Process for the on-line regeneration of rhodium phosphine complex catalyst, olefin hydroformylation reaction system, method

Abstract

The application discloses a rhodium phosphine complex catalyst online regeneration method, an olefin hydroformylation reaction system and method, and the method comprises the following steps: using an aqueous extractant solution to extract a reaction system containing a rhodium phosphine complex catalyst, then separating an oil phase and a water phase, and the regenerated rhodium phosphine complex catalyst exists in the oil phase; wherein the aqueous extractant solution is a solution obtained by mixing an extractant and water, and the extractant has the following structure: R1, R2, R3 and R4 are the same or different, and are independently selected from one of hydrogen, halogen, trihalomethyl, hydroxyl, nitro, sulfonic acid group and cyano. The use of the extractant can make the olefin hydroformylation reaction be carried out in a continuous mode, the reaction system can be kept pure for a long time in a running cycle, the catalyst performance can be maintained by regularly supplementing phosphine ligands, the catalyst life is greatly improved, the production cost is reduced, and strong technical support is provided for continuous production of high-quality products.

Description

Technical Field

[0001] This invention belongs to the field of petrochemicals and relates to a method for regenerating a rhodium phosphine complex catalyst, an olefin hydroformylation reaction system, and a method. Background Technology

[0002] Catalyst systems formed by the complexation of rhodium carbonyl precursors with organophosphorus ligands (monodentate, bidentate, tridentate, and tetradentate) containing phosphite structures exhibit high selectivity and catalytic activity, and are widely used in the hydroformylation of olefins. However, phosphites are highly unstable. During the continuous hydroformylation reaction, they compete with the carbonyl group on the precursor for complexation and are in dynamic chemical equilibrium. As the reaction proceeds, changes in CO partial pressure, excessively high local temperatures, trace amounts of water, and the presence of aldehydes in the product can all weaken the complexing ability of these ligands, causing the equilibrium to shift. This leads to the deterioration of the phosphite, producing free phosphate ester colloids, accelerating the loss rate of organophosphorus ligands, and causing a decrease in catalyst activity or even poisoning. Since rhodium metal is expensive, maintaining the activity stability of rhodium catalysts and extending their lifetime are currently critical technical problems that urgently need to be solved.

[0003] Existing technologies have reported some methods for maintaining the activity and stability of catalyst systems and extending catalyst lifetime by removing free phosphate esters generated by the deterioration of organic phosphite ligands.

[0004] Chinese patent CN88102776A discloses a purification method for rhodium metal ligand organic-based triphosphite. This patent uses water and Lewis bases to selectively remove organic phosphite diesters in the system to extend the catalyst lifetime. The Lewis bases used include alkali metals, hydroxides, quaternary ammoniums, etc. However, Lewis bases readily induce aldehydes to undergo self-condensation. This technology is limited to treating the catalyst solution alone and cannot be used under conditions where the products have not been separated, making it unsuitable for continuous reactions.

[0005] US Patent 5364950A discloses a method for inhibiting ligand deterioration by adding long-chain epoxides to a reaction system. Long-chain epoxides can react with phosphite ligands via hydrolysis to produce… α A five-membered heterocyclic compound is formed by the reaction of hydroxyphosphoric acid. This prevents α-hydroxyphosphate from further catalyzing the hydrolysis of phosphite ligands. In the continuous hydroformylation reaction of butene, adding a long-chain epoxide to the reaction system every 3 days maintains catalyst activity for more than 4 months without weakening. However, this technology involves long-term addition of epoxides to the reaction system, leading to impurity accumulation, and the lack of separation methods severely impacts product quality.

[0006] US Patent 5731472 discloses a method for maintaining the stability of a catalytic system by adding benzimidazole. Adding 4 wt% benzimidazole to the catalyst solution buffers strong acids and stabilizes the catalyst. After a period of use, the catalyst solution can be washed with a sodium phosphate buffer solution at pH 7, and then the benzimidazole in the aqueous phase can be extracted with pentanal, achieving regeneration and recycling. However, the benzimidazole used in this technique is highly miscible with the aldehyde products. Direct treatment of the aldehyde-containing reaction solution easily leads to the accumulation of benzimidazole in the system, which is difficult to remove. Therefore, it cannot be used under conditions where the products are not separated and is not suitable for continuous reactions.

