Method for judging inactivation temperature and inactivation characteristic of hydroformylation catalyst

Abstract

The invention provides a method for judging the inactivation temperature and the inactivation characteristic of a hydroformylation catalyst. The method comprises the following steps: S1, preparing a hydroformylation reaction solution; s2, measuring the reaction liquid, filling the reaction liquid into an adiabatic test instrument to simulate a hydroformylation reaction, and when the temperature is increased to T0, stopping heating and carrying out an adiabatic reaction; recording the temperature change, and obtaining the highest temperature Tm; s3, cooling the test ball, taking out half of a reaction material, adding a hydroformylation reaction raw material, heating to simulate a hydroformylation reaction, stopping heating when the temperature is increased to T1, carrying out an adiabatic reaction, and recording the highest temperature Tmf; s4, comparing T1, Tm and Tmf; if Tmf is equal to T1, the inactivation temperature of the catalyst is Tm, and irreversible inactivation is carried out; if Tmf is equal to Tm, the inactivation temperature of the catalyst is Tm, and reversible inactivation is carried out; if Tmfgt; and Tm, taking out the material in the test ball, and repeating the steps S2-S4. The judgment method disclosed by the invention is short in test period and high in safety, does not need separation and component analysis on a test sample, and has guiding significance on catalyst operation upper limit and homogeneous catalyst recovery temperature selection research.

Description

Technical Field

[0001] The invention relates to the technical field of catalyst thermal safety analysis, and in particular to a method for determining the deactivation temperature and deactivation characteristics of a hydroformylation catalyst. Background Art

[0002] Hydroformylation reaction, also known as carbonyl synthesis reaction, is a process in which the carbonylation raw material, CO and H2, under the action of a hydroformylation catalyst, simultaneously add hydrogen atoms and formyl groups to the unsaturated bonds to generate two isomeric aldehydes with one more carbon atom than the original olefin, or activate the anhydride molecules in situ to decompose them into aromatic carbonyl groups and one carbon atom. With the development of one-carbon chemistry, the number of hydroformylation reactions involving CO has gradually increased. Hydroformylation reactions are usually homogeneous catalytic reactions that occur in the presence of transition metal complex catalysts, and the reaction exotherm is generally large. The deactivation temperature of the catalyst is an important indicator for evaluating catalyst performance, and it is also a key parameter used in the concentration and recovery design of homogeneous catalysts and the reaction hazard assessment. Clarifying the deactivation temperature of the catalyst can not only accurately select the upper temperature limit for separation and concentration of the reaction liquid, reasonably set the upper temperature interlock value of the reaction temperature, and avoid high-temperature concentration or high-temperature reaction deactivation of the catalyst. It can also more accurately calculate the maximum temperature that the system can reach after the hydroformylation reaction system loses control, accurately guide the design of process protection measures, avoid excessive process protection design and venting cost investment, and reduce investment costs.

[0003] Currently, there is no public report on the method for exploring the deactivation temperature of hydroformylation catalysts. Summary of the invention

[0004] In order to solve the above-mentioned problems, the present invention provides a solution for determining the deactivation temperature and deactivation characteristics of a hydroformylation catalyst only through two or more groups of unconventional experiments using a thermal safety testing instrument. The experimental cycle is short, less materials are required, and the operation is safe. At the same time, there is no need to separate the catalyst and analyze the component content of the tested samples, which has a clear guiding role in the selection of the catalyst operating upper limit, the selection of the homogeneous catalyst recovery temperature, the reaction hazard research of related reaction scenarios, and the design of the discharge system.

[0005] In order to achieve the purpose of the present invention, the present invention adopts the following technical solutions:

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

[0007] S1. The fresh hydroformylation catalyst and the hydroformylation reaction raw materials are mixed to prepare a hydroformylation reaction solution;

[0008] S2. The prepared hydroformylation reaction solution is measured and loaded into the test ball of the adiabatic test instrument, and the synthesis gas is introduced into the test ball, and the temperature is raised to simulate the hydroformylation reaction. When the temperature rises to T0, the temperature is stopped and the reaction is continued under adiabatic conditions;

[0009] Record the temperature change of the material in the test ball and obtain the highest temperature T reached in the test ball m ;

[0010] S3. After cooling the test ball to room temperature, take out half of the reaction material in the test ball, add an equal amount of hydroformylation reaction raw materials, and introduce synthesis gas into the test ball, continue to heat up to simulate the hydroformylation reaction, and stop heating when the temperature reaches T1 and continue 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 in the test ball and obtain the highest temperature T reached in the test ball mf ;

[0012] S4. Comparison with 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 is irreversibly deactivated;

[0014] If T mf =T m , then the deactivation temperature of the hydroformylation catalyst is T m , the catalyst is reversibly deactivated;

[0015] If T mf >T m , take out the material in the test ball and repeat the above S2 to S4.

