A method for hydroformylation of allyl acetate capable of avoiding equipment overheating caused by reaction runaway

Abstract

The present invention provides a method for the hydroformylation of allyl acetate that can avoid runaway reaction and equipment overheating. Allyl acetate can undergo hydroformylation with a mixture of hydrogen and carbon monoxide in the presence of a complex catalyst. However, the heat of reaction of the allyl acetate hydroformylation reaction is as high as 1406 J / g. AAC The heat of reaction of the secondary decomposition reaction of allyl acetate is as high as 1167 J / g AAC If the reaction system's heat transfer rate is slower than its heat release rate or a secondary decomposition reaction of allyl acetate occurs, the system temperature may rise above 600°C, causing the reaction equipment to overheat and then overpressure. The present invention adds a suitable organic peroxide to the allyl acetate hydroformylation reaction system. The organic peroxide decomposes at high temperatures when abnormal operating conditions occur, generating active oxygen radicals that promptly destroy the complex catalyst structure and poison the catalyst. This prevents uncontrolled heat release from the allyl acetate hydroformylation reaction, which could lead to equipment overheating or the initiation of a secondary decomposition reaction of allyl acetate.

Description

Technical Field

[0001] The invention belongs to the field of chemical production safety, and particularly relates to a method for hydroformylating allyl acetate, which can avoid overheating of equipment caused by reaction runaway. Background Art

[0002] Aldehydes are common raw materials for the production of alcohols, acids, and esters, and are widely used in the production processes of medicines, foods, additives, and detergents. Currently, the synthesis of aldehydes is usually prepared by the hydroformylation reaction of olefins and a mixture of hydrogen and carbon monoxide catalyzed by precious metal catalysts.

[0003] 4-Acetoxybutyraldehyde is used as a raw material for the preparation of 1,4-butanediol. Currently, it is usually prepared by the hydroformylation reaction of allyl acetate catalyzed by a complex catalyst composed of metal rhodium and phosphine ligands. This method is a gas-liquid reaction under a homogeneous catalytic system with relatively mild reaction conditions and high catalytic efficiency. However, the reaction heat of the allyl acetate hydroformylation reaction is as high as 1406 J / g. AAC Moreover, the reaction heat of the secondary decomposition reaction of allyl acetate is as high as 1167 J / g AAC When production abnormalities occur, once the heat transfer rate of the reaction system is less than the heat release rate, the material temperature will rise rapidly and trigger a secondary decomposition reaction of the product 4-acetoxybutyraldehyde and the raw material allyl acetate. The system temperature may rise to above 600°C, causing the reaction equipment to overheat and then overpressure.

[0004] There are currently two common treatment methods for the runaway condition of allyl acetate hydroformylation reaction:

[0005] The first method is to use higher-level instrument protection measures to prevent system runaway. This method not only requires expensive instruments and control interlock systems, but also cannot fundamentally prevent system runaway under abnormal conditions because the instrument protection layer also has a probability of failure.

[0006] The second method is to use a large-caliber relief device for relief protection after the system reaction gets out of control. This method not only has the risk of reactor rupture due to overtemperature and overpressure after the bursting disc fails, but also the high-temperature and high-pressure material handling process after the relief is extremely complicated.

[0007] Therefore, it is necessary to find a way to fundamentally avoid the system response from being out of control under abnormal conditions. Summary of the Invention

[0008] The object of the present invention is to provide a method for the hydroformylation of allyl acetate which can avoid overheating of equipment caused by reaction runaway.

[0009] We have conducted a detailed study on the characteristics of the catalyst for the hydroformylation of allyl acetate in the presence of a rhodium and phosphine ligand complex catalyst. The study found that the high-temperature deactivation temperature of the rhodium and phosphine ligand complex catalyst is generally above 200°C. When abnormal operating conditions occur, the secondary decomposition reaction of the product 4-acetoxybutyraldehyde and the raw material allyl acetate has already been initiated before the high-temperature deactivation of the catalyst. Therefore, even if the hydroformylation reaction of allyl acetate is terminated above 200°C, the system temperature will still rise due to the secondary decomposition reaction of the product 4-acetoxybutyraldehyde and the raw material allyl acetate, especially the secondary decomposition reaction of allyl acetate (the heat of the secondary decomposition reaction of allyl acetate is 1167J / g). AAC ) and continue to rise, eventually leading to overheating and overpressure of the equipment.

