaction kettle2Raising the temperature to 80 ℃, introducing hexafluoropropylene and continuously supplementing to maintain the pressure of the hexafluoropropylene at 2MPaG, decompressing and emptying unreacted hexafluoropropylene after reacting for 5 hours, adding water into a liquid-phase reactant to stratify the hexafluoropropylene, wherein an oil phase is hexafluoropropylene oligomer, and obtaining hexafluoropropylene dimer (C6) through rectification separation;
2) adding aniline, aluminum powder and aluminum trichloride into a high-pressure stirring kettle, wherein the molar ratio of the aluminum powder to the aluminum trichloride is 3:1, the molar ratio of the aluminum trichloride to the aniline is 0.1, reacting at 170 ℃ for 1.5h, evacuating generated hydrogen and replacing the hydrogen with nitrogen, heating the reaction kettle to 270 ℃, introducing a hexafluoropropylene dimer prepared in the step 1) into a reactor, wherein the molar ratio of the hexafluoropropylene dimer to the aniline is 2.2, reacting for 8h, cooling to room temperature, adding a methanol quenching catalyst which is 30 times of the molar amount of an aluminum element, layering a reaction liquid, and obtaining 2, 6-difluoro branched chain alkyl aniline through rectification, wherein an oil phase is branched chain alkyl aniline (2, 6-substituted selectivity is 84%) substituted by the hexafluoropropylene dimer and unreacted hexafluoropropylene dimer;
3)2, 6-difluoro branched chain alkyl aniline, 2.2 times of molar weight of sodium chloroacetate and 1.1 times of molar weight of sodium hydroxide (10 wt% aqueous solution) are intensively stirred at 50 ℃ to react for 1 hour, then the mixture is cooled and layered, and an oil phase (2, 6-difluoro branched chain alkyl phenyl amino diacetic acid sodium) is acidified by hydrochloric acid and washed by water to obtain the target catalyst.
Nuclear magnetic analysis data: 1H NMR (300MHz, CDCl3), 4.22(m, 1H), 4.29(s, 4H), 6.8-7.0(m, 3H), 11(s, 2H); 19F NMR (376Hz, CDCl3), -190(s, 2F), -189(s, 2F), -172(s, 2F), -74.9(s, 6F), -73.6(s, 12F). Mass spectrometry data: chemical Formula C22H11F24NO4, m/z: 809.03 (100.0%), 810.03 (24.3%), 811.04 (2.8%).
The process of the catalyst 1 for catalyzing the hydration reaction of acrolein is as follows: in the reaction, n-hexane is used as a solvent of a catalyst, the volume ratio of the n-hexane to water is 1:9, the molar ratio of the catalyst to acrolein is 1:50, the mass ratio of the acrolein to the water is 30:70, the reaction temperature is 35 ℃, the reaction pressure is normal pressure (0MPaG), an emulsifying shear stirring kettle is adopted in the reactor, the Reynolds number of materials in the kettle is guaranteed, the aqueous solution of the acrolein and the catalyst solution (circulation) are continuously fed according to the feeding ratio, the product is continuously extracted, and the feeding rate guarantees the total retention time to be 8 hours. The coalescer was operated at 10 ℃ and atmospheric pressure (0 MPaG); the operating temperature of the oil-water separator is 10 ℃, and the operating pressure is normal pressure (0 MPaG); the oil phase is catalyst solution and is circulated back to the hydration reaction. The reaction was continuously run for 1000 hours, the conversion of acrolein was maintained at 81%, the selectivity of 3-HPA was maintained at 93%, no high polymer solid of acrolein was found in the reaction system, and the catalyst consumption corresponded to 0.005% by weight of the 3-HPA production.