[0016] In some specific embodiments, in S2, before introducing the synthetic gas into the test ball, nitrogen gas is used for replacement 1 to 10 times.

[0017] In some specific embodiments, the pressure of the synthetic gas introduced into the test ball 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 metal rhodium as an active center and a phosphine-based ligand;

[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-based ligand is any one or more combinations 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, and dialkyldiarylphosphine ligand; preferably triphenylphosphine;

[0022] The metal rhodium exists in the form of rhodium acetylacetonate and / or rhodium polychloride.

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

[0024] In some specific embodiments, based on the metal rhodium 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 determination method provided by the present invention, in S2 and S3, the temperature rise process in the test ball starts from room temperature and rises 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 accelerating calorimeter, VSP2, RSD, Thi-TEC, SEDEX or C80.

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

[0028] The judgment method provided by the present invention can judge the deactivation temperature and deactivation characteristics of the hydroformylation catalyst only through two or more groups of unconventional experiments of a thermal safety testing instrument, has a short experimental cycle, requires less materials, and has high operation safety.

[0029] The judgment method of the present invention does not require catalyst separation and component content analysis of the tested samples, and has a clear guiding role in the selection of the catalyst operation upper limit, the selection of the homogeneous catalyst recovery temperature, the reaction hazard research of the relevant reaction scenarios and the design of the discharge system. DETAILED DESCRIPTION

[0030] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

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

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

[0033] S1. The fresh hydroformylation catalyst and the hydroformylation reaction raw materials are mixed to prepare a hydroformylation reaction solution;

[0034] S2. The prepared hydroformylation reaction solution is measured and loaded into the test ball of the adiabatic test instrument, and the synthesis gas is introduced into the test ball, and the temperature is raised to simulate the hydroformylation reaction. When the temperature rises to T0, the temperature is stopped and the reaction is continued under adiabatic conditions;

[0035] Record the temperature change of the material in the test ball and obtain the highest temperature T reached in the test ball m ;

[0036] S3. After cooling the test ball to room temperature, take out half of the reaction material in the test ball, add an equal amount of hydroformylation reaction raw materials, and introduce synthesis gas into the test ball, continue to heat up to simulate the hydroformylation reaction, and stop heating when the temperature reaches T1 and continue 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 in the test ball and obtain the highest temperature T reached in the test ball mf ;

[0038] S4. Comparison with T1 and T m and T mf ;

[0039] If T mf =T1, then the deactivation temperature of the hydroformylation catalyst is determined to be T m , the catalyst is irreversibly deactivated;

[0040] If T mf =T m , then the deactivation temperature of the hydroformylation catalyst is determined to be T m , the catalyst is reversibly deactivated;

[0041] If T mf >T m , take out all the materials in the test ball and repeat the above S2 to S4.

[0042] In the specific implementation of the judgment method S4 of the present invention, when comparing T1 and T m and T mf When T mf >T m , you can follow the steps below:

[0043] S4.1 Take the prepared hydroformylation reaction liquid and put it into the test ball of the insulation test instrument, and introduce synthesis gas into the test ball, and start heating to simulate the hydroformylation reaction. When the temperature rises to T obtained in S2, m Then stop heating and continue the reaction under adiabatic conditions;

[0044] Record the temperature change of the material in the test ball and obtain the highest temperature T reached in the test ball m ';

[0045] S4.2 After cooling the test ball to room temperature, take out half of the reaction material in the test ball, add an equal amount of hydroformylation reaction raw materials, and introduce synthesis gas into the test ball, continue to heat up to simulate the hydroformylation reaction, and stop heating when the temperature reaches T1' and continue the reaction under adiabatic conditions; where T1' is taken from (T m '+T m ) / 2~(3T m '+T m ) / 4;

