Phase transfer enrichment functional catalyst for preparing 3-hydroxypropionaldehyde by hydration reaction of propenal and preparation method and application thereof

Abstract

The application discloses a phase transfer enrichment functional catalyst for preparing 3-hydroxypropionaldehyde through a propenal hydration reaction, and a preparation method and application thereof, and relates to the technical field of catalysts. In the application, macroporous styrene resin is used as a carrier, a dichlorine-containing active site intermediate is introduced through a Friedel-Crafts phosphorylation reaction of phosphorus oxychloride with the surface of the resin, and then an organic long-chain and a phosphoric acid hydroxyl functional group are respectively introduced through step-by-step esterification and hydrolysis reaction, so that a microenvironment catalytic system with synergistic action of an organic long-chain and an acid center is constructed, and the conversion rate and selectivity of the propenal hydration reaction are improved.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a phase transfer enrichment functional catalyst for the preparation of 3-hydroxypropional by the hydration reaction of acrolein, its preparation method, and its application. Background Technology

[0002] 3-Hydroxypropanal (3-HPA) is a key intermediate in the synthesis of 1,3-propanediol (1,3-PDO) and has a huge market demand. Currently, the main chemical route for the industrial production of 3-HPA is the acid-catalyzed hydration of acrolein, in which solid resin acid catalysts have been extensively studied and applied. This process has advantages such as mild reaction conditions and a wide range of raw material sources. However, in actual production, the reaction is limited by thermodynamic equilibrium, and it is often difficult to simultaneously achieve both high conversion rate and product selectivity: increasing the acidity to improve the conversion rate of acrolein will exacerbate side reactions such as acrolein polymerization and 3-HPA polycondensation; decreasing the acidity of the catalyst to suppress side reactions will lead to a severe decrease in conversion rate. Therefore, simply changing the acidity of the catalyst through conventional methods has significant limitations in the process of hydrating acrolein to produce 3-hydroxypropanal.

[0003] To address the aforementioned issues, acid-base synergistic catalytic modification of the catalyst surface is currently recognized as an effective method in the industry. This involves introducing basic centers onto the resin surface to enhance the nucleophilicity of water molecules, thereby achieving synergistic catalysis. For example, Chinese invention patent CN1830559A discloses a novel resin catalyst for the hydration of acrolein to 3-hydroxypropionaldehyde and its application, using styrene-divinylbenzene as a matrix and obtaining an acid-base synergistic resin catalyst with thiodiacetic acid functional groups on its surface through modification; Chinese invention patent CN1580024A discloses a method for the hydration of acrolein to prepare 3-hydroxypropionaldehyde, using a weakly acidic chelating cation exchange resin as a catalyst, anchoring diacetic acid or thiodiacetic acid as active centers on its surface for acid-base synergistic catalysis; and Chinese invention patent CN1170802C discloses a method for preparing 3-hydroxypropionaldehyde, also using an ion exchange resin with nitrogen-carboxylic acid on its surface for catalytic acrolein hydration. However, there are still many problems with enhancing the nucleophilicity of water molecules solely through acid-base synergistic catalysis. For example, at high concentrations, acrolein raw materials are still prone to polymerization and covering of carboxylic acid active sites on the resin surface, leading to catalyst deactivation. When the concentration of acrolein raw materials is low, using a stronger acid catalyst to improve the conversion rate will intensify acrolein polymerization. At the same time, the product 3-hydroxypropionaldehyde cannot be removed from the resin surface in time, and is prone to deep polymerization, thereby reducing selectivity.

[0004] In summary, existing acid-base co-catalyzing hydration resins mostly enhance the nucleophilicity of water molecules to lower the activation energy of the reaction, failing to specifically inhibit catalyst deactivation caused by the polymerization of raw materials and products. To meet the comprehensive requirements of acrolein hydration for both acidic active centers and inhibition of product side reactions, it is necessary to develop a novel resin catalyst that simultaneously possesses acidic centers and inhibits product accumulation. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a phase transfer enrichment functional catalyst for the preparation of 3-hydroxypropional by acrolein hydration reaction, its preparation method and application. Through esterification and hydrolysis reactions, an organophilic long chain and a phosphate hydroxyl functional group are introduced on the resin surface to construct a microenvironmental catalytic system with synergistic effect of organophilic side chain and acidic center.

