Catalyst for preparing hydroxyaldehyde by olefine aldehyde hydration and preparation method and application thereof

Abstract

The invention provides a catalyst for preparing hydroxyaldehyde through olefine aldehyde hydration and a preparation method and application thereof.The catalyst comprises a styrene acid resin matrix and metal ions bonded to the styrene acid resin matrix, the metal ions are combined with the styrene acid resin matrix through acid groups carried by the styrene acid resin matrix, the content of the metal ions in the catalyst is 10-10000 ppm, the acid equivalent is 3.5-5.4 mmol / g, and the content of the metal ions in the catalyst is 10-10000 ppm. The metal ions are selected from one or more of alkali metal ions, alkaline earth metal ions, transition metal ions and amphoteric metal ions. By utilizing the catalyst for preparing the hydroxyaldehyde through the hydration of the olefine aldehyde, the acidity of a reaction solution for preparing the hydroxyaldehyde through the hydration of the olefine aldehyde can be controlled, side reactions in a system can be reduced, the selectivity of the hydration reaction is improved, the service life of the catalyst for the subsequent hydrogenation reaction is prolonged, and the product quality can also be improved. The method can avoid the problem that the subsequent separation difficulty is increased due to the fact that organic acid is additionally added to adjust acidity and reduce the concentration of reaction raw materials to increase yield.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, and in particular to a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde, and a preparation method and application thereof. Background Art

[0002] As an important organic chemical raw material, 1,3-propylene glycol (1,3-PDO) has shown broad application prospects in the fields of pharmaceutical intermediates, PTT fibers, coatings, cosmetics, etc. Among the traditional production processes of 1,3-PDO, the acrolein hydration hydrogenation method is recognized as a method suitable for industrial production because of its mild reaction conditions, low equipment requirements, and wide sources of raw materials. The acrolein hydration hydrogenation method includes the hydration reaction of acrolein to generate hydroxy aldehydes, and the hydrogenation reaction of the generated hydroxy aldehydes to obtain 1,3-PDO, among which the hydration of acrolein to prepare hydroxy aldehydes is an important step in determining the reaction efficiency and selectivity.

[0003] However, there are two major technical challenges in the process of preparing hydroxy aldehydes by hydration of acrolein: First, the self-polymerization of acrolein and the formation of by-products: under the action of acidic and alkaline substances, the raw material acrolein is prone to self-polymerization and mutual condensation reactions, and adsorbed on the catalyst surface, resulting in reduced catalyst activity and decreased reaction selectivity. The self-polymerization reaction of acrolein is particularly significant under alkaline conditions, and the generated white flocculent precipitate will block the catalyst pores and affect the reaction efficiency. At the same time, hydroxy aldehydes are also prone to aldol condensation reactions or polymerization reactions under the action of alkaline substances, generating high-boiling impurities, further deteriorating product purity. Second, separation energy consumption and cost: In order to improve the selectivity of the hydration reaction, the existing technology usually controls the concentration of the acrolein aqueous solution at 15-20%, resulting in a concentration of the hydration product 3-hydroxypropanal ≤10%, which significantly increases the separation energy consumption and cost of the subsequent hydrogenation reaction to generate 1,3-PDO. CN1170802C adds aliphatic carboxylic acids of 3-8 carbon atoms (such as acetic acid and propionic acid) to the reaction system and adjusts the pH value to 1-5.5. Although the selectivity of 3-hydroxypropanal is improved to a certain extent, the additional addition of organic acid increases the difficulty and cost of subsequent separation. CN113105315B uses a cation exchange resin containing specific functional groups on the surface as a catalyst to carry out a hydration reaction at 40-60°C. Although the selectivity of 3-hydroxypropanal can reach 90%, the separation requirement of organic solvent and organic acid also increases the process complexity and production cost.

[0004] In summary, the existing technology mostly improves the selectivity of the product through the following two ways: First, organic acid is added to the system to control the acidity of the acrolein hydration reaction liquid and reduce the generation of impurities, but the added substances increase the difficulty of subsequent separation. Second, the content of olefinic aldehyde in the reaction liquid is reduced. The saturated solubility of acrolein in water is 20%. In order to control the impurity content during the reaction process, the hydration reaction conversion rate is generally 50%, and the 3-HPA concentration in the aqueous solution is ≤10%; the second step of hydrogenation reaction generally adopts a two-stage hydrogenation method, and the hydrogenation conversion rate and 1,3-PDO selectivity are close to 100%. The concentration of 1,3-PDO in the generated hydrogenated liquid is only about 10%. For every ton of 1,3-PDO produced, 9 to 10 tons of water need to be separated. The separation energy consumption and cost are high, and a large amount of coal or natural gas resources are consumed. These methods often sacrifice reaction efficiency or increase production costs, and fail to reach the ideal level of industrial application.

[0005] Therefore, there is an urgent need for a new method that can effectively achieve the hydration of enal to prepare hydroxy aldehydes (such as 3-hydroxypropionaldehyde) under high concentration conditions while maintaining high selectivity, reducing the formation of by-products, reducing energy consumption and costs, and extending the service life of catalytic hydrogenation catalysts, thereby improving the overall production efficiency and product quality of PDO. Summary of the invention

[0006] The main purpose of the present invention is to provide a catalyst for preparing hydroxy aldehydes by hydration of olefinic aldehydes, and a preparation method and application thereof, so as to solve the problem in the prior art that high selectivity, few by-products, and low subsequent separation energy consumption and cost cannot be taken into account simultaneously when preparing hydroxy aldehydes by hydration of olefinic aldehydes.

