An octene hydroformylation catalyst composition and method of use thereof

Abstract

The application provides an octene hydroformylation reaction catalyst composition and an application method thereof. The catalyst composition comprises a catalyst, an auxiliary agent and a solvent; wherein the active component of the catalyst comprises at least two of rhodium, cobalt and iridium; the auxiliary agent is a plurality of components; the auxiliary agent A is a phosphine-containing ligand with a general structure P(M1) x (M2) y wherein M1 is a phenyl group, M2 is a cyclohexyl group, x is an integer greater than or equal to 0, y is an integer greater than or equal to 1, and x+y=3; the auxiliary agent B is an epoxyfluoropropane; and the auxiliary agent C is 4-hydroxy-3-nitrophenyl arsenic acid. According to the differences in boiling points and the differences in the combination ability with active metals under different CO concentrations, the present application adjusts the generation of different normal and isomeric aldehydes in the hydroformylation reaction by regulating the ratios of different ligands and metals or changing the process conditions.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic chemical technology, and particularly relates to a catalyst composition for hydroformylation of octene and an application method thereof. BACKGROUND

[0002] In recent years, the market gap of isomeric aldehyde gradually increases. Taking isobutyl aldehyde as an example, with the vigorous development of isobutyl aldehyde downstream industries such as neopentyl glycol, alcohol ester 12, etc., the price of isobutyl aldehyde on the market is steadily rising. How to obtain high-quality, low-cost isomeric aldehyde raw materials has become the research focus of more and more practitioners.

[0003] Patent CN200610147735.2 discloses a catalyst optimization scheme, which can significantly improve the activity of rhodium / triphenylphosphine catalyst and increase the n-iso ratio of product butyraldehyde by adding bisphosphite to the rhodium / triphenylphosphine catalyst system. The process belongs to irreversible adjustment.

[0004] Patent CN88101206A discloses a method for carbonylation of olefinic unsaturated compounds catalyzed by palladium, which mainly catalyzes the carbonylation of olefinic unsaturated compounds by palladium compounds in the presence of organic phosphorus ligands in a protonic acid environment. The product is mainly carboxylic acid, anhydride, or ester compound corresponding to the olefin and solvent, and the isomerization of the corresponding carboxylic acid, anhydride, or ester is not disclosed in the process.

[0005] Patent CN102741209A discloses a method for optimizing reaction parameters, i.e. controlling the n-iso ratio of aldehydes by controlling the olefin partial pressure.

[0006] According to the above research, there is no production process in the prior art that can reversibly and flexibly adjust the production of olefin hydroformylation reaction products while maintaining the activity of noble metal catalysts. SUMMARY

[0007] The purpose of the present application is to provide a method for online adjustment of octene hydroformylation reaction to produce different n-iso ratio of nonaldehydes and a catalyst composition thereof, so that the target product ratio can be quickly and flexibly adjusted online according to the actual market demand, and the device efficiency is maximized.

[0008] To achieve the above invention purposes, the technical scheme adopted by the present application is as follows:

[0009] A catalyst composition for online adjustment of octene hydroformylation reaction, characterized in that the catalyst composition comprises a catalyst, an additive, and a solvent: the active component of the catalyst comprises at least two of rhodium, cobalt, and iridium; the additive is a plurality of components: additive A is a phosphine ligand with the general structure P(M1) x (M2) yWherein, M1 is phenyl, M2 is cyclohexyl, x is an integer ≥0, y is an integer ≥1, and x+y=3; the auxiliary B is epoxy fluoropropane; the auxiliary C is 4-hydroxy-3-nitrobenzoic acid.

[0010] The formation mechanism of normal and iso aldehydes is explained by taking the rhodium-triphenylphosphine catalyst which is relatively mature in the prior art as an example, and is specifically shown in the following formula.

[0011] A. The hydrogenated activated rhodium source or other active metal is coordinated with olefin to be stable after losing hydrogen coordination;

[0012] B. The rhodium or other active metal coordinated with olefin is continuously coordinated with CO, and is stable after addition with olefin to form a carbonyl compound;

[0013] C. The aldehyde generated after hydrogenation of the carbonyl compound is detached from the active metal;

[0014] D. The hydrogenated rhodium continues the next catalytic cycle.