[0006] The technical solution of this invention is as follows:

[0007] In a first aspect, the present invention provides a method for preparing a phase transfer enrichment functional catalyst for the acrolein hydration reaction to prepare 3-hydroxypropional, comprising the following steps:

[0008] Introduction of S1 dual active sites: In a dry aprotic solvent, using macroporous styrene resin as a support and phosphorus oxychloride as a phosphorylating agent, a Friedel-Crafts phosphorylation reaction occurs via electrophilic substitution of the aromatic ring under the action of a Lewis acid catalyst, generating a resin intermediate containing dichlorophosphoryl groups (-POCl2) on its surface; the amount of phosphorus oxychloride added is 0.03~0.05 mol / g macroporous styrene resin; the reaction process is as follows:

[0009] ;

[0010] S2 Organophilic Modification: A resin intermediate containing dichlorophosphoryl groups undergoes a monophilic nucleophilic substitution reaction with a fatty alcohol in an organic solvent under the catalysis of an acid-binding agent. One of the P-Cl bonds is esterified, introducing an organophilic long fatty chain onto the phosphorus atom, yielding an intermediate resin containing organophilic side chains. The molar ratio of fatty alcohol to phosphorus oxychloride is (0.85~0.95):1. The reaction process is as follows:

[0011] ;

[0012] S3 hydrolysis and acidification: An intermediate resin containing an organophilic side chain is hydrolyzed to convert the remaining P-Cl groups into catalytically active phosphate hydroxyl structures. After washing and drying, a phase transfer enrichment catalyst is obtained. The reaction process is as follows:

[0013] .

[0014] Preferably, in step S1, the macroporous styrene resin is pretreated before use: the macroporous styrene resin is washed with deionized water to remove free salts and impurities until the eluent is neutral, filtered, and dried to constant weight. The dried macroporous styrene resin is then added to dry dichloromethane and stirred to swell, and filtered to obtain swollen resin. During pretreatment, the drying temperature is 60~80℃, the drying time is 12~24h, and the stirring and swelling time is 12~18h.

[0015] Preferably, step S1 is specifically operated as follows: dissolve the Lewis acid catalyst in a dry aprotic solvent, then add phosphorus oxychloride and mix thoroughly to form a complex solution; add pre-swollen macroporous styrene resin to the complex solution and stir to carry out the phosphorylation reaction; after the reaction is completed, filter, and wash and filter the obtained resin with dry dichloromethane until the residual Lewis acid catalyst and phosphorus oxychloride are removed.

[0016] Preferably, the aprotic solvent is dichloromethane, 1,2-dichloroethane, or nitrobenzene, and the addition amount is 5~15 mL / g macroporous styrene resin; the Lewis acid catalyst is aluminum trichloride, ferric trichloride, or zinc chloride, and the addition amount is 0.003~0.005 mol / g macroporous styrene resin; the phosphorylation reaction temperature is 20~40℃, and the reaction time is 6~10 h.

[0017] Preferably, the specific operation of step S2 is as follows: the resin intermediate containing dichlorophosphoryl group obtained in step S1 is added to a dry organic solvent, stirred at -5~5℃ and fatty alcohol and acid-binding agent are added in sequence for reaction, the reaction time is 4~10h; after the reaction is completed, the intermediate resin containing organic side chain is obtained by filtration, and the filter is washed with dry dichloromethane to remove residual reagents and by-product salts.