Example 2
The structural formula of the catalyst 2 is
Figure BDA0001605711480000131
The preparation method comprises the following steps:
1) adding aniline, aluminum powder and aluminum trichloride into a high-pressure stirring kettle, wherein the molar ratio of the aluminum powder to the aluminum trichloride is 3:1, the molar ratio of the aluminum trichloride to the aniline is 0.1, reacting at 150 ℃ for 0.5h, evacuating generated hydrogen and replacing the hydrogen with nitrogen, heating the reaction kettle to 250 ℃, introducing octafluoroisobutylene into a reactor, wherein the molar ratio of the octafluoroisobutylene to the aniline is 2.1, reacting for 6h, cooling to room temperature, adding an ethanol quenching catalyst with the molar weight 25 times that of aluminum element, layering reaction liquid, and obtaining 2, 6-difluoro branched chain alkyl aniline through rectification, wherein an oil phase is octafluoroisobutane-substituted branched chain alkyl aniline (the 2, 6-substitution selectivity is 83%);
2)2, 6-difluoro branched chain alkyl aniline, 2.1 times of molar weight of sodium chloroacetate and 1.1 times of molar weight of sodium hydroxide (10 wt% aqueous solution) are intensively stirred at 30 ℃ to react for 0.5h, then the mixture is cooled and layered, and an oil phase (2, 6-difluoro branched chain alkyl phenyl amino diacetic acid sodium) is acidified by sulfuric acid and washed by water to obtain the target catalyst.
Nuclear magnetic analysis data: 1H NMR (300MHz, CDCl3), 4.28(s, 4H), 5.52(d, 2H, J)F-C-H57.3HZ), 6.8-6.9(m, 3H), 11(s, 2H); 19F NMR (376Hz, CDCl3), -137(s, 4F), -63.4(s, 12F); m/z: 610, 410, 175. Mass spectrometry data: chemical Formula C18H11F16NO4, m/z: 609.0 (100.0%), 610.0 (20.1%), 611.0 (2.7%).
The process of the catalyst 2 for catalyzing the hydration reaction of acrolein is as follows: the reaction uses isooctane as a solvent of a catalyst, the volume ratio of isooctane to water is 1:4, the molar ratio of a fed catalyst to acrolein is 1:30, the mass ratio of the acrolein to the water is 20:80, the reaction temperature is 50 ℃, the reaction pressure is 0.1MPaG, a circulating tube type reactor provided with an SL-type static mixer is adopted as the reactor, the flow rate ensures that the Reynolds number of materials in the reactor is 1000000, acrolein, water and a catalyst solution (circulation) are continuously fed according to the feeding ratio, products are continuously pumped out, and the feeding rate ensures that the total retention time is 4 hours. The coalescer was operated at 30 ℃ and 0.1 MPaG; the operation temperature of the oil-water separator is 30 ℃, and the operation pressure is 0.1MPaG under normal pressure; the oil phase is catalyst solution and is circulated back to the hydration reaction. The reaction is continuously operated for 1000h, the conversion rate of the acrolein is maintained at 84%, the selectivity of the 3-HPA is maintained at 95%, no acrolein high polymer solid is found in the reaction system, and the consumption of the catalyst is equivalent to 0.004 wt% of the yield of the 3-HPA.
Example 3
The structural formula of the catalyst 3 is
Figure BDA0001605711480000151
The preparation method comprises the following steps:
1) adding KHF with the content of 3 wt% into a reaction kettle2Raising the temperature to 100 ℃, introducing octafluoroisobutylene and continuously supplementing to ensure that the pressure of the octafluoroisobutylene is maintained at 4MPaG, decompressing and emptying unreacted octafluoroisobutylene after reacting for 3 hours, adding water into a liquid-phase reactant to stratify the liquid-phase reactant, wherein an oil phase is octafluoroisobutylene oligomer, and obtaining octafluoroisobutylene dimer (C8), trimer (C12) and tetramer (C16) through rectification separation;
2) adding aniline, aluminum powder and aluminum trichloride into a high-pressure stirring kettle, wherein the molar ratio of the aluminum powder to the aluminum trichloride is 3:1, the molar ratio of the aluminum trichloride to the aniline is 0.15, reacting at 190 ℃ for 3 hours, evacuating generated hydrogen and replacing the hydrogen with nitrogen, heating the reaction kettle to 290 ℃, introducing the octafluoroisobutylene dimer prepared in the step 1) into a reactor, wherein the molar ratio of the octafluoroisobutylene dimer to the aniline is 2.3, reacting for 10 hours, cooling to room temperature, adding a propanol quenching catalyst which is 20 times of the molar quantity of aluminum element, layering the reaction liquid, and rectifying an oil phase which is branched chain alkyl aniline (2, 6-substituted selectivity is 85%) substituted by the octafluoroisobutylene dimer and unreacted octafluoroisobutylene dimer to obtain 2, 6-difluoro branched chain alkyl aniline;
3)2, 6-difluoro branched chain alkyl aniline, 2.3 times of sodium chloroacetate and 1.2 times of sodium hydroxide (10 wt% aqueous solution) react under strong stirring at 60 ℃ for 1.5h, then the mixture is cooled and layered, and the oil phase (2, 6-difluoro branched chain alkyl phenyl amino diacetic acid sodium) is acidified by hydrochloric acid and washed by water to obtain the target catalyst.
