Method for determining the deactivation temperature and deactivation characteristics of a hydroformylation catalyst

Abstract

This invention provides a method for determining the deactivation temperature and deactivation characteristics of a hydroformylation catalyst, comprising: S1. preparing a hydroformylation reaction solution; S2. measuring the reaction solution and placing it in an adiabatic testing instrument to simulate a hydroformylation reaction, stopping the heating when the temperature reaches T0 and incubating the reaction under adiabatic conditions; recording the temperature change and obtaining the highest temperature T. m S3. After cooling the test ball, remove half of the reactant material, add the hydroformylation reaction raw material, and heat up to simulate the hydroformylation reaction. When the temperature reaches T1, stop heating and perform an adiabatic reaction. Record the highest temperature T. mf S4. Compare T1 and T m and T mf If T mf =T1, catalyst deactivation temperature is T m Irreversible inactivation; if T mf =T m The catalyst deactivation temperature is T m Reversible inactivation; if T mf >T m Remove the material from the test sphere and repeat steps S2 to S4. The judgment method of this invention has a short testing cycle, high safety, and eliminates the need for sample separation and component analysis. It provides guidance for research on catalyst operating limits and the selection of homogeneous catalyst recovery temperatures.

Description

Technical Field

[0001] This invention relates to the technical field of catalyst thermal safety analysis, specifically to a method for determining the deactivation temperature and deactivation characteristics of a hydroformylation catalyst. Background Technology

[0002] Hydroformylation, also known as carbonyl synthesis, is a process in which carbonylating raw materials react with CO and H2 under the action of a hydroformylation catalyst to simultaneously add hydrogen atoms and formyl groups to unsaturated bonds, generating two isomeric aldehydes with one more carbon atom than the original olefin, or to activate and decompose an acid anhydride molecule in situ into an aromatic carbonyl group and one carbon atom. With the development of one-carbon chemistry, hydroformylation reactions involving CO have gradually increased. Hydroformylation reactions are usually homogeneous catalytic reactions that occur in the presence of a transition metal complex catalyst, and the reaction is generally exothermic. The catalyst deactivation temperature is an important indicator for evaluating catalyst performance and a key parameter used in the concentration and recovery design of homogeneous catalysts and reaction hazard assessment. Determining the catalyst deactivation temperature not only allows for precise selection of the upper temperature limit for reaction liquid separation and concentration, and the reasonable setting of the upper temperature limit interlock value to avoid high-temperature concentration or high-temperature reaction deactivation of the catalyst, but also allows for more accurate calculation of the highest temperature the system can reach after a runaway hydroformylation reaction, precisely guiding the design of process protection measures, avoiding excessive process protection design and release costs, and reducing investment costs.

[0003] Currently, there are no publicly reported methods for investigating the deactivation temperature of hydroformylation catalysts. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a method for determining the deactivation temperature and deactivation characteristics of hydroformylation catalysts using only two or more sets of unconventional experiments with a thermal safety testing instrument. This method has a short experimental cycle, requires fewer materials, and offers high operational safety. Furthermore, it eliminates the need for catalyst separation and component content analysis of the tested samples, providing clear guidance for selecting the upper limit of catalyst operation, choosing the recovery temperature of homogeneous catalysts, studying reaction hazards in relevant reaction scenarios, and designing venting systems.

[0005] To achieve the objectives of this invention, the following technical solution is adopted:

[0006] This invention provides a method for determining the deactivation temperature and deactivation characteristics of a hydroformylation catalyst, characterized by comprising the following steps:

[0007] S1. Mix fresh hydroformylation catalyst and hydroformylation reaction raw materials to prepare hydroformylation reaction solution;

[0008] S2. Measure the prepared hydroformylation reaction solution and load it into the test ball of the adiabatic testing instrument. Then, introduce synthesis gas into the test ball and start heating to simulate the hydroformylation reaction. When the temperature reaches T0, stop heating and continue the reaction under adiabatic conditions.