[0010] Based on the above research, the technical solution of the present invention is as follows:

[0011] A method for the hydroformylation of allyl acetate can avoid equipment overheating caused by reaction runaway. Allyl acetate reacts with a mixture of hydrogen and carbon monoxide in the presence of a catalyst. A suitable organic peroxide is added to the hydroformylation reaction system. When the system temperature rises abnormally, active oxygen free radicals generated by the high-temperature decomposition of the organic peroxide are used to promptly poison the catalyst, thereby preventing the system temperature from continuing to rise.

[0012] To further illustrate the present invention, factors that cause abnormal temperature increases in the system include, but are not limited to, excessive addition of catalyst, lack of heat transfer, excessively high temperature of the heat transfer medium, too little allyl acetate feed, and too high initial reaction temperature, which can cause the system heat release rate to be greater than the heat transfer rate.

[0013] In the present invention, the catalyst for the hydroformylation of allyl acetate is a complex catalyst composed of a metal rhodium active center and a phosphine-based ligand;

[0014] The metal rhodium active center of the complex catalyst may be present in the form of one or more combinations of acetylacetonato carbonyl rhodium, rhodium trichloride, and dicarbonyl acetylacetonato rhodium;

[0015] The molar ratio of the rhodium metal active center to the raw material allyl acetate is 3×10 -7 ~8×10 -6 :1;

[0016] Wherein, the phosphine-based ligand is any one of triphenylphosphine, trialkylphosphine, dimethylphenylphosphine, tri(o-methylphenyl)phosphine, diphenyl-2-pyridylphosphine, triarylphosphite, phosphine heterocyclic ligand, 1,3,5-triaza-7-phosphinotricyclodecane, monooxyacylbisphosphine ligand, phosphite bisphosphine ligand, xanthene-type bisphosphine ligand, dialkyldiarylphosphine ligand or a combination of at least two thereof; wherein, the alkyl group is selected from a C1-C5 straight-chain or branched saturated alkane group, and the aryl group is selected from a benzene, toluene or ethylphenyl group; preferably, the phosphine-based ligand is triphenylphosphine;

[0017] Preferably, the molar ratio of the phosphine-based ligand to the active center rhodium is 3 to 100:1.

[0018] The molar ratio of hydrogen to carbon monoxide in the mixed gas is 0.8 to 1.5:1, and the partial pressure of the mixed gas during the allyl acetate hydroformylation reaction is 40 to 90 bar.

[0019] In the present invention, the reaction temperature of the allyl acetate hydroformylation reaction is 60 to 150° C., preferably 80 to 100° C., for example, 80° C., 90° C., etc.; the reaction pressure of the allyl acetate hydroformylation reaction is 50 to 100 barG; and the total reaction time of the allyl acetate hydroformylation reaction is 2 to 4 hours.

[0020] In the present invention, the organic peroxide has a significant decomposition temperature higher than the operating temperature of the allyl acetate hydroformylation, preferably 10-50°C higher, and lower than the TD24 temperature of the allyl acetate hydroformylation product, preferably 10°C or higher lower. Preferred organic peroxides are tert-butyl hydroperoxide, ethylbenzene hydroperoxide, and / or cumene hydroperoxide. The significant decomposition temperature refers to the temperature at which heat release is clearly detected on thermal safety testing equipment such as DSC or C80.

[0021] In the present invention, the molar ratio of the organic peroxide to the phosphine-based ligand is 5 to 10,000:1, more preferably 30 to 50:1.