[0018] Preferably, the fatty alcohol is a C6-C12 straight-chain alkyl alcohol; the acid binder is triethylamine, pyridine, or anhydrous sodium carbonate, and the molar ratio of the acid binder to the fatty alcohol is (1-1.1):1; the organic solvent is acetonitrile, and the amount added is 10-30 mL / g macroporous styrene resin.

[0019] Preferably, the specific operation of step S3 is as follows: the intermediate resin containing the organic side chain obtained in step S2 is added to a dilute hydrochloric acid solution, heated and stirred to carry out a hydrolysis reaction, so that the residual P-Cl bond is converted into a P-OH structure; after the reaction is completed, it is filtered, washed with deionized water until the eluent is neutral, and then vacuum dried to constant weight to obtain the phase transfer enrichment functional catalyst.

[0020] Preferably, the concentration of the dilute hydrochloric acid solution is 5~10 wt.%, the amount of dilute hydrochloric acid solution added is 10~20 mL / g macroporous styrene resin; the hydrolysis reaction temperature is 40~60℃, the hydrolysis reaction time is 6~10 h; and the vacuum drying temperature is 60~80℃.

[0021] Secondly, the present invention provides a phase transfer enrichment functional catalyst for the preparation of 3-hydroxypropanal by the acrolein hydration reaction, which is prepared by the above-described preparation method of the phase transfer enrichment functional catalyst for the preparation of 3-hydroxypropanal by the acrolein hydration reaction.

[0022] In the phase-transfer enrichment functional catalyst of this invention, the introduced organophilic long chain forms an "organic affinity region" around the acidic site. Van der Waals forces induce acrolein molecules containing carbon-carbon double bonds to be directionally enriched towards the active center, increasing the local material concentration at the active site even at lower feed concentrations, thereby enhancing the reaction conversion rate. Simultaneously, because the product 3-hydroxypropionaldehyde is significantly more polar than the feed, the polar repulsion between it and the nonpolar long chain effectively weakens the hydrogen bond adsorption strength of the product at the phosphate site, causing it to rapidly detach from the active site and diffuse into the aqueous phase. This suppresses the continuous condensation side reactions between the product and the feed, improving reaction selectivity.

[0023] Thirdly, this invention provides the application of the aforementioned phase transfer enrichment functional catalyst for the preparation of 3-hydroxypropional via the hydration reaction of acrolein. The catalyst is packed into a fixed-bed reactor, with an 8-15 wt.% aqueous solution of acrolein as feed, and the reaction is carried out at 30-50°C and a liquid hourly space velocity (LHSV) of 0.5-1.5 h⁻¹. -1 Under certain conditions, the acrolein is continuously fed to induce a hydration reaction, thereby producing 3-hydroxypropionaldehyde.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] 1. In traditional hydrophilic acidic resin catalytic systems, the hydration reaction of acrolein, containing nonpolar double bonds, is affected by the mass transfer resistance of the aqueous film. This invention introduces long-chain alkyl groups at the molecular scale, altering the wettability of the active site region and forming an (organic affinity region) near the active site. This organic affinity improves the partition coefficient of nonpolar reactants on the catalyst surface at the microscopic level, achieving cross-scale transfer from macroscopically dilute solutions to microscopically localized high concentrations. By modifying and introducing long-chain alkyl groups, acrolein molecules in aqueous solution can be actively drawn towards the acidic center, thereby increasing the local reaction concentration and improving the reaction conversion rate.

[0026] 2. As a multifunctional compound, the product 3-HPA readily forms strong intermolecular hydrogen bonds with the acidic groups on the resin surface. This strong interaction prolongs the product's residence time at the active site, leading to a condensation reaction with acrolein in the raw material. This is the main kinetic cause of the continuous condensation side reaction. The organic-loving hydrophobic side chain group introduced in this invention alters the surface free energy, reducing the resin's adsorption of 3-HPA and giving the system the characteristics of "weak adsorption and rapid desorption." This forces the generated 3-HPA product to rapidly detach from the active site and enter the aqueous phase, suppressing side reactions and improving selectivity. Attached Figure Description

[0027] Figure 1 These are test graphs showing the conversion rate of acrolein hydration reaction of the catalysts prepared in Examples 1-5 and Comparative Examples 1-3 of this invention.