[0007] US Patent 5763680 utilizes macroporous ion exchange resin Amberlyst A21 to remove phosphate esters generated by catalyst ligand deterioration, thus maintaining catalyst stability. This can be achieved by adding an ion exchange resin adsorption tower to the continuous hydroformylation reaction to treat the reaction solution. The ion exchange resin is regenerated with a 4 wt% sodium hydroxide solution and reused. However, ion exchange resins suffer significant loss of acidic centers above 80°C, and since hydroformylation reactions typically exceed 80°C, using ion exchange resins to treat high-temperature reaction solutions leads to severe deactivation, requiring frequent regeneration with sodium hydroxide. Furthermore, sodium hydroxide can trigger the self-condensation of aldehydes in the product, severely impacting product quality. Summary of the Invention

[0008] The main objective of this invention is to provide a method for online regeneration of rhodium-phosphine complex catalysts, an olefin hydroformylation reaction system, and an olefin hydroformylation method, in order to overcome the shortcomings of existing technologies such as short service life of rhodium-phosphine complex catalysts, the inability of existing catalyst regeneration methods to be used for continuous reactions, and the impact of existing catalyst regeneration methods on product quality.

[0009] To achieve the above objectives, the present invention provides a method for online regeneration of a rhodium phosphine complex catalyst, wherein an aqueous extractant solution is used to extract the reaction system containing the rhodium phosphine complex catalyst, and then the oil phase and the aqueous phase are separated, and the regenerated rhodium phosphine complex catalyst is present in the oil phase;

[0010] The extractant aqueous solution is a solution obtained by mixing the extractant with water, and the extractant has the following structure:

[0011]

[0012] R1, R2, R3, and R4 may be the same or different, and are independently selected from one of hydrogen, halogen, trihalomethyl, hydroxyl, nitro, sulfonic acid, and cyano groups.

[0013] The method for online regeneration of the rhodium phosphine complex catalyst of the present invention, wherein R1, R2, R3, and R4 are independently selected from one of hydrogen, halogen, and trihalomethyl; and the extractant is a water-soluble compound.

[0014] The method for online regeneration of the rhodium-phosphine complex catalyst according to the present invention, wherein the extractant is at least one of compounds L1 to L10, and R1, R2, R3, and R4 of compounds L1 to L10 are respectively:

[0015] L1: R1 = hydrogen, R2 = hydrogen, R3 = hydrogen, R4 = hydrogen;

[0016] L2: R1 = hydrogen, R2 = hydrogen, R3 = chlorine, R4 = chlorine;

[0017] L3: R1 = hydrogen, R2 = chlorine, R3 = chlorine, R4 = hydrogen;

[0018] L4: R1 = chlorine, R2 = chlorine, R3 = chlorine, R4 = hydrogen;

[0019] L5: R1 = chlorine, R2 = chlorine, R3 = chlorine, R4 = chlorine;

[0020] L6: R1 = hydrogen, R2 = chlorine, R3 = chlorine, R4 = chlorine;

[0021] L7: R1 = hydrogen, R2 = trichloromethyl, R3 = chlorine, R4 = chlorine;

[0022] L8: R1 = hydrogen, R2 = trifluoromethyl, R3 = chlorine, R4 = chlorine;

[0023] L9: R1 = hydrogen, R2 is trichloromethyl, R3 = hydrogen, R4 is chlorine;

[0024] L10: R1 = hydrogen, R2 is trifluoromethyl, R3 = hydrogen, R4 is chlorine.

[0025] The method for online regeneration of the rhodium-phosphine complex catalyst of the present invention comprises a reaction system being an olefin hydroformylation reaction system; the rhodium-phosphine complex catalyst being a catalyst system formed by complexing a carbonyl rhodium precursor with an organophosphine ligand containing a phosphite structure; and an extractant aqueous solution being used to extract 10-15% of the reaction system containing the rhodium-phosphine complex catalyst.