[0022] The beneficial effects of the present invention are:

[0023] By adding a suitable organic peroxide to the allyl acetate hydroformylation process, when the system temperature rises abnormally and reaches the decomposition temperature of the organic peroxide, the organic peroxide decomposes to release active oxygen free radicals. These active oxygen free radicals can promptly poison the complex catalyst, interrupting the allyl acetate hydroformylation reaction, preventing further temperature increases and the initiation of secondary decomposition reactions of allyl acetate, thereby preventing overheating and overpressure in the system. Reintroducing a phosphine-based ligand into the system after oxygen deactivation can restore the catalytic activity of the complex catalyst. Once the abnormal operating condition is resolved, there is no need to treat the reaction liquid and production can continue.

[0024] The method provided by the invention not only achieves inherently safe production, but also greatly reduces the time cost and material consumption of handling abnormal working conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the result of heat transfer failure in the allyl acetate hydroformylation system when comparative example 2 of the present invention does not contain an organic peroxide.

[0026] Figure 2 This is the consequence of heat transfer failure in the allyl acetate hydroformylation system when 0.03 mmol of cumene hydroperoxide is contained in Example 3 of the present invention. DETAILED DESCRIPTION

[0027] The specific embodiments of the present invention are further described below with reference to examples. It is easy to understand that according to the technical solution of the present invention, a variety of implementations that can be replaced with each other by a person skilled in the art without changing the essential spirit of the present invention. Therefore, the following specific embodiments and drawings are only exemplary descriptions of the technical solution of the present application and should not be regarded as the entirety of the present application or as a limitation or restriction of the technical solution of the application.

[0028] Comparative Example 1

[0029] Comparative Example 1 is used to illustrate the conversion rate and selectivity of the allyl acetate hydroformylation reaction when it is operated normally and no organic peroxide is added.

[0030] 50 g of allyl acetate raw material (containing 0.001 mmol of triphenylphosphine and 2×10 -4mmol acetylacetonato carbonyl rhodium complex catalyst) was initially replaced with 5 barG nitrogen five times. Synthesis gas with a 1:1 ratio of hydrogen and carbon monoxide was then introduced into the autoclave until the pressure reached 60 barG. Simultaneously, the reaction system was heated to 90°C. The reaction was initiated and, throughout the semi-batch reaction, synthesis gas with a 1:1 ratio of hydrogen and carbon monoxide was continuously introduced into the autoclave to maintain the system pressure at 60 barG. Heat transfer was used to maintain the temperature of the reactor at 90°C. Samples were continuously taken throughout the reaction for gas chromatography analysis to determine the conversion of the allyl acetate feedstock. The conversion gradually increased with reaction time. After 2 hours of reaction, the conversion of allyl acetate was 54.2%. After approximately 6 hours of reaction, the conversion reached 98.1%, with a selectivity of 90.8% for the target hydroformylation product.

[0031] Comparative Example 2

[0032] A mixture of 50 g of allyl acetate raw material (50 wt.%) and the target product of allyl acetate hydroformylation (50 wt.%) (containing 0.001 mmol of triphenylphosphine and 2×10 -4 mmol acetylacetonate carbonyl rhodium complex catalyst) was first replaced with 5 barG nitrogen five times, and then the test cell of the VSP2 was filled with synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 to 50 barG. The materials in the test cell were heated and stirred at 300 rpm. When the temperature reached 90°C, the external heating of the materials in the VSP2 test cell was cut off and the device entered the adiabatic mode. At the same time, once the system pressure fell below 58 bar after entering the adiabatic mode, the test cell was immediately replenished with synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 to 60 barG.

[0033] Comparative Example 2 is used to simulate how the temperature and pressure of the reaction system will change when the conversion rate of the allyl acetate hydroformylation reaction reaches 50% if the system fails to transfer heat. Figure 1 As shown, as the material temperature within the VSP2 test cell increases, the pressure within the cell gradually rises. At temperatures approaching 90°C, the hydroformylation reaction of allyl acetate begins to clearly occur, and the pressure rise rate slows. As the system enters adiabatic mode, the material temperature within the VSP2 test cell slowly rises, the pressure gradually decreases, and the frequency of gas replenishment increases. When the temperature reaches 220°C, the pressure no longer decreases due to high-temperature deactivation of the complex catalyst. However, the temperature has already exceeded the significant secondary decomposition temperature of allyl acetate, 194°C, initiating secondary reactions of the raw material allyl acetate. The temperature and pressure within the VSP2 test cell continue to rise, gradually spiraling out of control, ultimately exceeding the upper detection limit of the VSP2 equipment.

