Allyl alcohol hydroformylation method for regulating yield of 3-hydroxy-2-methylpropionaldehyde

Abstract

The invention relates to an allyl alcohol hydroformylation method for regulating the yield of 3-hydroxy-2-methylpropionaldehyde. The method comprises the following steps: mixing a raw material allyl alcohol with a solvent to prepare a solution with the mass fraction of 3-35%; adding the solution and a catalyst composition into a reaction kettle, and sealing; replacing the atmosphere in the kettle with nitrogen and synthesis gas in sequence; pressurizing the synthesis gas, heating the system to a reaction temperature, and controlling the temperature to be 55-95 DEG C and the pressure to be 0.5-1.5 Mpa; and when the gas is not further consumed, cooling the reaction kettle, releasing the pressure, and analyzing the reaction liquid by using gas chromatography to obtain the aldehyde solution with low normal / isomer ratio. According to the allyl alcohol hydroformylation method, a lower aldehyde product normal / isomerization ratio can be formed, and the lowest ratio can reach 2; according to the present invention, the high yield of the 3-hydroxy-2-methylpropionaldehyde can be achieved by the low n-iso-ratio product on the premise that the total capacity of the device is not substantially adjusted, and the high yield of the 2-methyl-1, 3-propylene glycol can be achieved after the hydrogenation so as to adapt to the change of the market demand.

Description

Technical Field

[0001] The invention relates to a hydroformylation reaction, in particular to an allyl alcohol hydroformylation method for regulating the yield of 3-hydroxy-2-methylpropanal. Background Art

[0002] The hydroformylation reaction of allyl alcohol has important industrial significance, and its reaction products include 2-hydroxytetrahydrofuran and 3-hydroxy-2-methylpropanal. Among them, 2-hydroxytetrahydrofuran can be used for hydrogenation to produce 1,4-butanediol, which is an important basic organic chemical and fine chemical raw material with a wide range of uses. It can be used as a raw material to derive a variety of high-value-added fine chemical products; 3-hydroxy-2-methylpropanal, as a reaction by-product, generally enters the subsequent hydrogenation process together to produce 2-methyl-1,3-propanediol (MPO), which has received less attention from the industry. It was not until 1990 that ARCO Chemical Company in the United States first introduced MPO as a new diol synthetic building block (Building Block) into the chemical industry. Due to its unique structure and transparent, low-toxic, fragrance-enhancing, antibacterial, hydration and biodegradable properties, it is promising in the fields of polyester resins, plasticizers, white appliance exterior paints, inks, personal care products, transparent resin crafts, etc., especially in the water-soluble polyester (COPET) raw material for high-tech products such as sea island fibers. In many aspects, it is superior to the currently widely used 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, etc., and its application research has gradually attracted attention.

[0003] In recent years, with the rise of the facial mask market, the demand for moisturizers has increased. MPO, as a transparent, colorless, low-viscosity, odorless, non-irritating liquid, has gradually been widely used in personal care products. As a major substitute for 1,3-butanediol, its selling price increased to about 20,000 yuan / ton in 2021, and it began to show its unique market value and prospects.

[0004] There are many methods for synthesizing MPO, such as allyl alcohol hydroformylation, 2-methylmalonic acid diethyl ester hydrolysis, tert-butoxy alkyl metal salt, and 3-hydroxy-2-methylpropanal reduction. However, most of them are laboratory research. Except for the industrialization of the process of producing 1,4-butanediol as a by-product MPO by allyl alcohol hydroformylation of ARCO Chemical Company in the United States, most of them are still in the laboratory research stage. Each process is still immature, and there are various reasons that limit its industrial application.

[0005] In the prior art, triphenylphosphine and rhodium catalysts are widely used in the hydroformylation reaction of allyl alcohol. Using a low-pressure rhodium carbonyl synthesis process, the reaction conditions are 75-95°C, 0.8-2.0MPa, the allyl alcohol conversion rate is 97-99%, the selectivity is 96-98%, and the product 1,4-butanediol:2-methyl-1,3-propanediol is 7-10. However, it is difficult to maintain a low level of normal-iso ratio in actual operation, and the actual adjustment range is limited, which is not enough to meet the market demand for MPO.