[0028] Figure 2 These are test graphs showing the selectivity of the acrolein hydration reaction of the catalysts prepared in Examples 1-5 and Comparative Examples 1-3 of this invention. Detailed Implementation

[0029] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention.

[0030] Example 1

[0031] The preparation method of the phase transfer enrichment functional catalyst for the acrolein hydration reaction to prepare 3-hydroxypropionaldehyde in this embodiment includes the following steps:

[0032] S1 dual active site introduction

[0033] Take 100g of commercially available LS1000 type macroporous styrene-based chelating ion exchange resin, place it in a Buchner funnel, wash and filter it with deionized water until the eluent is neutral, then place it in a forced-air drying oven at 70℃ for 18h to constant weight, obtaining 67g of dried resin. Take 20g of dried resin and place it in 400mL of dry dichloromethane, stir for 15h to swell, and filter to obtain swollen resin.

[0034] Separately, 10.67 g of aluminum trichloride (0.08 mol) was dissolved in 200 mL of dry dichloromethane, followed by the addition of 122.66 g of phosphorus oxychloride (0.8 mol), which was thoroughly mixed to form a complex solution. The swollen resin was added to the complex solution and reacted in a 30°C water bath with stirring. The phosphorylation modification was completed after 8 hours. After the reaction was completed, the mixture was filtered, and the resulting resin was washed and filtered three times with dry dichloromethane to remove residual aluminum trichloride and residual phosphorus oxychloride, yielding a phosphorylated resin with dual active sites, denoted as DCP-1.

[0035] S2 organic-friendly modification

[0036] The DCP-1 obtained in step S1 was added to 400 mL of dry acetonitrile. The system temperature was lowered to 0 °C with stirring. Then, using a constant-pressure dropping funnel, 93.77 g of n-octanol (0.72 mol) and 76.5 g of triethylamine (0.756 mol) were added sequentially to the system to initiate the esterification reaction. The reaction was stopped after 7 h. The reaction solution was filtered, washed with dry dichloromethane, and filtered three times to remove residual reagents and byproduct salts, yielding the organophilic modified resin, denoted as OCP-1.

[0037] S3 hydrolysis acidification

[0038] The OCP-1 obtained in step S2 was added to 300 mL of 8 wt.% dilute hydrochloric acid solution. The solution was heated to 50 °C in a water bath and stirred to carry out the hydrolysis reaction. The reaction was carried out for 8 h to convert the remaining P-Cl bonds into P-OH structures. After the reaction was completed, the solution was filtered and washed repeatedly with deionized water until the eluent was neutral. The modified resin was then placed at 70 °C overnight and vacuum dried to constant weight to obtain the phase transfer enrichment functional catalyst, denoted as OAP-1.

[0039] Example 2

[0040] The preparation method of the phase transfer enrichment functional catalyst for the acrolein hydration reaction to prepare 3-hydroxypropionaldehyde in this embodiment includes the following steps:

[0041] S1 dual active site introduction

[0042] Take 100g of commercially available LS1000 type macroporous styrene-based chelating ion exchange resin, place it in a Buchner funnel, wash and filter it with deionized water until the eluent is neutral, then place it in a forced-air drying oven at 60℃ for 12h to constant weight, obtaining 66.8g of dried resin. Take 20g of dried resin and place it in 400mL of dry dichloromethane, stir for 12h to swell, and filter to obtain swollen resin.

[0043] Separately, 9.73 g of ferric chloride (0.06 mol) was dissolved in 100 mL of dry 1,2-dichloroethane, followed by the addition of 92 g of phosphorus oxychloride (0.6 mol), which was thoroughly mixed to form a complex solution. The swollen resin was then added to the complex solution and reacted in a water bath at 20 °C with stirring for 6 h to complete the phosphorylation modification. After the reaction was complete, the mixture was filtered, and the resulting resin was washed three times with dry dichloromethane and filtered again to remove residual ferric chloride and phosphorus oxychloride, yielding a phosphorylated resin with dual active sites, denoted as DCP-2.