[0015] In the cycle, in process ①, when the ligand competition activity is insufficient (weak charge or insufficient ligand concentration) after hydrogen detachment, the chemical equilibrium moves to the CO coordination side, and finally causes the rhodium to aggregate and deactivate; in process ②, when the steric hindrance is large, the carbon at the α position of the olefin attacks the rhodium, and finally forms a normal aldehyde product, and when the steric hindrance is small, the carbon at the β position attacks the rhodium source, and finally generates an iso aldehyde product.

[0016]

[0017] It can be seen that, in order to reversibly and flexibly adjust the product of the olefin hydroformylation reaction, the core is to obtain new ligands with high electron effect and suitable steric hindrance according to the characteristics of different active metals. Meanwhile, CO itself as a reaction raw material has low steric hindrance performance, and the selected ligand competition needs to be higher than CO, so as to avoid the stable coordination of CO and rhodium, and cause the deactivation of the rhodium catalyst caused by step ①.

[0018] The auxiliary A in the application is a phosphine-containing ligand containing cyclohexane, and the cyclohexane is different from a benzene ring and has a non-planar structure and low steric hindrance. Meanwhile, the P charge distribution is more dispersed than that of triphenylphosphine, and the combination with rhodium is stronger, and it is not easy to combine with cobalt and iridium. Since the price of rhodium is relatively high, the auxiliary A is mainly used for protecting rhodium in the preparation of the catalyst, so as to avoid the rapid deactivation of rhodium and frequent addition of rhodium.

[0019] The synergism exists between the epoxy fluoro-propyl and the assistant A, which can protect the metal active center together with the A, but compared with the A, it is easier to combine with the cobalt and iridium to form the coordination, and then to generate the n-butyl aldehyde. When the ratio of n-butyl aldehyde to iso-butyl aldehyde is increased, the amount of the assistant B can be increased to increase the yield of the n-butyl aldehyde. Meanwhile, the assistant A contains certain oxidation, and by properly controlling the hydrogen partial pressure, the catalyst and the concentration of the assistant B in the system can be adjusted, and the ratio of the n-butyl aldehyde to the iso-butyl aldehyde can also be controlled.

[0020] The assistant C 4-hydroxy-3-nitrobenzenearsonic acid is used to control the content of the assistant B in the reaction system, and by adding the assistant C, the content of the assistant B is properly reduced to realize the rapid adjustment of the ratio of the products.

[0021] In the present application, the source form of the catalyst active component is one or more of inorganic metal salt, metal compound of di-carbonyl acetylacetone and metal compound of acetylacetone triphenyl phosphine carbonyl, and preferably the inorganic metal salt; preferably, the content of the catalyst active component is 50ppm-5000ppm, preferably 200ppm-3000ppm in terms of active metal, and the mass content of the active component in the catalyst composition is 50ppm-5000ppm, preferably 200ppm-3000ppm.

[0022] In the present application, the mass content of the assistant A in the catalyst composition is 0.1%-15%, preferably 1%-10%, and more preferably 3%-5%.

[0023] In the present application, the mass content of the assistant B in the catalyst composition is 0.5%-5%, preferably 1%-3%.

[0024] In the present application, the mass content of the assistant C in the catalyst composition is 0.5%-3%, preferably 0.8%-1.5%.

[0025] In the present application, the solvent is one or more of alcohol, ether, ester and aldehyde, and preferably the alcohol.

[0026] In an embodiment, the catalyst composition is used in the method for the hydroformylation of octene as follows: the octene, hydrogen and carbon monoxide are introduced from the bottom of the tank reactor with stirring paddle, and the target product is obtained by controlling the reaction temperature, pressure, catalyst composition feeding speed, octene mass space velocity and synthesis gas volume space velocity.

[0027] Another object of the present application is to provide a method for preparing the catalyst composition.

[0028] A method for preparing the catalyst composition described above, which comprises: after purging and replacing the solvent, the catalyst active component raw material, the assistant A, the assistant B and the assistant C are added to the solvent for dissolution, and the oxygen is prevented from entering.