[0009] Record the temperature change of the material inside the test sphere and obtain the highest temperature T reached inside the test sphere. m ;

[0010] S3. After cooling the test sphere to room temperature, remove half of the reaction material inside the test sphere, then add an equal amount of hydroformylation reaction raw material, and introduce syngas into the test sphere. Continue to heat to simulate the hydroformylation reaction. When the temperature reaches T1, stop heating and maintain the reaction under adiabatic conditions; wherein, T1 is taken from (T m +T0) / 2~(3T m +T0) / 4;

[0011] Record the temperature change of the material inside the test sphere and obtain the highest temperature T reached inside the test sphere. mf ;

[0012] S4. Compare T1 and T m and T mf ;

[0013] If T mf =T1, then the deactivation temperature of the hydroformylation catalyst is T. m The catalyst undergoes irreversible deactivation;

[0014] If T mf =T m The deactivation temperature of the hydroformylation catalyst is T. m The catalyst undergoes reversible deactivation;

[0015] If T mf >T m Remove the material from the test ball and repeat steps S2 to S4 above.

[0016] In some specific implementations, in S2, nitrogen is used to purge the test sphere 1 to 10 times before introducing synthesis gas.

[0017] In some specific embodiments, the pressure of the synthesis gas introduced into the test sphere is 20 to 200 barG;

[0018] The molar ratio of hydrogen to carbon monoxide in the synthesis gas is 0.5 to 2:1.

[0019] In a specific embodiment of the present invention, the hydroformylation catalyst is a complex catalyst composed of rhodium metal as the active center and phosphine-based ligands;

[0020] Preferably, the molar ratio of the phosphine-based ligand to the active center rhodium is 3 to 100:1.

[0021] In some specific embodiments, the phosphine ligand is any one or a combination of triphenylphosphine, trialkylphosphine, dimethylphenylphosphine, tris(o-methylphenyl)phosphine, diphenyl-2-pyridiniumphosphine, triaryl phosphite, phosphine heterocyclic ligand, 1,3,5-triaza-7-phosphatricyclodecane, monooxyacyl bisphosphine ligand, phosphite bisphosphine ligand, oxanthracene-type bisphosphine ligand, and dialkyldiarylphosphine ligand; preferably triphenylphosphine;

[0022] The metallic rhodium exists in the form of rhodium acetylacetone and / or rhodium polychloride.

[0023] In some specific embodiments, the hydroformylation reaction feedstock is an olefin and / or an olefin derivative.

[0024] In some specific embodiments, based on the rhodium metal in the hydroformylation catalyst, the molar ratio of the hydroformylation catalyst to the hydroformylation reaction raw material is 1:100 to 25000, preferably 1:5000 to 1:10000.

[0025] In the judgment method provided by the present invention, in S2 and S3, the heating process inside the test ball starts from room temperature and increases to the required temperature at a rate of 5 to 20 K / min.

[0026] In the determination method provided by the present invention, the adiabatic testing instrument is selected from adiabatic accelerated calorimeter, VSP2, RSD, Thi-TEC, SEDEX or C80.

[0027] The technical solution provided by this invention has the following beneficial effects:

[0028] The method provided by this invention can determine the deactivation temperature and deactivation characteristics of hydroformylation catalysts using only two or more sets of unconventional experiments with a thermal safety testing instrument. It has a short experimental cycle, requires less material, and is highly safe to operate.

[0029] The judgment method of the present invention does not require catalyst separation and component content analysis of the tested sample, and has a clear guiding role in the selection of the upper limit of catalyst operation, the selection of homogeneous catalyst recovery temperature, the study of reaction hazards in related reaction scenarios, and the design of venting systems. Detailed Implementation

[0030] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The term "and / or" may be used herein to include any and all combinations of one or more of the associated listed items.