[0007] In order to solve the above problems, the present invention provides a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde, the catalyst comprising a styrene acidic resin matrix and a metal ion bonded thereto, the styrene acidic resin matrix carries an acidic group, and the metal ion is combined with the acidic group; wherein the acidic group combined with the metal ion has at least one of the structures shown in formula (I), formula (II) and formula (III):

[0008]

[0009] X is a metal ion or H, and at least part of X in the catalyst is a metal ion; the content of the metal ion in the catalyst is 10 to 10000 ppm, the acid equivalent of the catalyst is 3.5 to 5.4 mmol / g, and the metal ion is selected from one or more of alkali metal ions, alkaline earth metal ions, transition metal ions and amphoteric metal ions.

[0010] Furthermore, the content of metal ions in the catalyst is 500 to 8000 ppm, the acid equivalent of the catalyst is 4 to 5 mmol / g, and the metal ions are Na + Mg2+ , Cu 2+ 、Zn 2+ , K + , Ca 2+ , Sr 2+ , Ba 2+ , Fe 2+ 、Co 2+ , Ga 2+ ,Ge 2+ , Sb 2+ and Al 3+ Preferably, the metal ion is Na + Mg 2+ and Cu 2+ One or more of .

[0011] According to another aspect of the present invention, a method for preparing a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde is provided, the method comprising the following steps: washing a styrene acid resin with an acid solution to obtain a first intermediate styrene resin; the styrene acid resin comprises at least one of the structures represented by formula (IV), formula (V) and formula (VI):

[0012]

[0013] The first intermediate styrene resin is subjected to a first water wash to obtain a second intermediate styrene resin; the second intermediate styrene resin is washed with an aqueous solution containing metal ions to obtain a third intermediate styrene resin; the third intermediate styrene resin is subjected to a second water wash to neutrality to obtain a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde.

[0014] Furthermore, the acid solution is one or more of an aqueous HCl solution, an HNO3 aqueous solution and an H3PO4 aqueous solution; preferably, the concentration of the acid solution is 0.1 to 10 mol / L; preferably, the concentration of the aqueous solution of metal ions is 0.01 to 1 mol / L; preferably, the rate at which the acid solution passes through the styrene acid resin is 1 to 5 BV / h; preferably, the rate at which the aqueous solution of metal ions passes through the second intermediate styrene resin is 0.5 to 5 BV / h.

[0015] According to the third aspect of the present invention, a method for preparing 3-hydroxypropionaldehyde by hydrating acrolein is also provided. The preparation method comprises hydrating acrolein and water under the catalytic action of the above-mentioned catalyst to obtain 3-hydroxypropionaldehyde.

[0016] Furthermore, the hydration reaction includes: preparing an extraction reaction device having an inner cavity, the inner cavity including a bottom extraction section, a reaction section and a top overflow section connected in sequence from bottom to top; wherein the reaction section is filled with a catalyst; feeding water from the upper part of the reaction section and feeding acrolein from the lower part of the reaction section, so that the water and acrolein are contacted and mixed in countercurrent, and then undergoing a hydration reaction under the action of the catalyst to obtain an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein; extracting the aqueous phase from the bottom extraction section to obtain 3-hydroxypropionaldehyde, and extracting the organic phase from the top overflow section; preferably, the aspect ratio of the reaction section is 2 to 50.

[0017] Furthermore, a condenser is connected above the overflow section at the top of the extraction reaction device, and the gas generated by the hydration reaction passes through the condenser and then is subjected to tail gas absorption.

[0018] Furthermore, the pH value of the acrolein hydration reaction system is 3.5 to 6.5.

[0019] Furthermore, the acrolein feed space velocity is 0.01 to 10 h -1 ; Preferably, the feed mass ratio of acrolein and water is (0.2-2):1.

[0020] Furthermore, the temperature of the hydration reaction is 20 to 80° C.; preferably, the pressure of the hydration reaction is 0.1 to 0.5 MPa.

[0021] The present invention mainly provides a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde, and its preparation method and application. The catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde proposed by the present invention includes a styrene acid resin matrix and metal ions bonded thereto, and the purpose of regulating the acidity of the reaction solution can be achieved by controlling the amount of bonded metal ions and controlling the acidity of the catalyst. The catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde described in the present invention can control the acidity in the reaction solution of preparing hydroxy aldehyde by hydration of olefinic aldehyde, and control the acidity of the system within an appropriate range. On the one hand, the generation of side reactions in the system can be reduced, and the selectivity of the hydration reaction can be improved; on the other hand, by controlling the acidity in the reaction solution, the loss of nickel and aluminum elements in the nickel-based catalyst caused by inappropriate acidity of the system in the subsequent hydrogenation reaction can be reduced, and the service life of the hydrogenation reaction catalyst can be extended, thereby further improving the product quality. In addition, the method of regulating the acidity in the reaction system by using a catalyst can avoid the problems of increasing the difficulty of subsequent separation caused by additional addition of organic acid to adjust the acidity or reducing the concentration of the reaction raw materials, and is suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0023] Figure 1 A schematic diagram of the extraction reaction device of the present invention is shown; wherein the above-mentioned figure includes the following figure marks: 1. tower bottom extraction section; 2. reaction section; 3. tower top overflow section; 4. condenser. DETAILED DESCRIPTION

[0024] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0025] As described in the background technology section, in the prior art, in the process of preparing hydroxy aldehyde by hydration of acrolein, the acidity of the acrolein hydration reaction liquid is generally controlled by adding an organic acid to the olefinic aldehyde hydration reaction system to improve the selectivity of the acrolein hydration reaction, reduce the occurrence of side reactions, and thus improve the selectivity of the synthesis; or by reducing the content of olefinic aldehyde in the reaction liquid to 15-20%, the selectivity of the acrolein synthesis reaction is improved. In the above two improved methods, although the side reactions are reduced to a certain extent and the selectivity of the reaction is improved, the addition of organic acid and the reduction of the olefinic aldehyde content in the olefinic aldehyde hydration reaction system will lead to the problem of further reduction of the product content, which increases the difficulty and cost of subsequent separation.