[0044] S2 organic-friendly modification

[0045] The DCP-2 obtained in step S1 was added to 200 mL of dry acetonitrile. The system temperature was lowered to -5 °C with stirring. Then, using a constant-pressure dropping funnel, 52.1 g of n-hexanol (0.51 mol) and 40.34 g of pyridine (0.51 mol) were added sequentially to the system to initiate the esterification reaction. The reaction was stopped after 4 h. The reaction solution was filtered, washed with dry dichloromethane, and filtered three times to remove residual reagents and byproduct salts, yielding the organophilic modified resin, denoted as OCP-2.

[0046] S3 hydrolysis acidification

[0047] The OCP-2 obtained in step S2 was added to 200 mL of 5 wt.% dilute hydrochloric acid solution. The solution was heated to 40 °C in a water bath and stirred to carry out the hydrolysis reaction for 6 h, so that the remaining P-Cl bonds were converted into P-OH structures. After the reaction was completed, the solution was filtered and washed repeatedly with deionized water until the eluent was neutral. The modified resin was then placed at 60 °C overnight and vacuum dried to constant weight to obtain the phase transfer enrichment functional catalyst, denoted as OAP-2.

[0048] Example 3

[0049] The preparation method of the phase transfer enrichment functional catalyst for the acrolein hydration reaction to prepare 3-hydroxypropionaldehyde in this embodiment includes the following steps:

[0050] S1 dual active site introduction

[0051] Take 100g of commercially available LS1000 type macroporous styrene-based chelating ion exchange resin, place it in a Buchner funnel, wash and filter it with deionized water until the eluent is neutral, then place it in a forced-air drying oven at 80℃ for 24h to constant weight, obtaining 66.9g of dried resin. Take 20g of dried resin and place it in 400mL of dry dichloromethane, stir for 18h to swell, and filter to obtain swollen resin.

[0052] Separately, 13.63 g of zinc chloride (0.1 mol) was dissolved in 300 mL of dry nitrobenzene, followed by the addition of 153.32 g of phosphorus oxychloride (1 mol) to form a complex solution. The swollen resin was then added to the complex solution and reacted in a 40°C water bath with stirring for 10 h to complete the phosphorylation modification. After the reaction was complete, the mixture was filtered, and the resulting resin was washed three times with dry dichloromethane and filtered again to remove residual zinc chloride and phosphorus oxychloride, yielding a phosphorylated resin with dual active sites, denoted as DCP-3.

[0053] S2 organic-friendly modification

[0054] The DCP-3 obtained in step S1 was added to 600 mL of dry acetonitrile. The system temperature was lowered to 5 °C with stirring. Then, using a constant-pressure dropping funnel, 177 g of n-dodecanool (0.95 mol) and 110.76 g of anhydrous sodium carbonate (1.045 mol) were added sequentially to the system to initiate the esterification reaction. The reaction was stopped after 10 h. The reaction solution was filtered, washed with dry dichloromethane, and filtered three times to remove residual reagents and byproduct salts, yielding the organophilic modified resin, denoted as OCP-3.

[0055] S3 hydrolysis acidification

[0056] The OCP-3 obtained in step S2 was added to 400 mL of 10 wt.% dilute hydrochloric acid solution. The solution was heated to 60 °C in a water bath and stirred to carry out hydrolysis reaction for 10 h, so that the remaining P-Cl bonds were converted into P-OH structures. After the reaction was completed, the solution was filtered and washed repeatedly with deionized water until the eluent was neutral. The modified resin was then placed at 80 °C overnight and vacuum dried to constant weight to obtain the phase transfer enrichment functional catalyst, denoted as OAP-3.