[0032] This invention provides a method for determining the deactivation temperature and deactivation characteristics of a hydroformylation catalyst, comprising the following steps:

[0033] S1. Mix fresh hydroformylation catalyst and hydroformylation reaction raw materials to prepare hydroformylation reaction solution;

[0034] S2. Measure the prepared hydroformylation reaction solution and load it into the test ball of the adiabatic testing instrument. Then, introduce synthesis gas into the test ball and start heating to simulate the hydroformylation reaction. When the temperature reaches T0, stop heating and continue the reaction under adiabatic conditions.

[0035] Record the temperature change of the material inside the test sphere and obtain the highest temperature T reached inside the test sphere. m ;

[0036] S3. After cooling the test sphere to room temperature, remove half of the reaction material inside the test sphere, then add an equal amount of hydroformylation reaction raw material, and introduce syngas into the test sphere. Continue to heat to simulate the hydroformylation reaction. When the temperature reaches T1, stop heating and maintain the reaction under adiabatic conditions; wherein, T1 is taken from (T m +T0) / 2~(3T m +T0) / 4;

[0037] Record the temperature change of the material inside the test sphere and obtain the highest temperature T reached inside the test sphere. mf ;

[0038] S4. Compare T1 and T m and T mf ;

[0039] If T mf If T = T1, then the deactivation temperature of the hydroformylation catalyst is determined to be T. m The catalyst undergoes irreversible deactivation;

[0040] If T mf =T m Then the deactivation temperature of the hydroformylation catalyst is determined to be T. m The catalyst undergoes reversible deactivation;

[0041] If T mf >T m Remove all the material from the test ball and repeat steps S2 to S4 above.

[0042] In a specific embodiment of the judgment method S4 of the present invention, when comparing T1 and T m and T mf At that time, T mf >T m The specific steps are as follows:

[0043] S4.1 Measure the prepared hydroformylation reaction solution and load it into the test sphere of the adiabatic testing instrument. Introduce synthesis gas into the test sphere and begin heating to simulate the hydroformylation reaction. When the temperature reaches the T obtained in S2... m Then stop heating and continue the reaction under adiabatic conditions;

[0044] Record the temperature change of the material inside the test sphere and obtain the highest temperature T reached inside the test sphere. m ';

[0045] S4.2 After cooling the test sphere to room temperature, remove half of the reaction material from the test sphere, then add an equal amount of hydroformylation reaction raw material, and introduce syngas into the test sphere. Continue heating to simulate the hydroformylation reaction. When the temperature reaches T1', stop heating and maintain the reaction under adiabatic conditions; wherein, T1' is taken from (T m '+T m ) / 2~(3T m '+T m ) / 4;

[0046] Record the temperature change of the material inside the test sphere and obtain the highest temperature T reached inside the test sphere. mf ';

[0047] S4.3 Comparison with T1' and T m 'and T mf ';

[0048] If T mf If '=T1', then the deactivation temperature of the hydroformylation catalyst is T. m The catalyst undergoes irreversible deactivation.

[0049] If T mf '=T m 'Then the deactivation temperature of the hydroformylation catalyst is T'. m The catalyst undergoes reversible deactivation.

[0050] If T mf '>T m Remove the material from the test ball and repeat the above three steps.

[0051] In the judgment method provided by this invention, in S3, the material temperature inside the test sphere reaches the highest temperature T. mThen, fresh material is added to the test sphere, and the initial adiabatic temperature is raised to a higher temperature T1 before the adiabatic reaction is repeated. This ensures that when the temperature inside the test sphere rises again from T1 to T1 under adiabatic conditions, the reaction proceeds smoothly. mf This eliminates the possibility that the catalyst is in T m The temperature inside the test sphere reached T due to the loss of catalytic activity. m The fact that the concentration no longer increased also ruled out the possibility of reaction cessation due to excessively low concentrations after the consumption of reactants; then, in S4, by comparing T1 and T... m and T mf The size of the catalyst indicates its state.