Nuclear magnetic analysis data: 1H NMR (300MHz, CDCl3), 3.76(m, 2H), 4.29(s, 4H), 6.9-7.0(m, 3H), 11(s, 2H); 19F NMR (376Hz, CDCl3), -117(s, 4F), -106(s, 4F), -63(m, 24F); m/z: 1010, 610, 175. Mass spectrometry data: chemical Formula C26H11F32NO4, m/z: 1009.02 (100.0%), 1010.02 (28.4%), 1011.02 (4.7%).
The process of catalyzing the hydration reaction of acrolein by the catalyst 3 is as follows: the reaction uses isododecane as a solvent of a catalyst, the volume ratio of isododecane to water is 1:1, the molar ratio of the catalyst to acrolein is 1:20, the mass ratio of acrolein to water is 15:85, the reaction temperature is 60 ℃, the reaction pressure is 0.2MPaG, the reactor is a Venturi jet loop reactor, the Reynolds number of the jet zone of the reactor is 5000000, acrolein, water and a catalyst solution (circulation) are continuously fed in the feeding ratio, products are continuously extracted, and the feeding rate ensures that the total retention time is 2 hours. The coalescer was operated at 40 ℃ and 0.2 MPaG; the operation temperature of the oil-water separator is 40 ℃, and the operation pressure is 0.2MPaG under normal pressure; the oil phase is catalyst solution and is circulated back to the hydration reaction. The reaction was continuously run for 1000 hours, the conversion of acrolein was maintained at 83%, the selectivity of 3-HPA was maintained at 96%, no high polymer solid of acrolein was found in the reaction system, and the catalyst consumption corresponded to 0.003 wt% of the 3-HPA production.
Example 4
The structural formula of the catalyst 4 is
Figure BDA0001605711480000161
The preparation method comprises the following steps:
1) adding aniline, aluminum powder and aluminum trichloride into a high-pressure stirring kettle, wherein the molar ratio of the aluminum powder to the aluminum trichloride is 3:1, the molar ratio of the aluminum trichloride to the aniline is 0.2, reacting at 210 ℃ for 4 hours, evacuating generated hydrogen and replacing the hydrogen with nitrogen, heating the reaction kettle to 320 ℃, introducing the octafluoroisobutylene trimer prepared in the step 1) in the embodiment 3 into a reactor, wherein the molar ratio of the octafluoroisobutylene trimer to the aniline is 2.4, reacting for 10 hours, cooling to room temperature, adding an isopropanol quenching catalyst which is 10 times of the molar weight of aluminum element, layering reaction liquid, and rectifying an oil phase which is branched chain alkyl aniline (2, 6-substituted selectivity is 86%) substituted by the octafluoroisobutylene trimer and unreacted octafluoroisobutylene trimer to obtain 2, 6-difluoro branched chain alkyl aniline;
2) reacting 2, 6-difluoro branched chain alkyl aniline with 2.4 times molar weight of sodium chloroacetate and 1.2 times molar weight of sodium hydroxide (10 wt% aqueous solution) at 70 ℃ under strong stirring for 1.5h, cooling, layering, acidifying oil phase (2, 6-difluoro branched chain alkyl phenyl amino diacetic acid sodium) with hydrochloric acid, and washing with water to obtain the target catalyst.