[0026] In order to solve the above problems, the present invention provides a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde, the catalyst comprising a styrene acid resin matrix and a metal ion bonded thereto, the styrene acid resin matrix carries an acidic group, and the metal ion is combined with the acidic group; wherein the acidic group combined with the metal ion has at least one of the structures shown in formula (I), formula (II) and formula (III):

[0027]

[0028] X is a metal ion or H, and at least part of X in the catalyst is a metal ion; the content of the metal ion in the catalyst is 10 to 10000 ppm, the acid equivalent of the catalyst is 3.5 to 5.4 mmol / g, and the metal ion is selected from one or more of alkali metal ions, alkaline earth metal ions, transition metal ions and amphoteric metal ions.

[0029] The catalyst for preparing hydroxy aldehyde by hydration of enal provided by the present invention comprises a styrene acid resin matrix and a metal ion bonded thereto, wherein the styrene acid resin matrix carries an acidic group, and the metal ion is combined with the acidic group; wherein the acidic group combined with the metal ion has at least one of the structures shown in formula (I), formula (II) and formula (III): formula (I) is an aminocarboxylic acid styrene resin carrying -NHCH2COOH, formula (II) is an aminophosphoric acid styrene resin carrying -NHCH2PO3H2, and formula (III) is an aminosulfonic acid styrene resin carrying -NHSO3H. X is a metal ion or H, and at least part of X in the catalyst is a metal ion; the amount of metal ions bonded to the catalyst can be controlled to be 10 to 10000 ppm, and the acid equivalent of the catalyst can be controlled to be 3.5 to 5.4 mmol / g, so that when the catalyst is applied to the reaction of preparing hydroxy aldehyde by hydration of enal, the acidity of the reaction system can be controlled to be within a suitable range. On the one hand, the hydration of alkenal to prepare hydroxy aldehyde reaction under suitable acidity conditions is beneficial to reduce the generation of side reactions in the system, improve the selectivity of the product, and then improve the product yield. On the other hand, by controlling the acidity in the reaction solution, the subsequent hydrogenation reaction can be favorably affected, the loss of nickel and aluminum elements in the nickel-based catalyst in the subsequent hydrogenation reaction can be reduced, the service life of the hydrogenation reaction catalyst is extended, and the product quality is further improved. In addition, the method for regulating the acidity in the reaction system by using a catalyst can avoid the problems such as the increase in subsequent separation difficulty caused by the additional addition of organic acid to adjust the acidity, and the problem of the increase in separation difficulty caused by the further reduction of the content of the alkenal in the hydration reaction system, which is suitable for large-scale industrial production. The catalyst of the present invention selects a styrene acid resin matrix because styrene is widely available, the polystyrene resin obtained after polymerization has a stable structure and is easy to modify, and the styrene acid resin matrix carries a styrene resin having at least one acidic group selected from -NHCH2COOH (as shown in Formula I), -NHCH2PO3H2 (as shown in Formula II) and -NHSO3H (as shown in Formula III). The above three groups can provide acidic protons. By controlling the metal loading of the above three groups, the acidity can be controlled, thereby achieving the purpose of regulating and controlling the properties of the catalyst.

[0030] In summary, the catalyst for preparing hydroxy aldehydes by hydration of enal according to the present invention can achieve effective control of the acidity of the reaction solution for preparing hydroxy aldehydes by hydration of enal, can improve the selectivity of the product and reduce the occurrence of side reactions, improve the product quality, and is also conducive to subsequent separation and purification, and is suitable for large-scale industrial production.

[0031] In a preferred embodiment, the content of metal ions in the catalyst is 500-8000 ppm, the acid equivalent of the catalyst is 4-5 mmol / g, and the metal ion is Na + Mg2+ , Cu 2+ 、Zn 2+ , K + , Ca 2+ , Sr 2+ , Ba 2+ , Fe 2+ 、Co 2+ , Ga 2+ ,Ge 2 + , Sb 2+ and Al 3+ One or more of; by optimizing the type and content of metal ions, controlling the content of metal ions in the catalyst and the acidity of the catalyst within the above range and making the metal ions bonded to the catalyst the above type, the performance of the catalyst is further improved, so that the obtained catalyst can control the acidity of the reaction solution within a more appropriate range, further improving the selectivity and yield of the hydroxyaldehyde preparation reaction system by hydration of olefinic aldehydes. Preferably, the metal ion is Na + Mg 2+ and Cu 2+ When the metal element bonded in the catalyst is one or more of Na, Mg and Cu, the above effect is better.

[0032] According to another aspect of the present invention, there is also provided a method for preparing a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehydes, the method comprising the following steps: washing a styrene acid resin with an acid solution to obtain a first intermediate styrene resin, wherein the styrene acid resin comprises at least one acidic group of the structure represented by formula (IV), formula (V) and formula (VI):

[0033]

[0034] The first intermediate styrene resin is subjected to a first water wash to obtain a second intermediate styrene resin; the second intermediate styrene resin is washed with an aqueous solution containing metal ions to obtain a third intermediate styrene resin; the third intermediate styrene resin is subjected to a second water wash to neutrality to obtain a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde.

[0035] In the above-mentioned method for preparing a catalyst for preparing hydroxy aldehyde by hydration of alkenal, firstly, the styrene acid resin is acid-washed with an acid solution so that the acidic groups on the styrene acid resin that do not exist as an acid can be fully converted; then the acidic solution attached to the styrene acid resin is eluted by a first water wash until the washed water becomes neutral; then the aqueous solution containing metal ions is further washed so that the metal ions can be bonded to the acidic groups on the styrene acid resin; finally, the excess metal ion solution attached to the styrene acid resin bonded with the metal ions is washed by water until the metal ion content in the washed water is ≤1ppm, and a catalyst for preparing hydroxy aldehyde by hydration of alkenal is obtained. The preparation method of the catalyst can achieve the purpose of effectively controlling the metal ion content and acidity of the catalyst. Moreover, the preparation method is simple and easy, low in cost, and the obtained catalyst has high activity, good stability and selectivity, is suitable for large-scale industrial production, and can effectively improve the efficiency of the alkenal hydration reaction and the economic benefits of the synthesis.