[0006] Patents CN101522602A and CN101652179A describe a catalytic reaction system for producing 4-hydroxybutyraldehyde. Although the product yield is improved, the obtained product has a very high iso-ratio, making it difficult to achieve stable product ratio modulation, and it is impossible to achieve efficient production of 3-hydroxy-2-methylpropanal.

[0007] Although the catalyst composition described in patent CN202111511391.X can obtain a larger range of adjustment of the iso-ratio, the process of obtaining the first ligand is relatively complicated, and multiple reagents are involved in the preparation process, which poses a risk of interfering with the main reaction.

[0008] With the advancement of science and technology and the development of the market, the development of the catalytic system for carbonyl synthesis of allyl alcohol can start with new, efficient, and easily available phosphine ligands to improve the activity of rhodium catalysts, improve product selectivity and stability, and at the same time efficiently and stably produce products with low normal-to-iso ratios. Low normal-to-iso ratios can achieve more 2-methyl-1,3-propanediol without major adjustments to industrial equipment to adapt to changing market demands. Summary of the invention

[0009] The present invention aims at the problems existing in the prior art and provides a method for adjusting the yield of 3-hydroxy-2-methylpropanal by hydroformylation of allyl alcohol. The method can achieve a large adjustment range of the normal-to-iso ratio of the product in the process of producing aldehyde by hydroformylation of allyl alcohol, achieve a lower normal-to-iso ratio, and has the characteristics of simple process, easy availability of catalyst ligands, etc.

[0010] The invention provides a method for hydroformylating allyl alcohol by using a catalyst composition. The method comprises the following steps: hydroformylating allyl alcohol in the presence of a solvent and the catalyst composition to obtain 2-hydroxytetrahydrofuran (4-hydroxybutyraldehyde) and 3-hydroxy-2-methylpropanal.

[0011] Reaction equation:

[0012]

[0013] The aldehydes produced by hydroformylation are then hydrogenated to give 1,4-butanediol and 2-methyl-1,3-propanediol.

[0014]

[0015] A method for hydroformylating allyl alcohol for regulating the yield of 3-hydroxy-2-methylpropanal is characterized in that the method comprises the following steps: hydroformylating allyl alcohol with carbon monoxide and hydrogen in the presence of a solvent and a catalyst composition to generate 2-hydroxytetrahydrofuran and 3-hydroxy-2-methylpropanal, wherein the catalyst composition comprises a rhodium compound, triphenylphosphine and 1,4-bis(diphenylphosphino)butane.

[0016] The specific steps include: mixing the raw material allyl alcohol with a solvent to prepare a solution with a mass fraction of 3-35%; adding the solution and the catalyst composition into a reaction kettle and sealing it; replacing the atmosphere in the kettle with nitrogen and synthesis gas (a mixture of CO and H2) in turn; pressurizing the synthesis gas, heating the system to the reaction temperature, controlling the temperature to 55-95°C and the pressure to 0.5-1.5Mpa, and observing the gas consumption; when the gas is not further consumed (reaction time 1-6 hours), cooling the reaction kettle, depressurizing it, analyzing the reaction liquid with gas chromatography, and obtaining an aldehyde solution with a low normal-to-iso ratio.

[0017] The molar ratio of triphenylphosphine to rhodium compound is preferably 30:1-120:1, more preferably 35:1-100:1.

[0018] The molar ratio of 1,4-bis(diphenylphosphino)butane to the rhodium compound is preferably 25:1-70:1, and more preferably 35:1-50:1.

[0019] The rhodium compound is preferably triphenylphosphine carbonyl rhodium acetylacetonate. The triphenylphosphine and 1,4-bis(diphenylphosphino)butane are both commercially available.

[0020] Preferred solvents for use in the process of the present invention include toluene, n-heptane and methyl tert-butyl ether.