[0029] Another object of the present application is to provide a method for preparing aldehyde.

[0030] A method for preparing aldehyde, the method employs the catalyst composition described above, or the catalyst composition prepared by the method described above, the method for preparing aldehyde is that: olefins, synthesis gas are fed alone, by adjusting the mass ratio of ligand to active metal in the catalyst composition, the target product with controllable normal-isomer ratio is obtained.

[0031] In the present application, the mass ratio of ligand to active metal in the catalyst composition in the method is 5-175:1.

[0032] In the present application, the mass space velocity of olefins in the method is 0.02-0.2h -1 .

[0033] In the present application, the synthesis gas in the method is hydrogen and carbon monoxide; preferably, the hydrogen gas volume space velocity is 8-80h -1 .

[0034] In the present application, the mass space velocity of the catalyst composition in the method is 0.02-0.2h -1 .

[0035] In the present application, the method controls the CO partial pressure in the reaction tail gas to be 0.05-0.5MPaG.

[0036] In an embodiment, according to the fast and slow response of different ligands to CO concentration, the normal and isomer product distribution is adjusted, and at the same time, the low-boiling-point auxiliary B can be distilled out of the reaction system, i.e. the catalyst + process parameter adjustment product distribution mode includes:

[0037] Dual active metal + CO partial pressure + auxiliary A + auxiliary B + auxiliary C

[0038] The isononyl aldehyde production increasing mode includes:

[0039] 1. Reduce the CO partial pressure, adopt the low CO partial pressure strategy (the CO partial pressure 0.18MPa is the boundary in the present application)

[0040] 2. Add auxiliary B

[0041] 3. Appropriately supplement the high active metal ratio in the dual active metal.

[0042] On the contrary, the normal nonyl aldehyde production increasing mode includes:

[0043] 1. Increase the CO partial pressure, adopt the high CO partial pressure strategy, which can be realized by increasing the CO feed

[0044] 2. Add auxiliary C content

[0045] 3. Appropriately supplement the low active metal ratio in the dual active metal.

[0046] In actual operation, since the active metal and the auxiliary agent B in the catalyst are consumables, the preparation method can be flexibly selected from the above combinations according to actual needs.

[0047] In the present application, the reaction temperature in the method is 70-110℃, preferably 80-90℃, and the pressure is 1.6-2.0 MPaG.

[0048] Another object of the present application is to provide an aldehyde with adjustable normal isomer ratio.

[0049] An aldehyde with adjustable normal isomer ratio, which is prepared by using the above-mentioned catalyst composition, or the catalyst composition prepared by using the above-mentioned preparation method, or the above-mentioned preparation method of the aldehyde, the aldehyde is a C4-C12 aldehyde, preferably a C8-C12 aldehyde, more preferably nonanal; preferably, the normal aldehyde / isomer aldehyde ratio in the aldehyde product can be flexibly adjusted in the range of 2.5-13.0:1.

[0050] Unless otherwise specified, the pressure in the present application is gauge pressure.

[0051] Compared with the prior art, the present application has the following beneficial effects:

[0052] (1) Compared with the traditional rhodium-triphenylphosphine catalytic system, the ligand dosage of the present application is 6%-8%, which is lower than the 10-13% of the traditional system,

[0053] (2) Compared with the traditional high nonanal normal isomer ratio catalytic system, the present application is more flexible, and can realize the flexible adjustment of the nonanal normal isomer ratio in the range of 2.3-13. DETAILED DESCRIPTION

[0054] The present application will be further described below by examples, but is not limited to the present examples.

[0055] The normal isomer ratio analysis method adopts Agilent chromatographic analysis, and the specific determination method of normal isomer nonanal is as follows: injection amount: 0.2 μL; column temperature: 50℃ for 4 min, increased to 60℃ at a rate of 3℃ / min, increased to 150℃ at a rate of 10℃ / min, increased to 230℃ at a rate of 20℃ / min, and maintained for 8 min; injection port temperature: 250℃; spacer pad purge gas flow rate: 3.0 mL / min; chromatographic column flow rate (N2): 1 mL / min; split injection, split ratio 30:1; detector: 280℃; hydrogen flow rate: 30 mL / min; air flow rate: 400 mL / min; tail gas flow rate: 25 mL / min.