[0034] Example 1

[0035] 50 g of allyl acetate raw material (containing 0.001 mmol of triphenylphosphine and 2×10 -4 mmol acetylacetonato carbonyl rhodium complex catalyst and 0.03 mmol tert-butyl hydroperoxide). After replacing the atmosphere with 5 barG nitrogen five times, the autoclave was filled with synthesis gas at a 1:1 ratio of hydrogen to carbon monoxide until the pressure reached 60 barG. Simultaneously, the reaction system was heated to 90°C. The reaction was initiated and, throughout the semi-batch reaction, the autoclave was continuously fed with synthesis gas at a 1:1 ratio of hydrogen to carbon monoxide to maintain the system pressure at 60 barG. Heat transfer was used to maintain the reactor temperature at 90°C. Samples were continuously taken throughout the reaction for gas chromatography analysis to determine the conversion of the allyl acetate feedstock. After 2 hours of reaction, the conversion of allyl acetate was 37.6%. After 3 hours of reaction, the conversion was 38.9%, with no significant increase thereafter. After 6 hours of reaction, the conversion of allyl acetate was 39.2%, with a selectivity of 27.8% for the target hydroformylation product. The content of organic peroxide in the solution after the reaction was titrated by iodine titration, and it was found that tert-butyl hydroperoxide had been completely decomposed.

[0036] The apparent decomposition temperature of the organic peroxide tert-butyl hydroperoxide selected in Example 1 is 78.5° C., compared with Comparative Example 1. When the apparent decomposition temperature of the selected organic peroxide is lower than or close to the operating temperature of the hydroformylation reaction, the organic peroxide will undergo a decomposition reaction during normal production to produce oxygen free radicals that gradually poison the triphenylphosphine complex catalyst, thereby affecting the normal hydroformylation production process.

[0037] Example 2

[0038] 50 g of allyl acetate raw material (containing 0.001 mmol of triphenylphosphine and 2×10 -4mmol acetylacetonato carbonyl rhodium complex catalyst and 0.03 mmol isopropylbenzene hydroperoxide). After replacing the atmosphere with 5 barG nitrogen five times, the autoclave was filled with synthesis gas at a 1:1 ratio of hydrogen to carbon monoxide until the pressure reached 60 barG. Simultaneously, the reaction system was heated to 90°C. The reaction was initiated and continued throughout the semi-batch reaction, maintaining the system pressure at 60 barG by continuously flowing synthesis gas at a 1:1 ratio of hydrogen to carbon monoxide into the autoclave. Heat transfer was used to maintain the reactor temperature at 90°C. Samples were continuously taken throughout the reaction for gas chromatography analysis to determine the conversion of the allyl acetate feedstock. After 2 hours of reaction, the conversion of allyl acetate was 54.1%. After approximately 6 hours of reaction, the conversion reached 97.4%, with a selectivity of 91.3% for the target hydroformylation product.

[0039] The apparent decomposition temperature of the organic peroxide selected in Example 2, cumene hydroperoxide, is 110°C. Compared with Comparative Example 1, when the apparent decomposition temperature of the selected organic peroxide is significantly higher than the operating temperature of the hydroformylation reaction by about 20°C, the addition of the organic peroxide to the reaction system does not significantly affect the conversion rate and selectivity of allyl acetate.