[0046] Record the temperature change of the material in the test ball and obtain the highest temperature T reached in the test ball mf ';

[0047] S4.3 vs. T1', T m ' and T mf ';

[0048] If T mf '=T1', then the deactivation temperature of the hydroformylation catalyst is T m ', the catalyst is irreversibly deactivated;

[0049] If T mf '=T m ', then the deactivation temperature of the hydroformylation catalyst is T m ', the catalyst is reversibly deactivated;

[0050] If T mf '>T m ', take out the material in the test ball and repeat the above three steps.

[0051] In the judgment method provided by the present invention, in S3, the temperature of the material in the test ball reaches the highest temperature T mAfter that, fresh materials are added to the test ball and the initial adiabatic temperature is raised to a higher temperature T1 and then adiabatic reaction is carried out again to ensure that when the temperature in the test ball rises from T1 to T1 again under adiabatic condition, mf This eliminates the possibility of the catalyst m The temperature inside the test ball reaches T due to loss of catalytic activity m On the other hand, it also eliminates the reaction suspension caused by the low concentration of the reaction raw materials after consumption; then in S4, by comparing T1, T m and T mf The size of can be used to determine the state of the catalyst.

[0052] In some specific embodiments, in S2, before introducing the synthetic gas into the test ball, nitrogen gas is used for replacement 1 to 10 times.

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

[0054] In the determination method of the present invention, the hydroformylation catalyst used is a complex catalyst composed of metal 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-based ligand is any one or more combinations 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, and dialkyldiarylphosphine ligand; preferably triphenylphosphine;

[0056] The metal rhodium exists in the form of rhodium acetylacetonate 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 metal rhodium in the hydroformylation catalyst, the molar ratio of the hydroformylation catalyst to the hydroformylation reaction raw material is 1:100-25000, 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, 1:5000-10000, for example, 1:6000, 1:7000, 1:8000.

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

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

[0061] The present invention is further described below by means of specific examples, but it should not be understood that the present invention is limited thereto.

[0062] Where specific experimental steps or conditions are not specified in the examples, the corresponding conventional experimental steps or conditions in the art can be used. The reagents used without specifying the manufacturer are all conventional reagents available in the art.

[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 were mixed in a molar ratio of 25000:1:100 to prepare a hydroformylation reaction solution;

[0066] S2. 4 g of the prepared hydroformylation reaction solution was taken and placed in the test ball of an adiabatic accelerating calorimeter (ARC), and replaced with nitrogen 1 to 10 times; then the pressure of the test ball was maintained at 50 barG by adjusting the opening of the inlet valve of the synthesis gas (the molar ratio of hydrogen to carbon monoxide was 1:1); the material in the test ball was heated from room temperature at a rate of 10 K / min to simulate the hydroformylation reaction, and the temperature was stopped after the temperature reached 110°C, the normal operating temperature (T0) of allyl acetate hydroformylation, and the reaction was continued under adiabatic conditions;

[0067] Adjust the adiabatic accelerating calorimeter to adiabatic tracking mode, record the temperature change of the material in the test ball, and obtain the highest temperature reached in the test ball (T m ) is 243°C;

[0068] S3. The material in the test ball of the adiabatic accelerating calorimeter is cooled to room temperature and 2 g of the test material in the test ball is taken out, and then 2 g of allyl acetate is added to the test ball, and the gas in the test ball is replaced with nitrogen 1 to 10 times; then the pressure of the test ball is always maintained 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 in the test ball was heated from room temperature to 180°C (T1) at a rate of 10K / min, then the temperature was stopped and the reaction was continued under adiabatic conditions. The adiabatic accelerating calorimeter was adjusted to adiabatic tracking mode, and the temperature change of the material in the test ball was recorded to obtain the highest temperature reached in the test ball (T mf ) is 180°C;

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

[0071] T1=T mf When the rhodium trichloride hydroformylation catalyst with triphenylphosphine as ligand catalyzes the hydroformylation reaction of allyl acetate, it will undergo irreversible deactivation at 243°C (deactivation temperature).