[0052] In some specific embodiments, in S2, nitrogen is used to purge the test sphere 1 to 10 times before introducing synthesis gas.

[0053] In some specific embodiments, the pressure of the syngas introduced into the test sphere is 20 to 200 barG, for example, 50 barG, 100 barG, or 150 barG; the molar ratio of hydrogen to carbon monoxide in the syngas is 0.5 to 2:1, for example, 1:1 or 1.5:1.

[0054] In the determination method of the present invention, the hydroformylation catalyst is a complex catalyst composed of metallic rhodium as the active center and a phosphine-based ligand; preferably, the molar ratio of the phosphine-based ligand to the active center rhodium is 3 to 100:1, for example, 10:1, 20:1, 30:1, 50:1, 60:1, 80:1, 90:1.

[0055] Specifically, the phosphine ligand is any one or a combination of triphenylphosphine, trialkylphosphine, dimethylphenylphosphine, tris(o-methylphenyl)phosphine, diphenyl-2-pyridiniumphosphine, triaryl phosphite, phosphine heterocyclic ligand, 1,3,5-triaza-7-phosphatricyclodecane, monooxyacyl bisphosphine ligand, phosphite bisphosphine ligand, oxanthracene-type bisphosphine ligand, and dialkyldiarylphosphine ligand; preferably triphenylphosphine;

[0056] The metallic rhodium exists in the form of rhodium acetylacetone and / or rhodium polychloride.

[0057] In the determination method provided by the present invention, the raw materials for the hydroformylation reaction are olefins and / or olefin derivatives.

[0058] In the determination method provided by the present invention, based on the rhodium metal in the hydroformylation catalyst, the molar ratio of the hydroformylation catalyst to the hydroformylation reaction raw material is 1:100 to 25000, for example, 1:500, 1:1000, 1:1500, 1:2000, 1:2500, 1:3000, 1:3500, 1:4000, 1:4500, 1:12000, 1:15000, 1:17000, 1:20000, 1:22000, 1:23000; preferably 1:5000 to 10000, for example, 1:6000, 1:7000, 1:8000.

[0059] In the judgment method provided by the present invention, in S2 and S3, the heating process inside the test ball starts from room temperature and increases to the required temperature at a rate of 5 to 20 K / min, for example, 10 K / min or 15 K / min.

[0060] In some specific implementations, the adiabatic testing instrument is selected from adiabatic accelerated calorimeter, VSP2, RSD, Thi-TEC, SEDEX, C80, etc.

[0061] The present invention will be further illustrated below with specific examples, but it should not be construed as the present invention being limited to these examples.

[0062] Where specific experimental steps or conditions are not specified in the examples, they can be performed according to the corresponding conventional experimental steps or conditions in this technical field. Reagents whose manufacturers are not specified are all conventional reagents already available in this field.

[0063] Example 1

[0064] The deactivation temperature and deactivation characteristics of the hydroformylation catalyst are determined according to the following steps, including:

[0065] S1. Allyl acetate, rhodium trichloride and triphenylphosphine are mixed in a molar ratio of 25000:1:100 to prepare a hydroformylation reaction solution;

[0066] S2. Measure 4g of the prepared hydroformylation reaction solution and place it into the test sphere of the adiabatic accelerated calorimeter (ARC). Replace the sphere with nitrogen 1 to 10 times. Then, maintain the pressure of the test sphere at 50 barG by adjusting the opening of the inlet valve of the synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:1). Start heating the material in the test sphere from room temperature at a rate of 10K / min to simulate the hydroformylation reaction. Stop heating when the temperature reaches the normal operating temperature (T0) of 110℃ for hydroformylation of allyl acetate and continue the reaction under adiabatic conditions.

[0067] The adiabatic accelerating calorimeter was adjusted to adiabatic tracking mode to record the temperature changes of the material in the test sphere and obtain the highest temperature reached inside the test sphere (T). m The temperature is 243℃.