[0021] The reaction conditions for the allyl alcohol hydroformylation are preferably a reaction temperature of 55-95° C. and a reaction pressure (gauge pressure) of 0.5-1.5 MPa, more preferably 60-80° C. and 0.8-1.2 MPa.

[0022] The molar ratio of carbon monoxide to hydrogen is 1: 1. The reaction time is 1-6 hours.

[0023] The initial mass fraction of allyl alcohol in the solvent for hydroformylation reaction is preferably 3-35%; more preferably 5-20%.

[0024] The technical solution provided by the present invention has the following beneficial effects:

[0025] (1) Compared with the prior art, the method for hydroformylation of allyl alcohol of the present invention can form a lower normal-to-iso ratio of aldehyde products, which can be as low as 2. The low normal-to-iso ratio product can achieve more 3-hydroxy-2-methylpropanal without major adjustments to the total capacity of the device, and can achieve more 2-methyl-1,3-propanediol after hydrogenation to adapt to changes in market demand.

[0026] (2) The present invention uses a catalyst composition to achieve a large range of adjustment of the normal iso-ratio while ensuring high reaction activity, especially low normal iso-ratio regulation, that is, to achieve regulation of the normal iso-ratio of the allyl alcohol hydroformylation reaction product within the range of 2-10. DETAILED DESCRIPTION

[0027] The present invention further illustrates its preparation and use methods through the following examples, but does not constitute a limitation on the protection scope of the present invention.

[0028] Example 1

[0029] The experiment was carried out in a 300mL autoclave. First, 10.8g of allyl alcohol was diluted to 100ml with toluene, and then the above solution, triphenylphosphine carbonyl rhodium acetylacetonate (2mmol), triphenylphosphine (3.9g) and 1,4-bis(diphenylphosphino)butane (4g) were added to the reactor and sealed. The atmosphere in the reactor was replaced three times with nitrogen and synthesis gas (C0 / H2 volume ratio 1:1) respectively. The synthesis gas was pressurized to 1.2MPa (gauge pressure), heated to 70°C, and the reactor pressure was maintained at 1.2MPa. The gas consumption was observed. When there was no further consumption of gas (reaction time 3.5 hours), the reactor was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0030] Example 2

[0031] The experiment was carried out in a 300mL autoclave. First, 10.8g of allyl alcohol was fixed to 100ml with n-heptane, and then the above solution, triphenylphosphine carbonyl rhodium acetylacetonate (2mmol), triphenylphosphine (2g) and 1,4-bis(diphenylphosphino)butane (4.4g) were added to the reactor and sealed. The atmosphere in the reactor was replaced three times with nitrogen and synthesis gas (C0 / H2 volume ratio 1:1) respectively. The synthesis gas was pressurized to 1MPa (gauge pressure), heated to 60°C, and the reactor pressure was maintained at 1MPa. The gas consumption was observed. When there was no further consumption of gas (reaction time 1 hour), the reactor was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0032] Example 3

[0033] The experiment was carried out in a 300mL autoclave. First, 4.36g of allyl alcohol was diluted to 100ml with toluene, and then the above solution, triphenylphosphine carbonyl rhodium acetylacetonate (2mmol), triphenylphosphine (5.2g) and 1,4-bis(diphenylphosphino)butane (6g) were added to the reactor and sealed. The atmosphere in the reactor was replaced three times with nitrogen and synthesis gas (C0 / H2 volume ratio 1:1) respectively. The synthesis gas was pressurized to a pressure (gauge pressure) of 0.8MPa, heated to 60°C, and the reactor pressure was maintained at 0.8MPa. The gas consumption was observed. When there was no further consumption of gas (reaction time 6 hours), the reactor was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0034] Example 4