[0057] Example 4

[0058] The preparation method of the phase transfer enrichment functional catalyst for the acrolein hydration reaction to prepare 3-hydroxypropionaldehyde in this embodiment includes the following steps:

[0059] S1 dual active site introduction

[0060] Following step S1 of Example 1, a phosphorylated resin DCP-1 with dual active sites was obtained.

[0061] S2 organic-friendly modification

[0062] The DCP-1 obtained in step S1 was modified according to step S2 of Example 2 to obtain an organophilic modified resin, denoted as OCP-4.

[0063] S3 hydrolysis acidification

[0064] Following step S3 of Example 1, OCP-4 was hydrolyzed and acidified to obtain a phase transfer enrichment functional catalyst, denoted as OAP-4.

[0065] Example 5

[0066] The preparation method of the phase transfer enrichment functional catalyst for the acrolein hydration reaction to prepare 3-hydroxypropionaldehyde in this embodiment includes the following steps:

[0067] S1 dual active site introduction

[0068] Following step S1 of Example 2, a phosphorylated resin DCP-2 with dual active sites was obtained.

[0069] S2 organic-friendly modification

[0070] The DCP-2 obtained in step S1 was modified according to step S2 of Example 3 to obtain an organophilic modified resin, denoted as OCP-5.

[0071] S3 hydrolysis acidification

[0072] Following step S3 of Example 3, OCP-5 was hydrolyzed and acidified to obtain a phase transfer enrichment functional catalyst, denoted as OAP-5.

[0073] Comparative Example 1

[0074] The difference from Example 1 is that the organic-affinity modification in step S2 is not performed. Instead, the phosphorylated resin DCP-1 obtained in step S1 is directly hydrolyzed and acidified in step S3 to obtain the resin catalyst, denoted as AP-1.

[0075] Comparative Example 2

[0076] The difference from Example 1 is that the pretreated swollen resin is not modified by phosphorylation in step S1, but is directly treated by steps S2 and S3 to obtain the resin catalyst, denoted as X-1.

[0077] Comparative Example 3

[0078] The difference from Example 1 is that the DCP-1 obtained in step S1 is first hydrolyzed and acidified in step S3, and then modified with an organophilic affinity in step S2 to obtain a resin catalyst, denoted as AOP-1.

[0079] Evaluation of acrolein hydration reaction performance:

[0080] The catalysts prepared in Examples 1-5 and Comparative Examples 1-3 were loaded into a fixed-bed reactor, and a 12 wt.% acrolein aqueous solution was used as feed. The reactor was heated at 40°C and a liquid hourly space velocity (LHSV) of 1 h⁻¹. -1 Under specific conditions, a hydration reaction was carried out continuously for 24 hours. Samples of the product liquid were collected hourly during the reaction. The contents of acrolein and 3-hydroxypropional were analyzed by gas chromatography using the internal standard method. The reaction conversion rate and selectivity were calculated. The results are as follows: Figure 1-2 As shown.

[0081] like Figure 1As shown, the phase transfer enrichment functional catalysts prepared in Examples 1-5 exhibited excellent and stable catalytic activity during a continuous 24-hour reaction, with acrolein conversion rates generally maintained between 80% and 85%. In contrast, the conversion rate of Comparative Example 2 resin catalyst X-1, which was not modified by phosphorylation, was only 21% to 22%, demonstrating that the dichlorinated active sites introduced by Friedel-Crafts phosphorylation are key to the acidic active center and the organophilic long-chain branches. Notably, although the conversion rate (84% to 87%) of Comparative Example 1 resin catalyst AP-1 was comparable to that of the examples, in the absence of organophilic long chains, its hydration product 3-hydroxypropanal failed to detach from the acidic active center in time, leading to a sharp increase in the degree of side reactions, and the overall selectivity remained at around 50%. Comparative Example 3 resin catalyst AOP-1, due to preferential hydrolysis and acidification, had converted most of the P-Cl bonds to P-OH structures, resulting in insufficient sites for subsequent organophilic modification and weakened 3-hydroxypropanal desorption capacity, thus exhibiting high conversion rates but only a selectivity of 78% to 79%.