[0040] Example 3

[0041] A mixture of 50 g of allyl acetate raw material (50 wt.%) and the target product of allyl acetate hydroformylation (50 wt.%) (containing 0.001 mmol of triphenylphosphine and 2×10 -4 mmol acetylacetonate carbonyl rhodium complex catalyst and 0.03 mmol isopropylbenzene hydroperoxide), after first replacing with 5 barG nitrogen five times, the test cell of VSP2 was filled with synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 to 50 barG, the materials in the test cell were heated and stirred at 300 rpm. When the temperature reached 90°C, the external heating of the materials in the VSP2 test cell was cut off and the device entered the adiabatic mode. At the same time, once the system pressure fell below 58 bar after entering the adiabatic mode, the test cell was immediately supplemented with synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 to 60 barG.

[0042] The results of Example 3 are as follows Figure 2As shown in the figure: as the material temperature in the VSP2 test cell increases, the pressure in the VSP2 test cell gradually increases. When the temperature approaches 90°C, the allyl acetate hydroformylation reaction begins to occur significantly, and the pressure rise rate slows down. As the system enters the adiabatic mode, the material temperature in the VSP2 test cell begins to rise slowly, and the pressure gradually decreases to below 58 barG. Synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 is added to the VSP2 test cell to 60 barG. Subsequently, when the temperature rises to 110°C, the obvious decomposition temperature of isopropylbenzene hydroperoxide, the complex catalyst is gradually poisoned, the system temperature rise rate slows down, and the air intake rate slows down. When the temperature rises to 116°C, the complex catalyst is completely deactivated. At this time, the temperature has not reached the TD24 temperature of the hydroformylation product of 147°C, and the system no longer releases heat, ensuring that the system can be safely stopped when the heat transfer failure condition occurs.

[0043] It can be seen that under the same reaction conditions as those in Comparative Example 2, by adding 30 times the amount of cumene hydroperoxide as the triphenylphosphine complex catalyst to the reaction system, the catalyst can be poisoned in time when the system fails to transfer heat, thereby avoiding system runaway and causing high temperature and high pressure.

[0044] Example 4

[0045] A mixture of 50 g of allyl acetate raw material (50 wt.%) and the target product of allyl acetate hydroformylation (50 wt.%) (containing 0.001 mmol of triphenylphosphine and 2×10 -4 mmol acetylacetonate carbonyl rhodium complex catalyst and 0.03 mmol 1,1-di-tert-butyl cyclohexyl peroxide), first replaced with 5 barG nitrogen five times, then the test cell of VSP2 was filled with synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 to 50 barG, the materials in the test cell were heated and stirred at 300 rpm. When the temperature reached 90°C, the external heating of the materials in the VSP2 test cell was cut off and the device entered the adiabatic mode. At the same time, once the system pressure fell below 58 bar after entering the adiabatic mode, the test cell was immediately supplemented with synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 to 60 barG.

[0046] As the temperature of the material within the VSP2 test cell increased, the pressure within the cell gradually increased. At temperatures approaching 90°C, the hydroformylation reaction of allyl acetate began to clearly occur, and the rate of pressure rise slowed. As the system entered adiabatic mode, the temperature within the VSP2 test cell began to slowly rise, and the pressure gradually decreased to below 58 barG. Syngas (a 1:1 molar ratio of hydrogen to carbon monoxide) was added to the VSP2 test cell to 60 barG, and the rate of temperature rise gradually increased. When the temperature exceeded 148°C, the apparent decomposition temperature of 1,1-di-tert-butylcyclohexylperoxide, the rate of temperature rise began to slow. However, since the temperature had already exceeded the TD24 temperature of the hydroformylation product, 147°C, the rate of temperature rise slowly increased again after exceeding 158°C. The temperature continued to rise, initiating a secondary decomposition reaction of allyl acetate. This secondary reaction within the system gradually spiraled out of control, ultimately exceeding the upper detection limit of the VSP2 equipment, with both the temperature and pressure exceeding the upper detection limit.