[0068] S3. Cool the material inside the test ball of the adiabatic accelerated calorimeter to room temperature and remove 2g of the test material from the test ball. Then add 2g of allyl acetate into the test ball and replace the gas inside the test ball with nitrogen 1 to 10 times. Then maintain the pressure of the test ball at 50 barG by adjusting the opening of the inlet valve of the synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:1).

[0069] The material inside the test sphere was heated from room temperature to 180℃ (T1) at a rate of 10K / min, then the heating was stopped and the reaction continued under adiabatic conditions. The adiabatic accelerated calorimeter was adjusted to adiabatic tracking mode, and the temperature change of the material inside the test sphere was recorded to obtain the highest temperature reached inside the test sphere (T1). mf The temperature is 180℃.

[0070] S4. Compare T1 and T above. m and T mf ;

[0071] T1 = T mf The rhodium trichloride hydroformylation catalyst with triphenylphosphine as a ligand will undergo irreversible deactivation at 243℃ (deactivation temperature) when catalyzing the hydroformylation reaction of allyl acetate.

[0072] Example 2

[0073] The deactivation temperature and deactivation characteristics of the hydroformylation catalyst are determined according to the following steps, including:

[0074] S1. A fresh hydroformylation catalyst is obtained by mixing rhodium acetylacetone and dimethylphenylphosphine in a molar ratio of 1:3.

[0075] The hydroformylation reaction feedstock was prepared by mixing n-octane and n-octene in a molar ratio of 2:1.

[0076] The above-mentioned fresh hydroformylation catalyst (based on the amount of rhodium in the catalyst) is mixed with the hydroformylation reaction raw materials at a molar ratio of 1:100 to prepare a hydroformylation reaction solution.

[0077] S2. Measure 50g of the prepared hydroformylation reaction solution and place it into the test ball of VSP2. Replace the gas in the test ball with nitrogen 1 to 10 times. Then, maintain the pressure in the test ball at 110 barG by adjusting the opening of the inlet valve of the synthesis gas (the molar ratio of hydrogen to carbon monoxide is 2:1). Start heating the material in the test ball from room temperature at a rate of 20K / min to simulate the hydroformylation reaction. When the temperature reaches the normal operating temperature (T0) of 120℃, stop heating and continue the reaction under adiabatic conditions.

[0078] The adiabatic accelerating calorimeter was adjusted to adiabatic tracking mode to record the temperature changes in the test sphere and obtain the highest temperature reached inside the test sphere (T). m The temperature is 212℃.

[0079] S3. Cool the material inside the test ball of VSP2 to room temperature and take out 25g of the test material inside the test ball. Then add 25g of the prepared hydroformylation reaction raw material into the test ball. By adjusting the opening of the gas inlet valve of the synthesis gas (the molar ratio of hydrogen to carbon monoxide is 2:1), the pressure of the test ball is always maintained at 110 barG.

[0080] The material inside the test sphere was heated to 185℃ (T1), then the heating was stopped and the reaction continued under adiabatic conditions. VSP2 was adjusted to adiabatic tracking mode to record the temperature change of the reaction inside the test sphere and obtain the highest temperature reached inside the test sphere (T). mf The temperature is 221℃.

[0081] S4. Compare T1 and T above. m and T mf ;

[0082] T mf >T m Then all the material inside the VSP2 test ball will be removed;

[0083] S4.1 Measure 50g of the prepared hydroformylation reaction solution and place it into the test sphere of VSP2. Replace the gas inside the test sphere with nitrogen 1-10 times. Then, maintain the pressure in the test sphere at 110 barG by adjusting the opening of the syngas (hydrogen to carbon monoxide molar ratio of 2:1) inlet valve. Start heating the material inside the test sphere from room temperature at a rate of 20K / min to simulate the hydroformylation reaction, and heat to 212℃ (T). m Then stop heating and continue the reaction under adiabatic conditions;