[0072] Example 2

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

[0074] S1. mixing rhodium acetylacetonate and dimethylphenylphosphine in a molar ratio of 1:3 to obtain a fresh hydroformylation catalyst;

[0075] The hydroformylation reaction raw material is prepared by mixing n-octane and n-octene in a molar ratio of 2:1;

[0076] The fresh hydroformylation catalyst (based on the metal rhodium in the catalyst) and the hydroformylation reaction raw materials are mixed at a molar ratio of 1:100 to prepare a hydroformylation reaction liquid;

[0077] S2. 50 g of the prepared hydroformylation reaction liquid is taken and placed in the test ball of VSP2, and the gas in the test ball is replaced with nitrogen for 1 to 10 times; then the pressure of the test ball is always maintained 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); the material in the test ball is heated from room temperature at a rate of 20 K / min to simulate the hydroformylation reaction, and when the temperature is raised to the normal operating temperature (T0) of the reaction of 120°C, the temperature is stopped and the reaction is continued under adiabatic conditions;

[0078] Adjust the adiabatic accelerating calorimeter to adiabatic tracking mode, record the temperature change of the reaction in the test ball, and obtain the maximum temperature reached in the test ball (T m ) is 212°C;

[0079] S3. The material in the test ball of VSP2 was cooled to room temperature and 25 g of the test material in the test ball was taken out, and then 25 g of the prepared hydroformylation reaction raw material was added to the test ball. The pressure of the test ball was always maintained at 110 barG by adjusting the opening of the inlet valve of the synthesis gas (the molar ratio of hydrogen to carbon monoxide was 2:1);

[0080] The material in the test ball is heated to 185°C (T1), then the temperature is stopped and the reaction is continued under adiabatic conditions. VSP2 is adjusted to adiabatic tracking mode, and the temperature change of the reaction in the test ball is recorded to obtain the highest temperature reached in the test ball (T mf ) is 221°C;

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

[0082] T mf >T m , then take out all the materials in the VSP2 test ball;

[0083] S4.1 50g of the prepared hydroformylation reaction liquid is weighed and placed in the test ball of VSP2. The gas in the test ball is replaced with nitrogen for 1 to 10 times. Then, the pressure of the test ball is maintained 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). The material in the test ball is heated from room temperature at a rate of 20K / min to simulate the hydroformylation reaction. The temperature is heated to 212°C (T m ) and then stop heating and continue the reaction under adiabatic conditions;

[0084] The VSP2 was adjusted to the adiabatic tracking mode, and the temperature change of the reaction in the test ball was recorded. The maximum temperature reached in the test ball was 221°C (T m ');

[0085] S4.2 After cooling the material in the VSP2 test ball to room temperature, take out 25g of the test material in the test ball, then add 25g of the prepared hydroformylation reaction raw material into the test ball, and replace the gas in the test ball with nitrogen for 1 to 10 times; then, by adjusting the opening of the 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 110barG, and the material in the test ball is heated from room temperature at a rate of 20K / min to simulate the hydroformylation reaction. After heating to 218°C (T1'), the temperature is stopped and the reaction is continued under adiabatic conditions;

[0086] The VSP2 was adjusted to the adiabatic tracking mode, and the temperature change of the reaction in the test ball was recorded. The highest temperature reached in the test ball was 218°C (T mf ');

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

[0088] T mf '=T1', the hydroformylation catalyst of acetylacetonato rhodium with dimethylphenylphosphine as ligand will be irreversibly deactivated at 221°C (deactivation temperature) when catalyzing the hydroformylation reaction 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. mixing rhodium acetylacetonate, triaryl phosphite and 1,3,5-triaza-7-phosphinotricyclodecane in a molar ratio of 1:20:25 to obtain a fresh hydroformylation catalyst;

[0092] The hydroformylation reaction raw material is prepared by mixing isobutane and isobutylene in a molar ratio of 1:2;

[0093] The fresh hydroformylation catalyst and the hydroformylation reaction raw materials are mixed in a ratio of 1:7000 of the key component metal rhodium to isobutylene to prepare a hydroformylation reaction liquid;