[0082] like Figure 2 As shown, the introduced organophilic side chain plays a crucial role in suppressing side reactions during the catalytic hydration of acrolein. The selectivity of the catalysts in Examples 1-5 remained consistently high at 90-97%, with the catalyst OAP-2 in Example 2, modified with a C6 straight-chain alkyl alcohol, achieving a selectivity of over 96%, demonstrating the significant optimization of the microenvironment catalytic system for the desorption process of the product 3-hydroxypropionaldehyde. In contrast, the resin catalyst AP-1 in Comparative Example 1, without the introduction of the organophilic side chain, showed a selectivity decrease to approximately 50%. The mechanism was analyzed to be due to the strong polarity of 3-hydroxypropionaldehyde forming a stable hydrogen bond adsorption with the phosphate site, preventing the product from diffusing into the aqueous phase in time, and thus leading to a severe continuous condensation side reaction with the raw material acrolein. Although the resin catalyst AOP-1 in Comparative Example 3 possesses both phosphate groups and long-chain alkyl groups, its selectivity is only maintained at 78-79% due to the "hydrolysis first, esterification later" modification sequence, which is significantly lower than that of the other examples. This indicates that it is difficult to accurately construct a synergistic microenvironment where "acidic sites are surrounded by organic affinity regions" when performing organophilic esterification in an environment containing a large amount of P-OH, and the distribution of active sites may even be uneven due to steric hindrance.

[0083] In summary, the catalyst with phase transfer enrichment function constructed by stepwise modification in this invention solves the technical problems of easy polymerization and low selectivity of the hydrated product 3-hydroxypropanal at the molecular scale while maintaining high conversion rate, and has significant technical application value.

Claims

1. A method for preparing a phase transfer enrichment functional catalyst for the acrolein hydration reaction to prepare 3-hydroxypropanal, characterized in that, Includes the following steps: Introduction of S1 dual active sites: In a dry aprotic solvent, using macroporous styrene resin as a carrier and phosphorus oxychloride as a phosphorylating agent, a Friedel-Crafts phosphorylation reaction is carried out through electrophilic substitution of aromatic rings under the action of Lewis acid catalyst to generate a resin intermediate containing dichlorophosphoryl groups on the surface; the amount of phosphorus oxychloride added is 0.03~0.05 mol / g macroporous styrene resin; S2 Organophilic Modification: A resin intermediate containing dichlorophosphoryl groups is subjected to a monophilic nucleophilic substitution reaction with a fatty alcohol in an organic solvent under the catalysis of an acid-binding agent, thereby esterifying one of the P-Cl bonds and introducing a long fatty chain with organophilic function onto the phosphorus atom to obtain an intermediate resin containing an organophilic side chain; the molar ratio of fatty alcohol to phosphorus oxychloride is (0.85~0.95):1; the fatty alcohol is a C6~C12 straight-chain alkyl alcohol; S3 hydrolysis acidification: The intermediate resin containing the organic side chain is hydrolyzed to convert the remaining P-Cl group into a phosphate hydroxyl structure. After washing and drying, the phase transfer enrichment functional catalyst is obtained.

2. The method for preparing the phase transfer enrichment functional catalyst for the acrolein hydration reaction to 3-hydroxypropionaldehyde as described in claim 1, characterized in that, In step S1, the macroporous styrene resin is pretreated before use: the macroporous styrene resin is washed with deionized water until the eluent is neutral, filtered, and dried to constant weight. The dried macroporous styrene resin is then added to dry dichloromethane and stirred to swell, and filtered to obtain swollen resin. During pretreatment, the drying temperature is 60~80℃, the drying time is 12~24h, and the stirring and swelling time is 12~18h.