[0056] Raw material sources:

[0057] Ethylene glycol, cyclohexyldiphenylphosphine (CHDP), dicyclohexyldiphenylphosphine (CHDDP), octene, epoxyfluoropropane, 4-hydroxy-3-nitrobenzoic acid. Arndt-Eistert reagent, purity greater than 98%;

[0058] Acetylacetone triphenylphosphine rhodium carbonyl, acetylacetone triphenylphosphine cobalt carbonyl, acetylacetone triphenylphosphine iridium carbonyl, Arndt-Eistert reagent, purity greater than 98%;

[0059] Steel cylinder gas (CO, H2), purity 99.9%, Yantai Mingtong gas.

[0060] Example 1

[0061] The catalyst preparation tank was replaced with nitrogen to an oxygen content of less than 0.1wt%, and ethylene glycol 556.82g, acetylacetone triphenylphosphine rhodium carbonyl 0.57g, acetylacetone cobalt 3.6g, additive A1 cyclohexyldiphenylphosphine 18.03g, additive B 18.00g, and additive C 3.00g were sequentially added to the preparation tank, heated to 50°C, and stirred for 120 min.

[0062] The above amount corresponds to: rhodium content (calculated as rhodium element) 200ppm, cobalt content 1000ppm, additive A1 cyclohexyldiphenylphosphine 3wt%, additive B 3wt%, and additive C 0.5wt%.

[0063] The catalytic system of the present application was evaluated by using the hydroformylation reaction of octene:

[0064] The reaction was carried out in a tank reactor with a stirring paddle (stirring tank volume 1L, stirring rate 200r / min), and 600g of the prepared catalyst composition was pre-added to the reactor. Octene, hydrogen, and carbon monoxide were continuously fed from the bottom of the reactor, the reaction temperature was 80°C, and the pressure was 1.6MPaG. The feeding rate of octene was 0.2g / min, the feeding rate of hydrogen was 107ml / min under standard conditions, and the feeding rate of the homogeneous catalyst was 0.2g / min. The CO partial pressure was controlled at 0.05MPa in the first stage, and after stable operation, the CO partial pressure was increased to 0.1MPa, and the reaction was stopped after 40h. The liquid level of the reactor was controlled stable during the process, and the results showed that the ratio of n- to iso-nonyl aldehyde was 2.5 in the first stage, and 8.0 in the second stage.

[0065] Example 2

[0066] The catalyst preparation tank was replaced with nitrogen to an oxygen content of less than 0.1wt%, and ethylene glycol 551.36g, acetylacetone triphenylphosphine rhodium carbonyl 0.86g, acetylacetone iridium 7.21g, additive A2 cyclohexyldiphenylphosphine 24.01g, additive B 12.00g, and additive C 4.80g were sequentially added to the preparation tank, heated to 50°C, and stirred for 120 min.

[0067] The above dosages correspond to: rhodium content (calculated as rhodium element) 300 ppm, iridium content 2000 ppm, additive A2 cyclohexyldiphenylphosphine 4 wt%, additive B 2 wt%, and additive C 0.8 wt%.

[0068] The catalytic system of the present invention was evaluated using the octene hydroformylation reaction:

[0069] The reaction was carried out in a stirred tank reactor equipped with a stirrer (1 L volume, stirring speed 200 r / min). 600 g of a pre-prepared catalyst composition was added to the reactor beforehand. Octene, hydrogen, and carbon monoxide were continuously introduced from the bottom of the reactor. The reaction temperature was 85 °C, and the pressure was 1.8 MPaG. The octene feed rate was 1 g / min, the hydrogen feed rate was 533 ml / min under standard conditions, and the homogeneous catalyst feed rate was 1 g / min. In the first stage of the reaction, the CO partial pressure was controlled at 0.3 MPa. After stabilization, the CO partial pressure was reduced by 0.2 MPa, and the reaction was stopped after 40 h. The liquid level in the reactor was kept stable throughout the process. The results showed that the ratio of n-isononal to n-nonal was 10 in the first stage and 3.0 in the second stage.