[0026] The method for online regeneration of the rhodium phosphine complex catalyst of the present invention includes adding an organophosphine ligand containing a phosphite structure to the oil phase, and then reusing the resulting oil phase for catalyzing the hydroformylation reaction of olefins.

[0027] To achieve the above objectives, the present invention also provides an olefin hydroformylation reaction system, comprising:

[0028] A reaction apparatus used for the hydroformylation of olefins;

[0029] Extractant storage tank, used for preparing or storing extractant solutions;

[0030] The two-phase separation device is connected to the reaction device and the extractant storage tank respectively, so as to transport the reaction system and the extractant solution to the two-phase separation device for extraction and phase separation to obtain the oil phase and the water phase.

[0031] The two-phase separation device is connected to the reaction device to recycle the oil phase back to the reaction device.

[0032] The olefin hydroformylation reaction system of the present invention further includes:

[0033] An evaporation device is connected to the reaction device and the two-phase separation device to evaporate a portion of the reaction system and then transport it to the two-phase separation device, while the remaining reaction system is discharged as a reaction product.

[0034] The olefin hydroformylation reaction system of the present invention further includes:

[0035] A coalescence separation device is connected to the reaction device and the two-phase separation device to dehydrate the oil phase and then transport it to the reaction device.

[0036] The olefin hydroformylation reaction system of the present invention includes a ligand replenishment port for periodically replenishing catalyst ligands.

[0037] To achieve the above objectives, the present invention further provides a method for hydroformylation of olefins, comprising the following steps:

[0038] Step 1: Olefins and syngas undergo hydroformylation under the catalysis of a rhodium phosphine complex catalyst;

[0039] Step 2: Extract part or all of the reaction mixture from Step 1 using an aqueous extractant solution to obtain an oil phase and an aqueous phase;

[0040] The oil phase is used for cyclic catalysis to carry out the hydroformylation reaction of olefins.

[0041] The olefin hydroformylation method of the present invention is a continuous reaction; the continuous reaction system is periodically replenished with ligands of the rhodium phosphine complex catalyst.

[0042] The beneficial effects of this invention are:

[0043] This invention employs a water-soluble pyridine extractant to extract the olefin hydroformylation reaction system. This effectively removes phosphate esters generated from the deterioration of phosphite esters in the rhodium-phosphine complex catalyst, promoting a shift in catalyst equilibrium towards the rhodium-phosphine complex catalyst. The use of this extractant allows the olefin hydroformylation reaction to proceed continuously, maintaining the purity of the reaction system over a long period. Furthermore, by periodically replenishing phosphine ligands, catalyst performance is maintained, significantly extending catalyst lifespan, reducing production costs, and providing strong technical support for the continuous production of high-quality products. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the olefin hydroformylation reaction system of the present invention.

[0045] In the attached figures, the following labels are used:

[0046] 1. Reaction apparatus

[0047] 2 Extractant Storage Tank

[0048] 3. Two-phase separation device

[0049] 4. Coagulation Separation Device

[0050] 5 Waste liquid tank

[0051] 6 Product Cans

[0052] 7 Evaporation apparatus

[0053] 8. Circulating pump

[0054] 9. Metering pump

[0055] 10 Metering pumps

[0056] 11 Circulating Pump Detailed Implementation

[0057] The following provides a detailed description of the embodiments of the present invention. These embodiments are implemented based on the technical solution of the present invention and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0058] This invention provides a method for online regeneration of a rhodium-phosphine complex catalyst. The rhodium-phosphine complex catalyst is a catalyst system formed by complexing a carbonyl rhodium precursor with an organophosphine ligand containing a phosphite structure. The rhodium-phosphine complex catalyst can be used for the hydroformylation reaction of olefins.

[0059] However, organophosphine ligands containing phosphite structures are unstable. In the continuous hydroformylation reaction, the complexation reaction between the carbonyl rhodium precursor and the organophosphine ligands containing phosphite structures is a dynamic chemical equilibrium. With changes in external factors, the equilibrium shifts, causing the phosphite to deteriorate and produce free phosphate esters. Moreover, phosphate esters accelerate the loss rate of organophosphine ligands, which leads to problems such as reduced catalyst activity, shortened catalyst lifetime, and decreased product quality. This, in turn, increases the amount of precious metal rhodium used, significantly increasing production costs.