[0036] It should be further explained here that the aminocarboxylic acid styrene resin, aminophosphoric acid styrene resin or aminosulfonic acid styrene resin in the styrene acid resin are all commercially available, and the corresponding acidic group structures of the aminocarboxylic acid styrene resin, aminophosphoric acid styrene resin or aminosulfonic acid styrene resin are shown in Formula IV, Formula V and Formula VI respectively, which are known materials in the prior art.

[0037] In a preferred embodiment, the acid solution is one or more of HCl aqueous solution, HNO3 aqueous solution and H3PO4 aqueous solution; preferably, the concentration of the acid solution is 0.1-10 mol / L; preferably, the concentration of the aqueous solution of metal ions is 0.01-1 mol / L; preferably, the rate of the acid solution passing through the styrene acid resin is 1-5 BV / h; preferably, the rate of the metal ion aqueous solution passing through the second intermediate styrene resin is 0.5-5 BV / h; preferably, the rate of the first water wash is 1-5 BV / h. By controlling the concentrations of the acid solution and the metal ion aqueous solution within the above range, the activity and selectivity of the catalyst can be further adjusted within a more preferred range, so that the obtained catalyst can be suitable for different reaction conditions and olefinic aldehyde raw materials, providing flexible process options for chemical synthesis. The aqueous solution containing metal ions can be any soluble salt corresponding to the metal ions, preferably chlorides and bases containing corresponding metal ions. Preferably, the amount of the acid solution used in the pickling process is 1 to 10 times the volume of the styrene acid resin by volume ratio; by controlling the amount of acid used in the pickling process within the above range, the acidic groups in the styrene acid resin can all exist in the form of hydrogen ions. Preferably, the rate of the first water washing is 1 to 5 BV / h.

[0038] According to a third aspect of the present invention, a method for preparing 3-hydroxypropanal by hydration of acrolein is also provided, in which acrolein and water are subjected to a hydration reaction under the catalytic action of the above-mentioned catalyst to obtain 3-hydroxypropanal. The preparation method not only improves the synthetic selectivity and yield of 3-hydroxypropanal, but also the use of the catalyst makes the reaction more efficient, reduces energy consumption and environmental pollution, and is suitable for green chemistry and sustainable industrial production.

[0039] In a preferred embodiment, the hydration reaction comprises: preparing an extraction reaction device having an inner cavity, the inner cavity comprising a tower bottom extraction section, a reaction section and a tower top overflow section which are connected in sequence from bottom to top; wherein the reaction section is filled with a catalyst; feeding water from the upper part of the reaction section and feeding acrolein from the lower part of the reaction section, making the water and acrolein contact and mix in countercurrent, and then carrying out a hydration reaction under the action of the catalyst to obtain a water phase containing 3-hydroxypropanal and an organic phase of unreacted acrolein; extracting the water phase from the tower bottom extraction section to obtain 3-hydroxypropanal, and extracting the organic phase from the tower top overflow section. Preferably, the aspect ratio of the reaction section is 2 to 50, and controlling the aspect ratio within the above range is conducive to further improving the conversion rate of the reaction and the recovery rate of the product.

[0040] When the reaction of preparing 3-hydroxypropionaldehyde by hydration of acrolein according to the present invention is carried out in the above-mentioned device, water is fed from the upper part of the reaction section, and acrolein is fed from the lower part of the reaction section, and water and acrolein are contacted and mixed in countercurrent, and then a hydration reaction is carried out under the action of a catalyst to obtain an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein; the unreacted acrolein in the system will be separated from the aqueous phase due to its solubility in water (the solubility of acrolein in water is about 20%), and then the aqueous phase can be extracted from the extraction section of the tower bottom to obtain 3-hydroxypropionaldehyde, and the organic phase can be extracted from the overflow section of the tower top. The reaction of preparing 3-hydroxypropionaldehyde by hydration of acrolein using the extraction reaction device can, on the one hand, make the acidity of the reaction system within a suitable range, thereby reducing the generation of side reactions in the system, improving the selectivity and yield of the product, and at the same time, it is also beneficial to the stability and life of the catalyst in the subsequent hydrogenation reaction; it also avoids the problem of increased difficulty in subsequent separation caused by additional addition of organic acid to adjust the acidity. On the other hand, the dynamic properties of the reaction system can increase the concentration of 3-hydroxypropanal in the aqueous phase, and the unreacted acrolein can be separated from the system in time, further reducing the cost of subsequent separation processes, while also avoiding the generation of by-products. In addition, the reaction device is reasonably designed and easy to operate, and can effectively separate the product and the unreacted raw material, thereby improving the conversion rate of the reaction and the recovery rate of the product, being suitable for continuous production, and greatly improving the production efficiency and economic benefits.

[0041] In a preferred embodiment, a condenser is also connected above the overflow section at the top of the extraction reaction device, and the gas generated by the hydration reaction passes through the condenser for tail gas absorption. By providing a condenser, the steam and unreacted acrolein generated during the reaction can be effectively recovered, reducing the waste of raw materials. At the same time, the tail gas absorption device can treat the harmful gases generated by the reaction, protect the environment, and comply with the concepts of green chemistry and sustainable development.