[0035] The experiment was carried out in a 300mL autoclave. First, 17g of allyl alcohol was fixed to 100ml with methyl tert-butyl ether, and then the above solution, acetylacetonate triphenylphosphine carbonyl rhodium (3mmol), triphenylphosphine (2.5g) and 1,4-bis(diphenylphosphino)butane (4.5g) were added to the reactor and sealed. The atmosphere in the reactor was replaced three times with nitrogen and synthesis gas (C0 / H2 volume ratio 1:1) respectively. The synthesis gas was pressurized to 0.8MPa (gauge pressure), heated to 80℃, and the reactor pressure was maintained at 0.8MPa. The gas consumption was observed. When there was no further consumption of gas (reaction time 2 hours), the reactor was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0036] Example 5

[0037] The experiment was carried out in a 300mL autoclave. First, 2.7g of allyl alcohol was fixed to 100ml with methyl tert-butyl ether, and then the above solution, triphenylphosphine carbonyl rhodium acetylacetonate (2mmol), triphenylphosphine (6.2g) and 1,4-bis(diphenylphosphino)butane (2.2g) were added to the reactor and sealed. The atmosphere in the reactor was replaced three times with nitrogen and synthesis gas (C0 / H2 volume ratio 1:1) respectively. The synthesis gas was pressurized to 1MPa (gauge pressure), heated to 95°C, and the reactor pressure was maintained at 1MPa. The gas consumption was observed. When there was no further consumption of gas (reaction time 4 hours), the reactor was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0038] Example 6

[0039] The experiment was conducted in a 300mL autoclave. First, 30g of allyl alcohol was diluted to 100ml with toluene, and then the above solution, triphenylphosphine carbonyl rhodium acetylacetonate (2.5mmol), triphenylphosphine (2.3g) and 1,4-bis(diphenylphosphino)butane (7.5g) were added to the reactor and sealed. The atmosphere in the reactor was replaced three times with nitrogen and synthesis gas (C0 / H2 volume ratio 1:1) respectively. The synthesis gas was pressurized to 0.5MPa (gauge pressure), heated to 55°C, and the reactor pressure was maintained at 0.5MPa. The gas consumption was observed. When there was no further consumption of gas (reaction time 3 hours), the reactor was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0040] Example 7

[0041] The experiment was carried out in a 300mL autoclave. First, 12.5g of allyl alcohol was fixed to 100ml with methyl tert-butyl ether, and then the above solution, acetylacetonate triphenylphosphine carbonyl rhodium (2mmol) and triphenylphosphine (3.9g) were added to the reactor and sealed. The atmosphere in the reactor was replaced three times with nitrogen and synthesis gas (C0 / H2 volume ratio 1:1) respectively. The synthesis gas was pressurized to 1.5MPa (gauge pressure), heated to 95°C, and the reactor pressure was maintained at 1.5MPa. The gas consumption was observed. When there was no further consumption of gas (reaction time 5 hours), the reactor was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0042] Example 8

[0043] The experiment was carried out in a 300mL autoclave. First, 5.6g of allyl alcohol was fixed to 100ml with toluene, and then the above solution, acetylacetonate triphenylphosphine carbonyl rhodium (2mmol) and triphenylphosphine (6.2g) were added to the reactor and sealed. The atmosphere in the reactor was replaced three times with nitrogen and synthesis gas (C0 / H2 volume ratio 1:1) respectively. The synthesis gas was pressurized to 1.5MPa (gauge pressure), heated to 65°C, and the reactor pressure was maintained at 1.5MPa. The gas consumption was observed. When there was no further consumption of gas (reaction time 5 hours), the reactor was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0044] Table 1

[0045]

[0046] In Examples 1-6, 1,4-bis(diphenylphosphino)butane was added, and the product normal-to-iso ratio was 2-4; in Examples 7 and 8, 1,4-bis(diphenylphosphino)butane was not added, and the product normal-to-iso ratio was 7-10; this indicates that the addition of 1,4-bis(diphenylphosphino)butane can efficiently and stably produce products with low normal-to-iso ratios, and low normal-to-iso ratios can achieve more 3-hydroxy-2-methylpropanal without major adjustments to industrial equipment, and more 2-methyl-1,3-propanediol after hydrogenation to meet the ever-changing market demand; in addition, by using the catalyst composition, a large normal-to-iso ratio adjustment range is obtained while ensuring high reaction activity, especially low normal-to-iso ratio regulation, that is, the normal-to-iso ratio of the allyl alcohol hydroformylation reaction product is regulated within the range of 2-10.