[0060] The online regeneration of the rhodium-phosphine complex catalyst of this invention refers to the timely removal of degraded substances such as phosphate esters from the catalyst, enabling the catalyst to be recycled for the hydroformylation reaction of olefins. This avoids further reduction of catalyst activity by degraded substances and prevents degraded substances from affecting the reaction process, thereby maintaining the activity stability of the catalyst during long-term operation.

[0061] The method for regenerating a rhodium phosphine complex catalyst of the present invention includes: extracting a reaction system containing a rhodium phosphine complex catalyst using an aqueous extractant solution, then separating the oil phase and the aqueous phase, wherein the regenerated rhodium phosphine complex catalyst is present in the oil phase;

[0062] The extractant aqueous solution is a solution obtained by mixing the extractant with water, and the extractant has the following structure:

[0063]

[0064] R1, R2, R3, and R4 may be the same or different, and are independently selected from one of hydrogen, halogen, trihalomethyl, hydroxyl, nitro, sulfonic acid, and cyano groups.

[0065] The pyridine extractant of this invention is readily soluble in water, slightly soluble in aldehydes, inert to complexed organophosphorus ligands, and exhibits a high affinity for free phosphate esters. Based on the difference in solubility of pyridine extractants in the water and oil phases and their high selectivity for free phosphate esters, the regeneration method of this invention can achieve rapid extraction and separation of free phosphate esters without damaging the original reaction system, thus maintaining the purity of the hydroformylation reaction system over a long period during the operating cycle. Therefore, the method of this invention is not only applicable to batch olefin hydroformylation reactions but also to continuous hydroformylation reactions.

[0066] The extractant of this invention is a water-soluble compound. In one embodiment, R1, R2, R3, and R4 in the extractant are independently selected from hydrogen, halogens, and trihalomethyl groups. In another embodiment, the extractant of this invention is at least one of compounds L1 to L10, wherein R1, R2, R3, and R4 in compounds L1 to L10 are respectively:

[0067] L1: R1 = hydrogen, R2 = hydrogen, R3 = hydrogen, R4 = hydrogen;

[0068] L2: R1 = hydrogen, R2 = hydrogen, R3 = chlorine, R4 = chlorine;

[0069] L3: R1 = hydrogen, R2 = chlorine, R3 = chlorine, R4 = hydrogen;

[0070] L4: R1 = chlorine, R2 = chlorine, R3 = chlorine, R4 = hydrogen;

[0071] L5: R1 = chlorine, R2 = chlorine, R3 = chlorine, R4 = chlorine;

[0072] L6: R1 = hydrogen, R2 = chlorine, R3 = chlorine, R4 = chlorine;

[0073] L7: R1 = hydrogen, R2 = trichloromethyl, R3 = chlorine, R4 = chlorine;

[0074] L8: R1 = hydrogen, R2 = trifluoromethyl, R3 = chlorine, R4 = chlorine;

[0075] L9: R1 = hydrogen, R2 is trichloromethyl, R3 = hydrogen, R4 is chlorine;

[0076] L10: R1 = hydrogen, R2 is trifluoromethyl, R3 = hydrogen, R4 is chlorine.

[0077] The present invention does not particularly limit the concentration of the extractant aqueous solution, for example, 0.05-0.3 mol / L. Furthermore, in one embodiment, the molar ratio between the extractant aqueous solution (calculated as extractant), the reaction system containing the rhodium-phosphine complex catalyst (calculated as organophosphine ligand), and the extractant aqueous solution is 1:3 to 1:8.

[0078] This invention does not specifically limit the extraction process. The extraction yields an oil phase and an aqueous phase. The oil phase mainly includes the products of the olefin hydroformylation reaction, organic reaction solvents, and rhodium-phosphine complexing catalysts, while the aqueous phase mainly includes the extractant aqueous solution and phosphate esters. The aqueous phase can be discharged as waste liquid, while the oil phase can be recycled for catalyzing the olefin hydroformylation reaction.