3. The method for preparing the phase transfer enrichment functional catalyst for the acrolein hydration reaction to 3-hydroxypropionaldehyde as described in claim 1, characterized in that, The specific operation of step S1 is as follows: dissolve the Lewis acid catalyst in a dry aprotic solvent, then add phosphorus oxychloride and mix thoroughly to form a complex solution; add pre-swollen macroporous styrene resin to the complex solution and stir to carry out the phosphorylation reaction; after the reaction is completed, filter, and wash and filter the obtained resin with dry dichloromethane until the residual Lewis acid catalyst and phosphorus oxychloride are removed.

4. The method for preparing the phase transfer enrichment functional catalyst for the acrolein hydration reaction to 3-hydroxypropionaldehyde as described in claim 3, characterized in that, The aprotic solvent is dichloromethane, 1,2-dichloroethane, or nitrobenzene, and the addition amount is 5~15 mL / g macroporous styrene resin; the Lewis acid catalyst is aluminum trichloride, ferric trichloride, or zinc chloride, and the addition amount is 0.003~0.005 mol / g macroporous styrene resin; the phosphorylation reaction temperature is 20~40℃, and the reaction time is 6~10 h.

5. The method for preparing the phase transfer enrichment functional catalyst for the acrolein hydration reaction to 3-hydroxypropionaldehyde as described in claim 1, characterized in that, The specific operation of step S2 is as follows: the resin intermediate containing dichlorophosphoryl group obtained in step S1 is added to a dry organic solvent, stirred at -5~5℃ and fatty alcohol and acid-binding agent are added in sequence for reaction, the reaction time is 4~10h; after the reaction is completed, the intermediate resin containing organic side chain is obtained by filtration, and the filter is washed with dry dichloromethane to remove residual reagents and by-product salts.

6. The method for preparing the phase transfer enrichment functional catalyst for the acrolein hydration reaction to 3-hydroxypropionaldehyde as described in claim 5, characterized in that, The acid-binding agent is triethylamine, pyridine, or anhydrous sodium carbonate, with a molar ratio of (1~1.1):1 to the fatty alcohol; the organic solvent is acetonitrile, and the addition amount is 10~30 mL / g of macroporous styrene resin.

7. The method for preparing the phase transfer enrichment functional catalyst for the acrolein hydration reaction to 3-hydroxypropionaldehyde as described in claim 1, characterized in that, The specific operation of step S3 is as follows: the intermediate resin containing the organic side chain obtained in step S2 is added to a dilute hydrochloric acid solution, heated and stirred to carry out the hydrolysis reaction; after the reaction is completed, it is filtered, washed with deionized water until the eluent is neutral, and then vacuum dried to constant weight to obtain the phase transfer enrichment functional catalyst.

8. The method for preparing the phase transfer enrichment functional catalyst for the acrolein hydration reaction to 3-hydroxypropionaldehyde as described in claim 7, characterized in that, The concentration of the dilute hydrochloric acid solution is 5~10 wt.%, and the amount of dilute hydrochloric acid solution added is 10~20 mL / g macroporous styrene resin; the hydrolysis reaction temperature is 40~60℃, the hydrolysis reaction time is 6~10 h; and the vacuum drying temperature is 60~80℃.

9. A phase transfer enrichment functional catalyst for the preparation of 3-hydroxypropanal from acrolein hydration, characterized in that, It was prepared by the method for preparing 3-hydroxypropional by the phase transfer enrichment functional catalyst for the acrolein hydration reaction as described in any one of claims 1-8.

10. The application of the phase transfer enrichment functional catalyst as described in claim 9 for the preparation of 3-hydroxypropional via the hydration reaction of acrolein, characterized in that, It is charged in a fixed bed reactor, and 8-15 wt.% of propenal aqueous solution is used as feed, and 3-hydroxypropionaldehyde is prepared by continuously feeding propenal under the conditions of 30-50℃, liquid space velocity 0.5-1.5 h -1 -1.

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