[0070] Example 3

[0071] The catalyst preparation vessel was purged with nitrogen until the oxygen content was below 0.1 wt%. 538.88 g of ethylene glycol, 5.75 g of cobalt acetylacetone, 10.81 g of iridium acetylacetone, 30.06 g of cyclohexylphosphine A3, 6.01 g of additive B, and 9.02 g of additive C were added to the vessel in sequence. The mixture was heated to 50 °C and stirred for 120 min.

[0072] The above dosages correspond to: cobalt content 2000ppm, iridium content 3000ppm, additive A3 cyclohexylphosphine 5wt%, additive B 1wt%, and additive C 1.5wt%.

[0073] The catalytic system of the present invention was evaluated using the octene hydroformylation reaction:

[0074] The reaction was carried out in a stirred tank reactor equipped with a stirrer (1 L volume, stirring speed 200 r / min). 600 g of a pre-prepared catalyst composition was added to the reactor beforehand. Octene, hydrogen, and carbon monoxide were continuously introduced from the bottom of the reactor. The reaction temperature was 90 °C, and the pressure was 2.0 MPaG. The octene feed rate was 2.0 g / min, the hydrogen feed rate was 1067 ml / min under standard conditions, and the homogeneous catalyst feed rate was 2 g / min. In the first stage of the reaction, the CO partial pressure was controlled at 0.2 MPa. After stabilization, the CO partial pressure was increased by 0.5 MPa, and the reaction was stopped after 40 h. The liquid level in the reactor was kept stable throughout the process. The results showed that the ratio of n-isononal to n-nonal was 13 in the first stage and 6.0 in the second stage.

[0075] Comparative Example 1

[0076] The catalyst preparation tank was replaced with nitrogen to an oxygen content of less than 0.1 wt%, and ethylene glycol 574.82 g, acetylacetone triphenylphosphine rhodium carbonyl 0.57 g, acetylacetone cobalt 3.60 g, adjuvant B 18.00 g, and adjuvant C 3.00 g were sequentially added to the preparation tank, heated to 50°C, and stirred for 120 min.

[0077] The above amounts correspond to a rhodium content (as rhodium element) of 200 ppm, a cobalt content (as cobalt element) of 1000 ppm, adjuvant B of 3 wt%, and adjuvant C of 0.5 wt%.

[0078] The catalytic system of the present application was evaluated using an octene hydroformylation reaction.

[0079] The reaction was carried out in a tank reactor with a stirring paddle (stirring tank volume 1 L, stirring rate 200 r / min), and 600 g of the prepared catalyst composition was pre-added to the reactor. Octene, hydrogen, and carbon monoxide were continuously fed from the bottom of the reactor, the reaction temperature was 80°C, and the pressure was 1.6 MPaG. The octene feed rate was 0.2 g / min, the hydrogen feed rate was 107 ml / min at standard conditions, and the homogeneous catalyst feed rate was 0.2 g / min. The CO partial pressure was controlled at 0.05 MPa in the first stage, and after stable operation, the CO partial pressure was increased to 0.1 MPa, and the reaction was stopped after 40 h. The reactor liquid level was controlled to be stable during the process, and the results showed that the n-iso-nonylaldehyde ratio was 7.5 in the first stage and 8.0 in the second stage.

[0080] Comparative Example 2

[0081] The catalyst preparation tank was replaced with nitrogen to an oxygen content of less than 0.1 wt%, and ethylene glycol 574.82 g, acetylacetone triphenylphosphine rhodium carbonyl 0.57 g, acetylacetone cobalt 3.60 g, adjuvant B 18.00 g, and adjuvant C 3.00 g were sequentially added to the preparation tank, heated to 50°C, and stirred for 120 min.

[0082] The above amounts correspond to a rhodium content (as rhodium element) of 200 ppm, a cobalt content (as cobalt element) of 1000 ppm, adjuvant B of 3 wt%, and adjuvant C of 0.5 wt%.