[0042] Preferably, if Figure 1 As shown, the extraction reaction device has an inner cavity, which includes a tower bottom extraction section 1, a reaction section 2 and a tower top overflow section 3 which are connected in sequence from bottom to top, and the reaction section 2 is filled with a catalyst. In the specific reaction process, the reaction raw material water A enters from the upper part of the reaction section 2, and the reaction raw material acrolein B enters from the lower part of the reaction section 2, and the water A and acrolein B are contacted and mixed in countercurrent, and then a hydration reaction is carried out under the action of the catalyst in the reaction section 2 to obtain a water phase containing 3-hydroxypropanal and an organic phase of unreacted acrolein; the water phase is extracted from the tower bottom extraction section 1 to obtain the 3-hydroxypropanal C, and the organic phase is extracted from the tower top overflow section to obtain unreacted acrolein B. Preferably, a condenser 4 is also connected above the tower top overflow section 3 of the extraction reaction device, and the gas D generated by the hydration reaction is further processed after passing through the condenser.

[0043] In a preferred embodiment, the pH value in the acrolein hydration reaction system is 3.5 to 6.5. By controlling the pH value of the reaction system within the above range, the activity and selectivity of the catalyst can be further optimized, the yield of 3-hydroxypropanal can be increased, and the generation of by-products can be reduced.

[0044] In a preferred embodiment, the acrolein feed space velocity is 0.01 to 10 h -1 ; Preferably, the feed mass ratio of acrolein to water is (0.2-2):1. By controlling the feed space velocity of acrolein and the feed mass ratio of acrolein to water within the above range, the reaction can be carried out more fully, the selectivity and yield of the reaction can be further improved, and the 3-hydroxypropanal extracted from the overflow section at the top of the tower can have a higher concentration, which is conducive to subsequent separation.

[0045] In a preferred embodiment, the temperature of the hydration reaction is 20 to 80° C.; preferably, the pressure of the hydration reaction is 0.1 to 0.5 MPa. Controlling the reaction time and the reaction temperature of the hydration of acrolein to prepare 3-hydroxypropionaldehyde within the above range can make the reaction more complete, which is beneficial to improving the yield of 3-hydroxypropionaldehyde.

[0046] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0047] In order to further understand the scheme of the present invention, it is necessary to further explain here that the extraction reaction device used in the process of preparing 3-hydroxypropanal in the present invention is the extraction reaction device in the accompanying drawings of the present invention. Figure 1 The device of the structure shown in the figure, the aminocarboxylic acid styrene resin, aminophosphoric acid styrene resin and aminosulfonic acid styrene resin used in the preparation of the catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde are all purchased from Xi'an Lanxiao Technology Co., Ltd.

[0048] Example 1

[0049] 100 mL of aminocarboxylic acid styrene resin is placed in an exchange column, and 600 mL of 1 mol / L HCl aqueous solution is pumped into the catalyst bed containing the aminocarboxylic acid styrene resin for acid washing, wherein the rate of the HCl aqueous solution is 1 BV / h; after the acid washing is completed, water is pumped into it again for the first water washing; after the water washing is completed, 43.5 mL of 0.01 mol / L NaOH aqueous solution is pumped into the catalyst bed of the washed aminocarboxylic acid styrene resin for washing and replacement, wherein the rate of the NaOH aqueous solution is 0.5 BV / h, after the metal ion exchange is completed, water is pumped into it again for the second water washing to neutrality, and a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde is obtained. The metal ion content in the obtained catalyst is 100 ppm, and the acid equivalent is 5.3 mmol / g.

[0050] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 20 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 20 g / h, and the mass space velocity of acrolein feeding was 0.2 h -1 ; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 45° C. and the pressure is 0.1 MPa, to obtain an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0051] Example 2

[0052] 100mL of aminophosphoric acid styrene resin is placed in an exchange column, and 600mL of 1mol / L HCl aqueous solution is pumped into the catalyst bed containing aminophosphoric acid styrene resin for pickling, wherein the rate of the HCl aqueous solution is 2BV / h; after the pickling is completed, water is pumped into it again for the first water washing; after the water washing is completed, 415mL of 0.01mol / L MgCl2 aqueous solution is pumped into the catalyst bed of the washed aminophosphoric acid styrene resin for washing and replacement, wherein the rate of the MgCl2 aqueous solution is 1BV / h, after the metal ion exchange is completed, water is pumped into it again for the second water washing to neutrality, and a catalyst for preparing hydroxy aldehyde by hydration of alkenal is obtained. Wherein, the metal ion content in the obtained catalyst is 1000ppm, and the acid equivalent is 4.9mmol / g.

[0053] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 20 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 30 g / h and acrolein feeding space velocity of 0.3 h -1 ; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 35° C. and the pressure is 0.1 MPa; an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein are obtained; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0054] Example 3

[0055] 100 mL of aminosulfonic acid styrene resin is placed in an exchange column, and 400 mL of 2 mol / L HCl aqueous solution is pumped into the catalyst bed containing the aminosulfonic acid styrene resin for acid washing, wherein the rate of the HCl aqueous solution is 2 V / h; after the acid washing is completed, water is pumped into it again for the first water washing; after the water washing is completed, 780 mL of 0.01 mol / L CuCl2 aqueous solution is pumped into the catalyst bed of the washed aminosulfonic acid styrene resin for washing and replacement, wherein the rate of the CuCl2 aqueous solution is 1 BV / h, after the metal ion exchange is completed, water is pumped into it again for the second water washing to neutrality, and a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde is obtained. The metal ion content in the obtained catalyst is 5000 ppm, and the acid equivalent is 4.2 mmol / g.

[0056] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 20 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 10 g / h and acrolein feeding space velocity of 0.1 h -1; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 55° C. and the pressure is 0.3 MPa; an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein are obtained; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0057] Example 4

[0058] 100 mL of aminocarboxylic acid styrene resin is placed in an exchange column, and 600 mL of 1 mol / L HCl aqueous solution is pumped into the catalyst bed containing the aminocarboxylic acid styrene resin for acid washing, wherein the rate of the HCl aqueous solution is 1 BV / h; after the acid washing is completed, water is pumped into it again for the first water washing; after the water washing is completed, 5 mL of 0.01 mol / L NaOH aqueous solution is pumped into the catalyst bed of the washed aminocarboxylic acid styrene resin for washing and replacement, wherein the rate of the NaOH aqueous solution is 0.5 BV / h, after the metal ion exchange is completed, water is pumped into it again for the second water washing to neutrality, and a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde is obtained. The metal ion content in the obtained catalyst is 10 ppm, and the acid equivalent is 5.4 mmol / g.