[0047] It can be seen that under the same reaction conditions as those in Comparative Example 2, after adding 30 times the amount of 1,1-di-tert-butyl cyclohexyl peroxide as the triphenylphosphine complex catalyst to the reaction system, since the obvious decomposition temperature of 1,1-di-tert-butyl cyclohexyl peroxide is higher than the TD24 temperature of the hydroformylation product of 147°C, after the system undergoes heat transfer failure, although the oxygen free radicals generated by the decomposition of 1,1-di-tert-butyl cyclohexyl peroxide at around 148°C can poison the catalyst and stop the main hydroformylation reaction, the secondary decomposition reaction of the hydroformylation product has already been triggered at this time, so it is still impossible to avoid the runaway secondary reaction and cause the system to overheat and overpressure.

[0048] Example 5

[0049] A mixture of 50 g of allyl acetate raw material (50 wt.%) and the target product of allyl acetate hydroformylation (50 wt.%) (containing 0.001 mmol of triphenylphosphine and 2×10 -4 mmol acetylacetonate carbonyl rhodium complex catalyst and 0.001 mmol isopropylbenzene hydroperoxide), after first replacing with 5 barG nitrogen five times, the test cell of VSP2 was filled with synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 to 50 barG, the materials in the test cell were heated and stirred at 300 rpm. When the temperature reached 90°C, the external heating of the materials in the VSP2 test cell was cut off and the device entered the adiabatic mode. At the same time, once the system pressure fell below 58 bar after entering the adiabatic mode, the test cell was immediately supplemented with synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 to 60 barG.

[0050] As the temperature of the material in the VSP2 test cell increased, the pressure in the VSP2 test cell gradually increased. When the temperature approached 90°C, the hydroformylation reaction of allyl acetate began to occur significantly, and the pressure rise rate slowed. As the system entered adiabatic mode, the temperature of the material in the VSP2 test cell began to rise slowly, and the pressure gradually decreased to below 58 barG. Synthesis gas with a 1:1 molar ratio of hydrogen and carbon monoxide was added to the VSP2 test cell to 60 barG. Subsequently, when the temperature rose to 110°C, the obvious decomposition temperature of isopropylbenzene hydroperoxide, the complex catalyst was gradually poisoned, the system temperature rise rate slowed down, and the air intake rate slowed down. However, when the temperature rose to 116°C, the system continued to heat up at a relatively low rate. After approximately 110 minutes, the system temperature reached the temperature of the hydroformylation product TD24, 147°C. The temperature continued to rise, initiating a secondary decomposition reaction of allyl acetate. The secondary reaction of the material in the system gradually became uncontrolled, and ultimately the temperature and pressure exceeded the detection limit of the VSP2 equipment.

[0051] It can be seen that under the same reaction conditions as those in Comparative Example 2, by adding 1 times the amount of cumene hydroperoxide as the triphenylphosphine complex catalyst to the reaction system, although the decomposition of cumene hydroperoxide at 110° C. to produce oxygen free radicals can poison part of the catalyst, since the selectivity of the decomposition of organic peroxide to produce oxygen is not 100% and the selectivity is greatly affected by the pH of the system, if less organic peroxide is added, it is still impossible to avoid the runaway secondary reaction and the resulting overtemperature and overpressure of the system.

[0052] Example 6

[0053] To a 100 ml VSP2 test cell, 50 g of allyl acetate raw material (47.5 wt.%), a mixture of allyl acetate hydroformylation target product (47.5 wt.%) and cumene hydroperoxide (5 wt.%) (containing 0.001 mmol of triphenylphosphine and 2×10 -4 mmol acetylacetonate carbonyl rhodium complex catalyst), after first replacing with 5 barG nitrogen five times, the test cell of the VSP2 was filled with synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 to 50 barG, the materials in the test cell were heated and stirred at 300 rpm. When the temperature reached 90°C, the external heating of the materials in the VSP2 test cell was cut off and the device entered the adiabatic mode. At the same time, once the system pressure fell below 58 bar after entering the adiabatic mode, the test cell was immediately supplemented with synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 to 60 barG.