[0083] The catalytic system of the present application is evaluated by using the hydroformylation reaction of octene: the reaction is carried out in a stirred tank reactor (stirred tank volume 1 L, stirring rate 200 r / min), 600 g of the prepared catalyst composition is added into the reactor in advance. Octene, hydrogen and carbon monoxide are continuously fed from the bottom of the reactor, the reaction temperature is 85°C, and the pressure is 1.8 MPa. The feeding rate of octene is 1 g / min, the feeding rate of hydrogen is 533 ml / min under standard conditions, and the feeding rate of the homogeneous catalyst is 1 g / min. The CO partial pressure is controlled at 0.3 MPa in the first stage, after stable operation, the CO partial pressure is reduced to 0.2 MPa, and the reaction is stopped after 40 h, the liquid level of the reactor is controlled stable during the process, and the sample is taken after the end of the reaction, and the n-iso ratio of the reaction product is measured, the results show that the n-iso ratio of nonyl aldehyde in the first stage is 8.2, and the n-iso ratio of nonyl aldehyde in the second stage is 7.6.

[0084] Comparative Example 3

[0085] The catalyst preparation tank is replaced by nitrogen to an oxygen content of less than 0.1 wt%, and the following is sequentially added into the preparation tank: ethylene glycol 547.88 g, cobalt acetylacetonate 5.75 g, iridium acetylacetonate 10.81 g, additive A3 cyclohexyl phosphine 30.06, and additive B 6.01 g, heated to 50°C, and stirred for 120 min.

[0086] The above amount corresponds to: cobalt content 2500 ppm, iridium content 3000 ppm, additive A3 cyclohexyl phosphine 5 wt%, and additive B 1 wt%.

[0087] The catalytic system of the present application is evaluated by using the hydroformylation reaction of octene:

[0088] The reaction is carried out in a stirred tank reactor (stirred tank volume 1 L, stirring rate 200 r / min), 600 g of the prepared catalyst composition is added into the reactor in advance. Octene, hydrogen and carbon monoxide are continuously fed from the bottom of the reactor, the reaction temperature is 90°C, and the pressure is 2.0 MPa. The feeding rate of octene is 2.0 g / min, the feeding rate of hydrogen is 1067 ml / min under standard conditions, and the feeding rate of the homogeneous catalyst is 2 g / min. The CO partial pressure is controlled at 0.2 MPa in the first stage, after stable operation, the CO partial pressure is increased to 0.5 MPa, and the reaction is stopped after 40 h, the liquid level of the reactor is controlled stable during the process, and the results show that the n-iso ratio of nonyl aldehyde in the first stage is 6.5, and the n-iso ratio of nonyl aldehyde in the second stage is 7.1.

[0089] In the above cases, the difference between Example 1 and Comparative Example 1 is that no component A1 cyclohexyl diphenyl phosphine is contained, and the rest of the catalyst composition and reaction conditions are consistent, and the presence of component A1 is less, and the normal-isomer ratio is adjusted from 2.5-8 of the example to 7.5-8 of the comparative example; the difference between Example 2 and Comparative Example 2 is that no component B epoxy fluoropropane is contained, and the rest of the catalyst composition and reaction conditions are consistent, and the presence of component B is less, and the normal-isomer ratio is adjusted from 10 of the example to 3 to 8.2 of the comparative example to 7.6; the difference between Example 3 and Comparative Example 3 is that no component C 4-hydroxy-3-nitrobenzoic acid is contained, and the rest of the catalyst composition and reaction conditions are consistent, and the presence of component C is less, and the normal-isomer ratio is adjusted from 6-13 of the example to 6.5-7.1 of the comparative example. From the above cases, it can be seen that the normal-isomer ratio of the aldehyde product changes in the range of less than any one of components A, B and C, and the function of online adjusting the distribution of aldehyde product cannot be realized.

[0090] The above is only a few embodiments of the present application, which is described in more detail, but should not be understood as limiting the application to the disclosed content. It should be clear that without departing from the core idea of the present application, a number of corresponding modifications and improvements can be made, and any simple modification belongs to the protection scope of the present application.