[0059] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 20 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 20 g / h, and the mass space velocity of acrolein feeding was 0.2 h -1 ; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 45° C. and the pressure is 0.1 MPa, to obtain an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0060] Example 5

[0061] 100 mL of aminocarboxylic acid styrene resin is placed in an exchange column, and 600 mL of 1 mol / L HCl aqueous solution is pumped into the catalyst bed containing the aminocarboxylic acid styrene resin for acid washing, wherein the rate of the HCl aqueous solution is 1 BV / h; after the acid washing is completed, water is pumped into it again for the first water washing; after the water washing is completed, 435 mL of 0.1 mol / L NaOH aqueous solution is pumped into the catalyst bed of the washed aminocarboxylic acid styrene resin for washing and replacement, wherein the rate of the NaOH aqueous solution is 0.5 BV / h, after the metal ion exchange is completed, water is pumped into it again for the second water washing to neutrality, and a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde is obtained. The metal ion content in the obtained catalyst is 10000 ppm, and the acid equivalent is 3.5 mmol / g.

[0062] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 20 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 20 g / h, and the mass space velocity of acrolein feeding was 0.2 h -1 ; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 45° C. and the pressure is 0.1 MPa, to obtain an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0063] Example 6

[0064] 100 mL of aminocarboxylic acid styrene resin is placed in an exchange column, and 600 mL of 1 mol / L HCl aqueous solution is pumped into the catalyst bed containing the aminocarboxylic acid styrene resin for acid washing, wherein the rate of the HCl aqueous solution is 1 BV / h; after the acid washing is completed, water is pumped into it again for the first water washing; after the water washing is completed, 218 mL of 0.01 mol / L NaOH aqueous solution is pumped into the catalyst bed of the washed aminocarboxylic acid styrene resin for washing and replacement, wherein the rate of the NaOH aqueous solution is 0.5 BV / h, after the metal ion exchange is completed, water is pumped into it again for the second water washing to neutrality, and a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde is obtained. The metal ion content in the obtained catalyst is 500 ppm, and the acid equivalent is 5.0 mmol / g.

[0065] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 20 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 20 g / h, and the mass space velocity of acrolein feeding was 0.2 h -1; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 45° C. and the pressure is 0.1 MPa, to obtain an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0066] Example 7

[0067] 100 mL of aminocarboxylic acid styrene resin is placed in an exchange column, and 600 mL of 1 mol / L HCl aqueous solution is pumped into the catalyst bed containing the aminocarboxylic acid styrene resin for acid washing, wherein the rate of the HCl aqueous solution is 1 BV / h; after the acid washing is completed, water is pumped into it again for the first water washing; after the water washing is completed, 180 mL of 0.05 mol / L NaOH aqueous solution is pumped into the catalyst bed of the washed aminocarboxylic acid styrene resin for washing and replacement, wherein the rate of the NaOH aqueous solution is 0.5 BV / h, after the metal ion exchange is completed, water is pumped into it again for the second water washing to neutrality, and a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde is obtained. The metal ion content in the obtained catalyst is 2000 ppm, and the acid equivalent is 4.5 mmol / g.

[0068] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 20 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 20 g / h, and the mass space velocity of acrolein feeding was 0.2 h -1 ; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 45° C. and the pressure is 0.1 MPa, to obtain an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0069] Example 8

[0070] 100mL of aminophosphoric acid styrene resin is placed in an exchange column, and 100mL of 10mol / L HNO3 aqueous solution is pumped into the catalyst bed with aminophosphoric acid styrene resin for pickling, wherein the rate of the HNO3 aqueous solution is 1BV / h; after the pickling is completed, water is pumped into it again for the first water washing; after the water washing is completed, 930mL of 0.01mol / L MgCl2 aqueous solution is pumped into the catalyst bed of the washed aminophosphoric acid styrene resin for washing and replacement, wherein the rate of the MgCl2 aqueous solution is 0.5BV / h, after the metal ion exchange is completed, water is pumped into it again for the second water washing to neutrality, and a catalyst for preparing hydroxy aldehyde by hydration of alkenal is obtained. Wherein, the metal ion content in the obtained catalyst is 2000ppm, and the acid equivalent is 4.6mol / g.

[0071] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 20 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 30 g / h and acrolein feeding space velocity of 0.3 h -1 ; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 35° C. and the pressure is 0.1 MPa; an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein are obtained; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0072] Example 9

[0073] 100mL of aminophosphoric acid styrene resin is placed in an exchange column, and 1000mL of 0.1mol / L H3PO4 aqueous solution is pumped into the catalyst bed containing aminophosphoric acid styrene resin for pickling, wherein the rate of the H3PO4 aqueous solution is 5BV / h; after the pickling is completed, water is pumped into it again for the first water washing; after the water washing is completed, 34mL of 1mol / L MgCl2 aqueous solution is pumped into the catalyst bed of the washed aminophosphoric acid styrene resin for washing and replacement, wherein the rate of the MgCl2 aqueous solution is 5BV / h, after the metal ion exchange is completed, water is pumped into it again for the second water washing to neutrality, and a catalyst for preparing hydroxy aldehyde by hydration of alkenal is obtained. Wherein, the metal ion content in the obtained catalyst is 8000ppm, and the acid equivalent is 4.0mmol / g.