Nuclear magnetic analysis data: 1H NMR (300MHz, CDCl3), 3.92(m, 2H), 4.27(s, 4H), 6.9-7.0(m, 3H), 11(s, 2H); 19F NMR (376Hz, CDCl3), -117(m, 8F), -106(m, 4F), -63(m, 36F); m/z: 1410, 810, 175. Mass spectrometry data: chemical Formula C34H11F48NO4, m/z 1408.99 (100.0%), 1410.00 (37.1%), 1411.00 (7.5%), 1412.00 (1.1%).
The process of the catalyst 4 for catalyzing the hydration reaction of acrolein is as follows: the reaction uses isomeric hexadecane as a solvent of a catalyst, the volume ratio of the isomeric hexadecane to water is 4:1, the molar ratio of the catalyst to acrolein is 1:10, the mass ratio of the acrolein to the water is 10:90, the reaction temperature is 70 ℃, the reaction pressure is 0.5MPaG, the reactor is an emulsifying shearing stirring kettle, the Reynolds number of materials in the kettle is guaranteed to be 10000, acrolein, water and a catalyst solution (circulation) are continuously fed according to the feeding ratio, products are continuously pumped out, and the feeding rate guarantees that the total retention time is 0.5 h. The coalescer was operated at 50 ℃ and 0.5 MPaG; the operation temperature of the oil-water separator is 50 ℃, and the operation pressure is 0.5MPaG under normal pressure; the oil phase is catalyst solution and is circulated back to the hydration reaction. The reaction was continuously run for 1000 hours, the conversion of acrolein was maintained at 91%, the selectivity of 3-HPA was maintained at 97%, no high polymer solid of acrolein was found in the reaction system, and the catalyst consumption corresponded to 0.002 wt% of the 3-HPA production.
Example 5
Of catalyst 5Structural formula is
Figure BDA0001605711480000181
The preparation method comprises the following steps:
1) adding aniline, aluminum powder and aluminum trichloride into a high-pressure stirring kettle, wherein the molar ratio of the aluminum powder to the aluminum trichloride is 3:1, the molar ratio of the aluminum trichloride to the aniline is 0.2, reacting at 230 ℃ for 5 hours, evacuating generated hydrogen and replacing the hydrogen with nitrogen, heating the reaction kettle to 350 ℃, introducing an octafluoroisobutylene tetramer prepared in the step 1) of the embodiment 3 into a reactor, wherein the molar ratio of the octafluoroisobutylene tetramer to the aniline is 2.5, reacting for 12 hours, cooling to room temperature, adding an excessive ethanol quenching catalyst which is 10 times of the molar weight of an aluminum element, layering reaction liquid, and rectifying an oil phase which is branched chain alkyl aniline (2, 6-substituted selectivity is 87%) substituted by the octafluoroisobutylene tetramer and unreacted octafluoroisobutylene tetramer to obtain 2, 6-difluoro substituted branched chain alkyl aniline;
2)2, 6-difluoro branched chain alkyl aniline, 2.5 times of molar weight of sodium chloroacetate and 1.3 times of molar weight of sodium hydroxide (10 wt% aqueous solution) are intensively stirred at 70 ℃ for reaction for 2h, then cooled and layered, and an oil phase (2, 6-difluoro branched chain alkyl phenyl amino diacetic acid sodium) is acidified by hydrochloric acid and washed by water to obtain the target catalyst.
Nuclear magnetic analysis data: 1H NMR (300MHz, CDCl3), 3.76(m, 2H), 4.26(s, 4H), 6.9-7.0(m, 3H), 11(s, 2H); 19F NMR (376Hz, CDCl3), -119(m, 8F), -117(m, 4F), -106(m, 4F), -61(m, 48F), m/z: 1810, 1010, 175. Mass spectrometry data: chemical Formula C42H11F64NO4, m/z: 1808.97 (100.0%), 1809.97 (45.7%), 1810.97 (11.1%), 1811.98 (1.5%).