[0054] As the temperature of the material in the VSP2 test cell increased, the pressure in the VSP2 test cell gradually increased. When the temperature approached 90°C, the allyl acetate hydroformylation reaction began to occur significantly, and the pressure rise rate slowed. As the system entered adiabatic mode, the material temperature in the VSP2 test cell began to slowly increase, and the pressure gradually decreased to below 58 barG. Synthesis gas with a molar ratio of hydrogen and carbon monoxide of 1:1 was added to the VSP2 test cell to 60 barG. Subsequently, when the temperature rose to about 110°C, the reaction aspiration phenomenon obviously stopped, but the temperature continued to rise slowly. After approximately 154 minutes, the system temperature reached the temperature of the hydroformylation product TD24, 147°C. The temperature continued to rise, and a secondary decomposition reaction of allyl acetate was initiated. The secondary reaction of the material in the system gradually got out of control, and ultimately the temperature and pressure exceeded the detection limit of the VSP2 equipment.

[0055] It can be seen that under the same reaction conditions as Comparative Example 2, by adding 2.5 g of cumene hydroperoxide to the reaction system, although the cumene hydroperoxide decomposes to produce oxygen free radicals at 110° C. and can completely stop the hydroformylation reaction, due to the generally high secondary decomposition heat of organic peroxides (the secondary decomposition heat release of cumene hydroperoxide itself reaches 1520 J / g), adding too much organic peroxide will also cause a large temperature rise in the system, thereby potentially triggering a secondary decomposition reaction of the hydroformylation product, resulting in a runaway secondary reaction and causing overtemperature and overpressure in the system. At the same time, adding too much organic peroxide will also increase the separation load of the product.

Claims

1. A method for the hydroformylation of allyl acetate that can avoid overheating of the equipment due to runaway reaction, characterized in that: Allyl acetate reacts with a mixture of hydrogen and carbon monoxide in the presence of a catalyst. A suitable organic peroxide is added to the hydroformylation reaction system. When the system temperature rises abnormally, the active oxygen free radicals generated by the high-temperature decomposition of the organic peroxide are used to poison the catalyst in a timely manner, thereby preventing the system temperature from continuing to rise. The catalyst is a complex catalyst composed of a metal rhodium active center and a phosphine-based ligand, wherein the metal rhodium active center is selected from one or more of acetylacetonato carbonyl rhodium and rhodium trichloride, and the phosphine-based ligand is any one or a combination of at least two of triphenylphosphine, trialkylphosphine, dimethylphenylphosphine, tri(o-methylphenyl)phosphine, diphenyl-2-pyridylphosphine, triarylphosphite, 1,3,5-triaza-7-phosphatricyclodecane, monooxyacylbisphosphine ligand, phosphite bisphosphine ligand, xanthene-type bisphosphine ligand, and dialkyldiarylphosphine ligand; The organic peroxide has an apparent decomposition temperature that is 10 to 50° C. higher than the allyl acetate hydroformylation reaction temperature and 10° C. or higher lower than the TD24 temperature of the allyl acetate hydroformylation product. The organic peroxide is selected from tert-butyl hydroperoxide, ethylbenzene hydroperoxide, and / or isopropylbenzene hydroperoxide. The molar ratio of the organic peroxide to the phosphine-based ligand is 30 to 50:

1.

2. The method according to claim 1, characterized in that The molar ratio of the rhodium metal active center to the raw material allyl acetate is 3×10 -7 ~8×10 -6 :

1.

3. The method according to claim 1 or 2, characterized in that The molar ratio of the phosphine-based ligand to the metal rhodium active center is 3 to 100:

1.

4. The method according to claim 1, characterized in that The reaction temperature of the allyl acetate hydroformylation reaction is 60-150°C.

5. The method according to claim 4, characterized in that: The reaction temperature of the allyl acetate hydroformylation reaction is 80-100°C.

6. The method according to claim 1, characterized in that The molar ratio of hydrogen to carbon monoxide in the mixed gas is 0.8 to 1.5:

1.

7. The method according to claim 1, characterized in that The reaction pressure of the allyl acetate hydroformylation reaction is 50-100 barG.

Images