[0074] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 20 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 30 g / h and acrolein feeding space velocity of 0.3 h -1; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 35° C. and the pressure is 0.1 MPa; an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein are obtained; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0075] Example 10

[0076] The catalyst used in the preparation of 3-hydroxypropanal in Example 10 is the catalyst for preparing hydroxy aldehyde by hydrating the olefinic aldehyde obtained in Example 3.

[0077] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 5 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 1 g / h and acrolein feeding space velocity of 0.01 h -1 ; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 20° C. and the pressure is 0.1 MPa; an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein are obtained; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0078] Embodiment 11

[0079] The catalyst used in the preparation of 3-hydroxypropanal in Example 11 is the catalyst for preparing hydroxy aldehyde by hydrating the olefinic aldehyde obtained in Example 3.

[0080] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 500 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 1000 g / h and acrolein feeding space velocity of 10 h -1 ; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 80° C. and the pressure is 0.5 MPa; an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein are obtained; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section at the top of the tower.

[0081] Comparative Example 1

[0082] The aminocarboxylic acid styrene acid resin was loaded in a fixed bed, and a 15% acrolein aqueous solution was heated at 0.05 h. -1A mass space velocity of 3-hydroxypropionaldehyde was passed therein, and a hydration reaction was carried out at 55° C. under the action of the catalyst to obtain a reaction solution containing 3-hydroxypropionaldehyde, the concentration of 3-hydroxypropionaldehyde in the reaction solution was 8.7%, the pH value was 3.0, and the catalyst acid equivalent was 5.5 mmol / g.

[0083] Comparative Example 2

[0084] 100 mL of aminocarboxylic acid styrene resin is placed in an exchange column, and 300 mL of 0.1 mol / L HCl aqueous solution is pumped into the catalyst bed containing the aminocarboxylic acid styrene resin for acid washing, wherein the rate of the HCl aqueous solution is 1 BV / h; after the acid washing is completed, water is pumped into the catalyst bed containing the aminocarboxylic acid styrene resin for first water washing; after the water washing is completed, 870 mL of 0.01 mol / L NaOH aqueous solution is pumped into the catalyst bed containing the aminocarboxylic acid styrene resin for washing and replacement, wherein the rate of the NaOH aqueous solution is 0.5 BV / h, and after the metal ion exchange is completed, water is pumped into the catalyst bed for second water washing to neutrality to obtain a catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde. The metal ion content in the obtained catalyst is 20000 ppm, and the acid equivalent is 2.5 mmol / g.

[0085] The catalyst prepared above was filled into the reaction section of the extraction reaction device. Water was fed from the upper part of the reaction section at a water feeding rate of 20 g / h; acrolein was fed from the lower part of the reaction section at a feeding rate of 30 g / h and acrolein feeding space velocity of 0.3 h -1 ; Water and acrolein are contacted and mixed in countercurrent in the reaction section, and a hydration reaction is carried out under the action of a catalyst, wherein the temperature of the hydration reaction is 35° C. and the pressure is 0.1 MPa; an aqueous phase containing 3-hydroxypropionaldehyde and an organic phase of unreacted acrolein are obtained; the aqueous phase containing 3-hydroxypropionaldehyde is extracted from the extraction section of the bottom of the tower, and the organic phase of unreacted acrolein is extracted from the overflow section of the top of the tower.

[0086] Comparative Example 3

[0087] 100g of 15% acrolein aqueous solution was put into a 250mL reaction bottle, 10g of styrylaminophosphoric acid was added as a catalyst, and the reaction was stirred at 50°C for 4h. After the reaction, a sample of the reaction liquid was taken and analyzed. The acrolein conversion rate was 55.3%, the selectivity of 3-hydroxypropanal was 83.5%, the concentration of 3-hydroxypropanal in the reaction liquid was 9.1%, and the pH of the reaction liquid was 3.1.

[0088] The relevant data in the above examples and comparative examples were recorded and tested, and the results were compiled in Table 1. Among them, the test methods and meanings of the data in the table are further explained as follows:

[0089] pH of the hydration reaction solution: obtained by testing the reaction solution sample collected after 4 hours of reaction using a Mettler Toledo pH meter;

[0090] Hydration reaction 3-hydroxypropionaldehyde content: It is tested by gas chromatography method, which can reflect the concentration of 3-hydroxypropionaldehyde in the hydration reaction solution;

[0091] Conversion rate: Acrolein conversion rate = (acrolein feed mass × acrolein content - tower top material mass × acrolein content - tower bottom material mass × acrolein content) / (acrolein feed mass × acrolein content);

[0092] 3-hydroxypropionaldehyde selectivity: 3-hydroxypropionaldehyde selectivity = (mass of material withdrawn from the bottom of the tower × content of 3-hydroxypropionaldehyde / 74 + mass of material withdrawn from the top of the tower × content of 3-hydroxypropionaldehyde / 74) / (mass of acrolein feed × content of acrolein / 56 - mass of material withdrawn from the top of the tower × content of acrolein / 56 - mass of material withdrawn from the bottom of the tower × content of acrolein / 56).

[0093] Table 1

[0094]

[0095]

[0096] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0097] In Examples 1 to 11 of the present invention, the catalyst for preparing hydroxy aldehyde by hydrating olefinic aldehyde prepared by the preparation method of the present invention is used to prepare hydroxy aldehyde by controlling the acid equivalent and metal ion content of the catalyst within the range described in the present application, so that the acidity of the obtained hydration reaction liquid can be suitable, and the purpose of improving the conversion rate of acrolein and the selectivity of 3-hydroxypropionaldehyde can be achieved. The selectivity of 3-hydroxypropionaldehyde in the above examples is above 90%. However, in Comparative Example 1, conventional unmodified aminocarboxylic acid styrene acid resin is used, and a fixed bed is used for reaction, and the pH of the reaction liquid of 3-hydroxypropionaldehyde obtained is low, and the conversion rate of acrolein and the selectivity of 3-hydroxypropionaldehyde are also low. The acid equivalent in the catalyst for preparing hydroxy aldehyde by hydrating olefinic aldehyde used in Comparative Example 2 is low, resulting in insufficient acidity in the reaction system, and the purpose of improving the conversion rate and selectivity of the hydration reaction cannot be achieved, and the conversion rate of acrolein and the selectivity of 3-hydroxypropionaldehyde are not good. Comparative Example 3 uses unmodified styrylaminophosphoric acid as a catalyst and uses a reactor as a reaction vessel for the reaction. The acidity of the system, the conversion rate of acrolein and the selectivity of 3-hydroxypropionaldehyde are also relatively poor compared with the results in the examples of the present invention.