[0084] The VSP2 was set to adiabatic tracking mode, and the temperature changes in the test sphere were recorded. The highest temperature reached inside the test sphere was 221℃ (T). m ');

[0085] S4.2 After cooling the material inside the VSP2 test sphere to room temperature, remove 25g of the test material from the test sphere, and then add 25g of the prepared hydroformylation reaction raw material into the test sphere. Replace the gas inside the test sphere with nitrogen 1 to 10 times. Then, by adjusting the opening of the syngas (hydrogen to carbon monoxide molar ratio of 2:1) inlet valve, the pressure of the test sphere is always maintained at 110 barG. The material inside the test sphere is heated from room temperature at a rate of 20K / min to simulate the hydroformylation reaction. After heating to 218℃ (T1'), the heating is stopped and the reaction continues under adiabatic conditions.

[0086] The VSP2 was set to adiabatic tracking mode, and the temperature changes in the test sphere were recorded. The highest temperature reached inside the test sphere was 218℃ (T). mf ');

[0087] S4.3 Compare the above T1' and T m and T mf ';

[0088] T mf =T1, the hydroformylation catalyst of acetylacetone rhodium with dimethylphenylphosphine as ligand will undergo irreversible deactivation at 221℃ (deactivation temperature) when catalyzing the hydroformylation of n-octene.

[0089] Example 3

[0090] The deactivation temperature and deactivation characteristics of the hydroformylation catalyst are determined according to the following steps, including:

[0091] S1. A fresh hydroformylation catalyst was obtained by mixing rhodium acetylacetone, triaryl phosphite and 1,3,5-triazine-7-phosphatane in a molar ratio of 1:20:25.

[0092] Isobutane and isobutene were prepared as hydroformylation reaction feedstock in a molar ratio of 1:2.

[0093] The above-mentioned fresh hydroformylation catalyst and hydroformylation reaction raw materials were mixed according to the key component metal rhodium and isobutylene molar ratio of 1:7000 to prepare a hydroformylation reaction solution.

[0094] S2. Measure 6g of the prepared hydroformylation reaction solution and place it into the test ball of the RSD instrument. Replace the gas in the test ball with nitrogen 1 to 10 times. Then, maintain the pressure in the test ball at 200 barG by adjusting the opening of the inlet valve of the synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:2). Start heating the material in the test ball from room temperature at a rate of 5K / min to simulate the hydroformylation reaction. When the temperature reaches the normal operating temperature (T0) of 100℃, stop heating and continue the reaction under adiabatic conditions.

[0095] Adjust the RSD instrument to adiabatic tracking mode, record the temperature change of the reaction in the test sphere, and obtain the highest temperature reached inside the test sphere (T). m The temperature was 193℃.

[0096] S3. Cool the material inside the test ball of the RSD instrument to room temperature and remove 3g of the test material from the test ball. Then add 3g of the prepared reaction raw material into the test ball and replace the gas inside the test ball with nitrogen 1 to 10 times. Then maintain the pressure of the test ball at 200 barG by adjusting the opening of the inlet valve of the synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:2).

[0097] The material inside the test sphere was heated to 169℃ (T1), then the heating was stopped and the reaction continued under adiabatic conditions. The RSD instrument was adjusted to adiabatic tracking mode to record the temperature change of the reaction inside the test sphere, and the highest temperature reached inside the test sphere (T1) was obtained. mf The temperature was 193℃.

[0098] S4. Compare T1 and T above. m and T mf ;

[0099] T mf =T m The acetylacetone rhodium catalyst with triaryl phosphite and 1,3,5-triazine-7-phosphatane as ligands will undergo reversible deactivation at 193°C (deactivation temperature) when catalyzing the hydroformylation of isobutylene.