The process of the catalyst 5 for catalyzing the hydration reaction of acrolein is as follows: the reaction uses isomeric eicosane as a solvent of a catalyst, the volume ratio of the isomeric eicosane to water is 9:1, the molar ratio of the catalyst to acrolein is 1:5, the mass ratio of the acrolein to the water is 5:95, the reaction temperature is 100 ℃, the reaction pressure is 1MPaG, a circulating tube type reactor provided with an SV type static mixer is adopted as the reactor, the flow rate ensures that the Reynolds number of materials in the reactor is 500000, acrolein, water and a catalyst solution (circulation) are continuously fed according to the feeding ratio, products are continuously pumped out, and the feeding rate ensures that the total retention time is 0.2 h. The operating temperature of the coalescer was 80 ℃ and the operating pressure 1 MPaG; the operation temperature of the oil-water separator is 80 ℃, and the operation pressure is 1MPaG under normal pressure; the oil phase is catalyst solution and is circulated back to the hydration reaction. The reaction was continuously run for 1000 hours, the conversion of acrolein was maintained at 95%, the selectivity of 3-HPA was maintained at 97%, no high polymer solid of acrolein was found in the reaction system, and the catalyst consumption corresponded to 0.001 wt% of the 3-HPA production.
Example 6
The structural formula of the catalyst 6 is
Figure BDA0001605711480000191
The preparation method comprises the following steps:
1) the preparation method of the 2, 6-difluoro branched chain alkyl aniline is the same as that of the example 3;
2)2, 6-difluoro branched chain alkyl aniline and 1.2 times of equivalent of chloromethyl methyl phosphate dimethyl ester are intensively stirred for 1 hour at 50 ℃, then cooled and layered, and the oil phase (2, 6-difluoro branched chain alkyl phenyl amino methyl phosphate) is hydrolyzed to obtain the target catalyst.
Nuclear magnetic analysis data: 1H NMR (300MHz, CDCl3), 3.78(m, 2H), 3.1(d, J ═ 11.9, 2H), 4.0(s, 1H), 6.9-7.0(m, 3H), 12(s, 2H); 19F NMR (376Hz, CDCl3), -117(s, 4F), -106(s, 4F), -63(m, 24F); m/z: 986, 588, 170. Mass spectrometry data: chemical Formula C23H10F32NO3P, m/z: 986.99 (100.0%), 987.99 (25.4%), 989.00 (3.0%).
The process of the catalyst 6 for catalyzing the hydration reaction of acrolein is as follows: cyclohexane is used as a solvent of a catalyst in the reaction, the volume ratio of cyclohexane to water is 1:9, the molar ratio of the catalyst to acrolein is 1:50, the mass ratio of acrolein to water is 30:70, the reaction temperature is 35 ℃, the reaction pressure is 0MPaG, a Venturi jet loop reactor is adopted as the reactor, the Reynolds number of a jet zone of the reactor is 5000000, acrolein, water and a catalyst solution (circulation) are continuously fed according to the feeding ratio, products are continuously extracted, and the feeding rate ensures that the total retention time is 8 hours. The coalescer was operated at 10 ℃ and 0 MPaG; the operation temperature of the oil-water separator is 10 ℃, and the operation pressure is 0MPaG under normal pressure; the oil phase is catalyst solution and is circulated back to the hydration reaction. The reaction was continuously run for 1000 hours, the conversion of acrolein was maintained at 88%, the selectivity of 3-HPA was maintained at 94%, no high polymer solid of acrolein was found in the reaction system, and the catalyst consumption corresponded to 0.005% by weight of the 3-HPA production.
Example 7
The structural formula of the catalyst 7 is
Figure BDA0001605711480000201
The preparation method comprises the following steps:
1) the preparation method of the 2, 6-difluoro branched chain alkyl aniline is the same as that of the example 4;
2)2, 6-difluoro branched chain alkyl aniline and 1.4 times of equivalent of chloromethyl diisopropyl phosphate are intensively stirred for 1.5h at 70 ℃, then cooled and layered, and the oil phase (2, 6-difluoro branched chain alkyl phenyl amino phosphoric acid diisopropyl ester) is hydrolyzed to obtain the target catalyst.
Nuclear magnetic analysis data: 1H NMR (300MHz, CDCl3), 3.92(m, 2H), 3.2(d, J ═ 11.9, 2H); 4.0(s, 1H); 6.9-7.0(m, 3H), 12(s, 2H); 19F NMR (376Hz, CDCl3), -117(m, 8F), -106(m, 4F), -63(m, 36F); m/z: 1387, 788, 170. Mass spectrometry data: chemical Formula C31H10F48NO3P, m/z: 1386.96 (100.0%), 1387.97 (33.8%), 1388.97 (6.1%).