[0047] The technical solutions disclosed and proposed by the present invention can be realized by those skilled in the art by referring to the contents of this article and appropriately changing the conditions, routes and other links. Although the methods and preparation techniques of the present invention have been described through preferred embodiments, relevant technicians can obviously modify or re-combine the methods and technical routes described herein without departing from the content, spirit and scope of the present invention to realize the final preparation technology. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art, and they are all considered to be included in the spirit, scope and content of the present invention.

Claims

1. A method for hydroformylating allyl alcohol to adjust the yield of 3-hydroxy-2-methylpropanal, characterized in that: The invention comprises the following steps: in the presence of a solvent and a catalyst composition, allyl alcohol undergoes a hydroformylation reaction with carbon monoxide and hydrogen to generate 2-hydroxytetrahydrofuran and 3-hydroxy-2-methylpropanal; the catalyst composition comprises a rhodium compound, triphenylphosphine and 1,4-bis(diphenylphosphino)butane.

2. The method for hydroformylation of allyl alcohol for regulating the yield of 3-hydroxy-2-methylpropanal as claimed in claim 1, characterized in that: The raw material allyl alcohol is mixed with a solvent to prepare a solution with a mass fraction of 3-35%; the solution and the catalyst composition are added into a reaction kettle and sealed; the atmosphere in the kettle is replaced with nitrogen and synthesis gas in turn; the synthesis gas is pressurized, the system is heated to 55-95° C., and the pressure is 0.5-1.5Mpa. When the gas is not further consumed, the reaction kettle is cooled and the pressure is released to obtain an aldehyde solution with a low normal-to-iso ratio.

3. The method for hydroformylation of allyl alcohol for regulating the yield of 3-hydroxy-2-methylpropanal as claimed in claim 1, characterized in that: The molar ratio of triphenylphosphine:rhodium compound is 30:1-120:

1.

4. The method for hydroformylation of allyl alcohol for regulating the yield of 3-hydroxy-2-methylpropanal as claimed in claim 1, characterized in that: The molar ratio of triphenylphosphine:rhodium compound is 35:1-100:

1.

5. The method for hydroformylation of allyl alcohol for regulating the yield of 3-hydroxy-2-methylpropanal as claimed in claim 1, characterized in that: The molar ratio of 1,4-bis(diphenylphosphino)butane:rhodium compound is 25:1-70:

1.

6. The method for hydroformylation of allyl alcohol for regulating the yield of 3-hydroxy-2-methylpropanal as claimed in claim 1, characterized in that: The molar ratio of 1,4-bis(diphenylphosphino)butane:rhodium compound is 35:1-50:

1.

7. The method for hydroformylation of allyl alcohol for regulating the yield of 3-hydroxy-2-methylpropanal as claimed in claim 1, characterized in that: The rhodium compound is triphenylphosphine carbonyl rhodium acetylacetonate.

8. The method for hydroformylation of allyl alcohol for regulating the yield of 3-hydroxy-2-methylpropanal as claimed in claim 1, characterized in that: Solvents include toluene, n-heptane and methyl tert-butyl ether.

9. The method for hydroformylation of allyl alcohol for regulating the yield of 3-hydroxy-2-methylpropanal as claimed in claim 1, characterized in that: The reaction temperature of allyl alcohol hydroformylation is 60-80°C and the reaction pressure is 0.8-1.2Mpa.

10. The method for hydroformylation of allyl alcohol for regulating the yield of 3-hydroxy-2-methylpropanal as claimed in claim 1, characterized in that: The molar ratio of carbon monoxide to hydrogen is 1:1; and the reaction time is 1-6 hours.

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