Claims

1. A method for determining the deactivation temperature and deactivation characteristics of a hydroformylation catalyst, characterized in that, Includes the following steps: S1. Mix fresh hydroformylation catalyst and hydroformylation reaction raw materials to prepare hydroformylation reaction solution; S2. Measure the prepared hydroformylation reaction solution and put it into the test ball of the adiabatic testing instrument. Then, introduce synthesis gas into the test ball and start heating to simulate the hydroformylation reaction. When the temperature reaches T0, stop heating and continue the reaction under adiabatic conditions. Record the temperature change of the material inside the test sphere and obtain the highest temperature T reached inside the test sphere. m ; S3. After cooling the test sphere to room temperature, remove half of the reaction material inside the test sphere, then add an equal amount of the hydroformylation reaction raw material, and introduce synthesis gas into the test sphere. Continue to heat the sphere to simulate the hydroformylation reaction. When the temperature reaches T1, stop heating and maintain the reaction under adiabatic conditions; wherein, T1 is taken from (T m +T0) / 2~(3T) m +T0) / 4; Record the temperature change of the material inside the test sphere and obtain the highest temperature T reached inside the test sphere. mf ; S4. Compare T1 and T m and T mf ; If T mf = T1, then the deactivation temperature of the hydroformylation catalyst is T m The catalyst undergoes irreversible deactivation; If T mf = T m The deactivation temperature of the hydroformylation catalyst is T. m The catalyst undergoes reversible deactivation; If T mf >T m Remove the material from the test ball and repeat steps S2 to S4 above; T0 is the normal operating temperature at which the catalyst can carry out the catalytic reaction.

2. The judgment method according to claim 1, characterized in that, In S2, before introducing synthesis gas into the test sphere, nitrogen is used to purge it 1 to 10 times.

3. The judgment method according to claim 2, characterized in that, The pressure of the synthesis gas introduced into the test sphere is 20~200 barG.

4. The judgment method according to claim 3, characterized in that, The molar ratio of hydrogen to carbon monoxide in the synthesis gas is 0.5 to 2:

1.

5. The judgment method according to any one of claims 1 to 4, characterized in that, The hydroformylation catalyst is a complex catalyst composed of rhodium as the active center and phosphine-based ligands.

6. The judgment method according to claim 5, characterized in that, The molar ratio of the phosphine-based ligand to the active center rhodium is 3~100:

1.

7. The determination method according to claim 5, characterized in that, The phosphine ligand is any one or a combination of triphenylphosphine, trialkylphosphine, dimethylphenylphosphine, tris(o-methylphenyl)phosphine, diphenyl-2-pyridiniumphosphine, triaryl phosphite, phosphine heterocyclic ligand, 1,3,5-triaza-7-phosphatricyclodecane, monooxyacyl bisphosphine ligand, phosphite bisphosphine ligand, oxanthracene-type bisphosphine ligand, and dialkyldiarylphosphine ligand; The metallic rhodium exists in the form of rhodium acetylacetone and / or rhodium polychloride.

8. The determination method according to claim 7, characterized in that, The phosphine-based ligand is triphenylphosphine.

9. The judgment method according to any one of claims 1-4 and 6-8, characterized in that, The hydroformylation reaction feedstock is an olefin and / or an olefin derivative.

10. The determination method according to claim 9, characterized in that, Based on the rhodium metal in the hydroformylation catalyst, the molar ratio of the hydroformylation catalyst to the hydroformylation reaction raw material is 1:100~25000.

11. The determination method according to claim 10, characterized in that, Based on the rhodium metal in the hydroformylation catalyst, the molar ratio of the hydroformylation catalyst to the hydroformylation reaction raw material is 1:5000~10000.

12. The judgment method according to any one of claims 1-4, 6-8, and 10-11, characterized in that, In S2 and S3, the temperature inside the test sphere is increased from room temperature to the required temperature at a rate of 5~20 K / min.

13. The determination method according to claim 12, characterized in that, The adiabatic testing instrument is selected from adiabatic accelerated calorimeter, VSP2, RSD, Thi-TEC, SEDEX or C80.