The process of the catalyst 7 for catalyzing the hydration reaction of acrolein is as follows: the reaction uses p-xylene as a solvent of a catalyst, the volume ratio of the p-xylene to water is 1:4, the molar ratio of the catalyst to acrolein is 1:30, the mass ratio of the acrolein to the water is 20:80, the reaction temperature is 50 ℃, the reaction pressure is 0.1MPaG, a circulating tube type reactor provided with an SV type static mixer is adopted as the reactor, the flow rate ensures that the Reynolds number of materials in the reactor is 2000000, acrolein, water and a catalyst solution (circulation) are continuously fed according to the feeding ratio, products are continuously pumped out, and the feeding rate ensures the total retention time to be 4 h. The coalescer was operated at 30 ℃ and 0.1 MPaG; the operating temperature of the oil-water separator is 30 ℃, and the operating pressure is 0.1 MPaG; the oil phase is catalyst solution and is circulated back to the hydration reaction. The reaction is continuously operated for 1000h, the conversion rate of the acrolein is maintained at 81%, the selectivity of the 3-HPA is maintained at 95%, no acrolein high polymer solid is found in the reaction system, and the consumption of the catalyst is equivalent to 0.004 wt% of the yield of the 3-HPA.
Example 8
The structural formula of the catalyst 8 is
Figure BDA0001605711480000221
The preparation method comprises the following steps:
1) the preparation method of 2, 6-difluoro branched chain alkyl aniline is the same as that of the example 5;
2)2, 6-difluoro branched chain alkyl aniline and 1.5 times of equivalent of chloromethyl sodium phosphate are intensively stirred for 2h at the temperature of 80 ℃, then cooled and layered, and the oil phase (2, 6-difluoro branched chain alkyl phenyl amino sodium phosphate) is acidified by sulfuric acid and washed by water to obtain the target catalyst.
Nuclear magnetic analysis data: 1H NMR (300MHz, CDCl3), 3.76(m, 2H), 3.0(d, J ═ 11.9, 2H); 4.0(s, 1H); 6.9-7.0(m, 3H), 12(s, 2H); 19F NMR (376Hz, CDCl3), -119(m, 8F), -117(m, 4F), -106(m, 4F), -61(m, 48F); m/z: 1818, 1002, 170. Mass spectrometry data: chemical Formula C39H10F64NO3P, m/z 1786.94 (100.0%), 1787.94 (42.4%), 1788.94 (9.4%), 1789.95 (1.4%).
The process of the catalyst 8 for catalyzing the hydration reaction of acrolein is as follows: the reaction uses isododecane as a solvent of a catalyst, the volume ratio of isododecane to water is 1:4, the molar ratio of the catalyst to acrolein is 1:20, the mass ratio of acrolein to water is 15:85, the reaction temperature is 60 ℃, the reaction pressure is 0.2MPaG, a circulating pipe type reactor provided with an SX type static mixer is adopted as the reactor, the flow rate ensures that the Reynolds number of materials in the reactor is 4000000, acrolein, water and a catalyst solution (circulation) are continuously fed in the feeding ratio, products are continuously extracted, and the feeding rate ensures that the total retention time is 2 h. The coalescer was operated at 40 ℃ and 0.2 MPaG; the operating temperature of the oil-water separator is 40 ℃, and the operating pressure is 0.2 MPaG; the oil phase is catalyst solution and is circulated back to the hydration reaction. The reaction was continuously run for 1000 hours, the conversion of acrolein was maintained at 85%, the selectivity of 3-HPA was maintained at 95%, no high polymer solid of acrolein was found in the reaction system, and the catalyst consumption corresponded to 0.003 wt% of the 3-HPA production.

Claims (16)

1. A catalyst for preparing 3-hydroxypropionaldehyde by acrolein hydration, the structural formula of the catalyst is shown as a formula I and/or a formula II,
Figure FDA0002586844040000011
wherein R is1And R2Is a fluorinated branched aliphatic radical, R1And R2The number of carbon atoms of (a) is 4 to 16.