[0094] S2. 6 g of the prepared hydroformylation reaction solution was taken and placed in the test ball of the RSD instrument, and the gas in the test ball was replaced with nitrogen for 1 to 10 times; then the pressure of the test ball was maintained at 200 barG by adjusting the opening of the inlet valve of the synthesis gas (the molar ratio of hydrogen to carbon monoxide was 1:2); the material in the test ball was heated from room temperature at a rate of 5 K / min to simulate the hydroformylation reaction, and when the temperature was raised to the normal operating temperature (T0) of the reaction of 100°C, the temperature was stopped and the reaction was continued under adiabatic conditions;

[0095] Adjust the RSD instrument to adiabatic tracking mode, record the temperature change of the reaction in the test ball, and obtain the maximum temperature reached in the test ball (T m ) is 193°C;

[0096] S3. Cool the material in the test ball of the RSD instrument to room temperature and take out 3g of the test material in the test ball, then add 3g of the prepared reaction raw material into the test ball, and replace the gas in the test ball with nitrogen for 1 to 10 times; then adjust the opening of the inlet valve of the synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1:2) to always maintain the pressure of the test ball at 200barG;

[0097] The material in the test ball is heated to 169°C (T1), then the temperature is stopped and the reaction is continued under adiabatic conditions. The RSD instrument is adjusted to adiabatic tracking mode, and the temperature change of the reaction in the test ball is recorded to obtain the highest temperature reached in the test ball (T mf ) is 193°C;

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

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

Claims

1. A method for determining the deactivation temperature and deactivation characteristics of a hydroformylation catalyst, characterized in that: The following steps are involved: S1. The fresh hydroformylation catalyst and the hydroformylation reaction raw materials are mixed to prepare a hydroformylation reaction solution; S2. The prepared hydroformylation reaction solution is measured and loaded into the test ball of the adiabatic test instrument, and the synthesis gas is introduced into the test ball, and the temperature is raised to simulate the hydroformylation reaction. When the temperature rises to T0, the temperature is stopped and the reaction is continued under adiabatic conditions; Record the temperature change of the material in the test ball and obtain the highest temperature T reached in the test ball m ; S3. After cooling the test ball to room temperature, take out half of the reaction material in the test ball, add an equal amount of the hydroformylation reaction raw material thereto, and introduce synthesis gas into the test ball, continue to heat up to simulate the hydroformylation reaction, and stop heating when the temperature reaches T1 and continue 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 in the test ball and obtain the highest temperature T reached in the test ball mf ; S4. Comparison with T1 and T m and T mf ; If T mf =T1, then the deactivation temperature of the hydroformylation catalyst is T m , the catalyst is irreversibly deactivated; If T mf =T m , then the deactivation temperature of the hydroformylation catalyst is T m , the catalyst is reversibly deactivated; If T mf >T m , take out the material in the test ball and repeat the above S2 to S4.

2. The determination method according to claim 1, characterized in that: In S2, before introducing the synthesis gas into the test ball, nitrogen gas was used for replacement 1 to 10 times.

3. The determination method according to claim 2, characterized in that: The pressure of the synthesis gas introduced into the test ball is 20-200 barG; Preferably, the molar ratio of hydrogen to carbon monoxide in the synthesis gas is 0.5 to 2:

1.

4. The determination method according to any one of claims 1 to 3, characterized in that: The hydroformylation catalyst is a complex catalyst composed of metal rhodium as an active center and a phosphine-based ligand.

5. The determination method according to claim 4, characterized in that: The molar ratio of the phosphine-based ligand to the active center rhodium is 3 to 100:

1.

6. The determination method according to claim 4, characterized in that: The phosphine-based ligand is any one or more 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, and the like; preferably triphenylphosphine; The metal rhodium exists in the form of rhodium acetylacetonate and / or rhodium polychloride.

7. The determination method according to any one of claims 1 to 6, characterized in that: The hydroformylation reaction raw materials are olefins and / or olefin derivatives.

8. The determination method according to claim 7, characterized in that: Based on the metal rhodium 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 10000.

9. The determination method according to any one of claims 1 to 8, characterized in that: In S2 and S3, the temperature inside the test ball is raised from room temperature to the required temperature at a rate of 5 to 20 K / min.

10. The determination method according to claim 9, characterized in that: The adiabatic testing instrument is selected from adiabatic accelerating calorimeter, VSP2, RSD, Thi-TEC, SEDEX or C80.