Claims

1. An on-line adjustment of a catalyst composition for the hydroformylation of octenes, characterized in that, The catalyst composition comprises a catalyst, an auxiliary A, an auxiliary B, an auxiliary C, and a solvent. The catalyst active component is selected from at least two of rhodium, cobalt, and iridium. wherein the adjuvant A is a phosphine-containing ligand having the general structure P(M1) x (M2) y wherein M1 is a phenyl group, M2 is a cyclohexyl group, x is an integer > 0, y is an integer > 1, and x + y = 3; the adjuvant B is an epoxy fluoro-propane; the adjuvant C is 4-hydroxy-3-nitrobenzoic acid; The source form of the catalyst active component is one or more of an inorganic metal salt, a metal compound of di-carbonyl acetylacetone, and a metal compound of acetylacetone triphenyl phosphine carbonyl.

2. The catalyst composition of claim 1, wherein, The source form of the catalyst active component is an inorganic metal salt.

3. The catalyst composition of claim 2, wherein, The content of the catalyst active component is 50 ppm to 5000 ppm in mass of active metal in the catalyst composition.

4. The catalyst composition of claim 3, wherein, The content of the catalyst active component is 200 ppm to 3000 ppm in mass of active metal in the catalyst composition.

5. The catalyst composition of claim 1 or 2, wherein The mass content of the auxiliary A in the catalyst composition is 0.1% to 15%.

6. The catalyst composition of claim 5, wherein, The mass content of the auxiliary A in the catalyst composition is 1% to 10%.

7. The catalyst composition of claim 6, wherein, The mass content of the auxiliary A in the catalyst composition is 3% to 5%.

8. The catalyst composition of claim 1, wherein, The mass content of the auxiliary B in the catalyst composition is 0.5% to 5%.

9. The catalyst composition of claim 8, wherein, The mass content of the auxiliary B in the catalyst composition is 1% to 3%.

10. The catalyst composition of claim 1, wherein, The mass content of the auxiliary C in the catalyst composition is 0.5% to 3%.

11. The catalyst composition of claim 10, wherein, The mass content of the auxiliary C in the catalyst composition is 0.8% to 1.5%.

12. The catalyst composition of claim 1, wherein, The solvent is one or more of an alcohol, an ether, an ester, and an aldehyde.

13. The catalyst composition of claim 12, wherein, The solvent is an alcohol.

14. A process for preparing the catalyst composition of any one of claims 1-13, characterized in that, The method is: after purging and replacing the solvent, the catalyst active component raw material, the auxiliary A, the auxiliary B, and the auxiliary C are added to the solvent for dissolution, and oxygen is prevented from entering.

15. The method of claim 14, wherein, The purging makes the oxygen content in the upper gas phase of the solvent less than 0.1 vol.%.

16. A process for the preparation of an aldehyde, said process employing a catalyst composition according to any one of claims 1 to 13, or a catalyst composition prepared according to the process of claim 14 or 15, characterized in that, The preparation method of the aldehyde is: olefins and synthesis gas are separately fed, the ratio of ligand to active metal in the catalyst composition is adjusted, the target product with a controllable normal-isomer ratio is obtained, and the product is nonanal.

17. The method for preparing aldehydes according to claim 16, characterized in that, The mass ratio of ligand to active metal in the catalyst composition is 5-175:1 in the method. and / or, the olefin mass space velocity in the process is 0.02 to 0.2 h -1 ; And / or, the synthesis gas in the method is hydrogen and carbon monoxide. and / or, the catalyst composition mass space velocity in the process is 0.02 to 0.2 h -1 ; And / or, the CO partial pressure in the tail gas is controlled to be 0.05-0.5 MPaG in the method. And / or, the reaction temperature is 70-110°C and the pressure is 1.6-2.0 MPaG in the method.

18. The method for preparing aldehydes according to claim 17, characterized in that, In the method, the hydrogen gas hourly space velocity ranges from 8 to 80 h -1 ; And / or, the reaction temperature is 80-90°C in the method.

Images