2. The catalyst of claim 1, wherein R is1And R2Independently of each other, are selected from the following substituents:
Figure FDA0002586844040000012
3. the catalyst according to claim 1 or 2, characterized in that the catalyst of formula I is selected from one or more of the compounds of the following structural formula:
Figure FDA0002586844040000013
Figure FDA0002586844040000021
the catalyst of formula II is selected from one or more of the compounds of the following structural formula:
Figure FDA0002586844040000022
4. catalysis according to claim 1Agent, characterized in that said R1And R2The number of carbon atoms of (a) is 8 to 12.
5. The catalyst according to claim 1, wherein the preparation method of the catalyst of formula I comprises the following steps: reacting 2, 6-difluoro branched alkyl aniline with sodium chloroacetate to prepare 2, 6-difluoro branched alkyl phenylamino diacetate sodium, and then acidifying the 2, 6-difluoro branched alkyl phenylamino diacetate sodium to obtain a catalyst shown in the formula I;
the preparation method of the catalyst of the formula II comprises the following steps: 2, 6-difluoro branched chain alkyl aniline reacts with chloromethyl phosphate ester to prepare 2, 6-difluoro branched chain alkyl phenyl phosphoramidate, and then the 2, 6-difluoro branched chain alkyl phenyl phosphoramidate is hydrolyzed to obtain a catalyst shown in a formula II; or reacting 2, 6-difluoro branched chain alkyl aniline with chloromethyl phosphate to prepare 2, 6-difluoro branched chain alkyl phenyl amino phosphate, and then acidifying the 2, 6-difluoro branched chain alkyl phenyl amino phosphate to obtain the catalyst shown in the formula II.
6. The catalyst according to claim 5, wherein the process for preparing 2, 6-difluorobranched-chain alkylaniline comprises the steps of: the 2, 6-difluoro branched chain alkyl aniline is prepared by alkylation reaction of aniline and fluoro olefin with 4-16 carbon atoms.
7. The catalyst of claim 6 wherein the fluoroolefin is selected from one or more of hexafluoropropylene oligomer, octafluoroisobutylene oligomer and octafluoroisobutylene.
8. The catalyst of claim 7 wherein the fluoroolefin is selected from one or more of hexafluoropropylene dimer, hexafluoropropylene trimer, hexafluoropropylene tetramer, hexafluoropropylene pentamer, octafluoroisobutylene dimer, octafluoroisobutylene trimer and octafluoroisobutylene tetramer.
9. A process for the preparation of 3-hydroxypropanal over the catalyst of any of claims 1 to 8, comprising the steps of: the acrolein and water are subjected to hydration reaction in the presence of a catalyst and a nonpolar solvent.
10. The method of claim 9, wherein the non-polar solvent comprises one or more of an alkane, an alkene, a cycloalkane, and an aromatic hydrocarbon.
11. The process according to claim 10, wherein the non-polar solvent is selected from one or more of isooctane, isononane, isododecane and isohexadecane.
12. The method of claim 9, wherein the oil phase and the water phase obtained after the hydration reaction are separated, and wherein the oil phase containing the catalyst is recycled back to the hydration reaction for reuse.
13. The method according to claim 9, wherein the volume ratio of the non-polar solvent to water is 1:9 to 9: 1; the molar ratio of the catalyst to the acrolein is 1: 50-1: 5; the mass ratio of the acrolein to the water is 5: 95-30: 70.
14. The method according to claim 13, wherein the volume ratio of the non-polar solvent to water is 2:8 to 8: 2; the molar ratio of the catalyst to the acrolein is 1: 20-1: 10; the mass ratio of the acrolein to the water is 10: 90-20: 80.
15. The method according to claim 9, wherein the reaction temperature of the hydration reaction is 35-100 ℃; the reaction pressure is 0-1 MPaG; the reaction residence time is 0.2-8 h.
16. The method according to claim 15, wherein the reaction temperature of the hydration reaction is 50-70 ℃; the reaction pressure is 0-0.2 MPaG; the reaction residence time is 0.5-4 h.
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CN109134224A (en) * 2018-09-30 2019-01-04 浙江工业大学 A kind of method of preparing 3-hydroxy propanal by hydrating acrolein
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