[0098] In summary, the use of the catalyst for preparing hydroxy aldehydes by hydration of olefinic aldehydes according to the present invention in combination with the preparation method according to the present invention can greatly improve the conversion rate of acrolein and the selectivity of 3-hydroxypropanal, and can also make the acidity of the hydration reaction liquid more suitable, which has many advantages.

[0099] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A catalyst for preparing hydroxy aldehydes by hydration of olefinic aldehydes, characterized in that: The catalyst comprises a styrene acid resin matrix and a metal ion bonded thereto, wherein the styrene acid resin matrix carries an acidic group, and the metal ion is combined with the acidic group; wherein the acidic group combined with the metal ion has at least one of the structures shown in formula (I), formula (II) and formula (III): wherein X is the metal ion or H, and at least part of X in the catalyst is the metal ion; The content of the metal ions in the catalyst is 10 to 10000 ppm, the acid equivalent of the catalyst is 3.5 to 5.4 mmol / g, and the metal ions are selected from one or more of alkali metal ions, alkaline earth metal ions, transition metal ions and amphoteric metal ions.

2. The catalyst for preparing hydroxy aldehydes by hydration of olefinic aldehydes according to claim 1, characterized in that The content of the metal ion in the catalyst is 500 to 8000 ppm, the acid equivalent of the catalyst is 4 to 5 mmol / g, and the metal ion is Na + Mg 2+ , Cu 2+ 、Zn 2+ , K + , Ca 2+ , Sr 2+ , Ba 2+ , Fe 2+ 、Co 2+ , Ga 2+ ,Ge 2+ , Sb 2+ and Al 3+ One or more of; Preferably, the metal ion is Na + Mg 2+ and Cu 2+ One or more of .

3. A method for preparing a catalyst for preparing hydroxy aldehydes by hydration of olefinic aldehydes according to claim 1 or 2, characterized in that: The preparation method comprises the following steps: The styrene acid resin is acid-washed with an acid solution to obtain a first intermediate styrene resin; the styrene acid resin includes at least one acidic group of the structure represented by formula (IV), formula (V) and formula (VI): The first intermediate styrene resin is subjected to a first water washing to obtain a second intermediate styrene resin; washing the second intermediate styrene resin with an aqueous solution containing the metal ions to obtain a third intermediate styrene resin; The third intermediate styrene resin is subjected to a second water wash to be neutralized to obtain the catalyst for preparing hydroxy aldehyde by hydration of olefinic aldehyde.

4. The method for preparing a catalyst for preparing hydroxy aldehydes by hydration of olefinic aldehydes according to claim 3, characterized in that: The acid solution is one or more of HCl aqueous solution, HNO3 aqueous solution and H3PO4 aqueous solution; Preferably, the concentration of the acid solution is 0.1 to 10 mol / L; Preferably, the concentration of the aqueous solution of metal ions is 0.01 to 1 mol / L; Preferably, the rate at which the acid solution passes through the styrene acid resin is 1 to 5 BV / h; Preferably, the rate at which the aqueous metal ion solution passes through the second intermediate styrene resin is 0.5 to 5 BV / h.

5. A method for preparing 3-hydroxypropionaldehyde by hydrating acrolein, characterized in that: Under the catalytic action of the catalyst described in claim 1 or 2, acrolein and water are subjected to a hydration reaction to obtain the 3-hydroxypropionaldehyde.

6. The method for preparing 3-hydroxypropionaldehyde by hydrating acrolein according to claim 5, characterized in that: The hydration reaction comprises: An extraction reaction device is prepared, which has an inner cavity, wherein the inner cavity includes a tower bottom extraction section, a reaction section and a tower top overflow section which are connected in sequence from bottom to top; wherein the reaction section is filled with the catalyst; The water is fed from the upper part of the reaction section, and the acrolein is fed from the lower part of the reaction section, so that the water and the acrolein are contacted and mixed in countercurrent, and the hydration reaction is carried out under the action of the catalyst to obtain a water phase containing the 3-hydroxypropanal and an organic phase of unreacted acrolein; Extract the aqueous phase from the tower bottom extraction section to obtain the 3-hydroxypropanal, and extract the organic phase from the tower top overflow section; Preferably, the aspect ratio of the reaction section is 2-50.

7. The method for preparing 3-hydroxypropionaldehyde by hydrating acrolein according to claim 6, characterized in that: A condenser is also connected above the overflow section at the top of the extraction reaction device, and the gas generated by the hydration reaction passes through the condenser for tail gas absorption.

8. The method for preparing 3-hydroxypropionaldehyde by hydrating acrolein according to any one of claims 5 to 7, characterized in that: The pH value of the acrolein hydration reaction system is 3.5 to 6.

5.

9. The method for preparing 3-hydroxypropionaldehyde by hydrating acrolein according to any one of claims 5 to 7, characterized in that: The acrolein feed space velocity is 0.01 to 10 h -1 ; Preferably, the feed mass ratio of the acrolein to the water is (0.2-2):

1.

10. The method for preparing 3-hydroxypropionaldehyde by hydrating acrolein according to any one of claims 5 to 7, characterized in that: The temperature of the hydration reaction is 20 to 80°C; Preferably, the pressure of the hydration reaction is 0.1-0.5 MPa.

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