[0079] In one embodiment, the aqueous extractant of the present invention is used to extract 10-15% of the total weight of the reaction system containing the rhodium phosphine complex catalyst, and the remaining amount of the reaction system can be output as a product. In one embodiment, the olefin hydroformylation reaction of the present invention is a continuous reaction. Before the oil phase is recycled for catalyzing the olefin hydroformylation reaction, an organophosphine ligand containing a phosphite structure is added. This ensures that the catalyst maintains high catalytic activity, significantly improves catalyst life, and reduces production costs.

[0080] In one embodiment, in the rhodium phosphine complex catalyst system containing a phosphite ligand structure of the present invention, the general formula of the phosphite is: R is selected from phenyl, naphthyl, o-tolyl, 2-ethylphenyl, 2,6-dimethylphenyl, 4-tert-butylphenyl, 4-isopentylphenyl, nonylphenyl, benzyl, 2-phenylethyl, 4-phenylbutyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-octyl, n-decyl, isodecyl, n-dodecyl, cyclohexyl, cyclopentyl, 4-methylcyclohexyl, p-methoxyphenyl, p-hydroxyphenyl, 2-ethoxyethyl, 2-hydroxyethyl, etc. However, this invention is not limited thereto.

[0081] The method of the present invention is used for the hydroformylation reaction of olefins, but is not limited to the hydroformylation of a pure single olefin. It can be a mixture of olefins or a mixture mainly containing olefins, such as a mixed C4.

[0082] This invention also provides an olefin hydroformylation reaction system, using a rhodium phosphine complex catalyst as the catalyst, such as... Figure 1 As shown, it includes a reaction device 1, an extractant storage tank 2, and a two-phase separation device 3.

[0083] The reaction apparatus 1 is used for the hydroformylation reaction of olefins; the extractant storage tank 2 is used for the preparation or storage of the extractant solution; the two-phase separation device 3 is connected to the reaction apparatus 1 and the extractant storage tank 2 respectively, so as to transport the reaction system in the reaction apparatus 1 and the extractant solution in the extractant storage tank 2 to the two-phase separation device 3 for extraction and phase separation to obtain the oil phase and the aqueous phase.

[0084] The two-phase separation device 3 is connected to the reaction device 1 to circulate the oil phase back to the reaction device 1.

[0085] The olefin hydroformylation reaction system of this invention can be used for continuous olefin hydroformylation reactions. By timely removing phosphate esters from the reaction system through extraction, the purity of the reaction system can be ensured, shifting the equilibrium reaction of the catalyst in a direction favorable to catalytic activity, improving catalyst activity stability, extending catalyst lifetime, fully utilizing the catalytic performance of the precious metal rhodium, significantly reducing production costs and improving product quality. Simultaneously, the olefin hydroformylation reaction system of this invention does not contaminate the reaction system and does not disrupt the olefin hydromethylation reaction.

[0086] In one embodiment, the olefin hydroformylation reaction system of the present invention further includes an evaporation device 7, such as a falling film evaporator. The evaporation device 7 is connected to the reaction device 1 and the two-phase separation device 3 to evaporate a portion of the reaction system in the reaction device 1 and then transfer it to the two-phase separation device 3, while the remaining reaction system is discharged as a reaction product. In another embodiment, the evaporation device 7 is connected to a product tank 6, and the remaining reaction system (i.e., the unevaporated reaction system) is input into the product tank 6 as a reaction product. In yet another embodiment, the evaporation device 7 is connected to the reaction device 1 via a circulation pump 11 to circulate a portion of the reaction system within the evaporation device 7 back to the reaction device 1 for continued reaction.

[0087] In one embodiment, a metering pump 10 is installed on the pipeline connecting the two-phase separation device 3 and the reaction device 1. In another embodiment, the metering pump 10 is installed on the pipeline connecting the two-phase separation device 3 and the evaporation device 7. A metering pump 9 is installed on the pipeline connecting the two-phase separation device 3 and the extractant storage tank 2. The reaction system in the reaction device 1 and the extractant solution in the extractant storage tank 2 are metered by the metering pump 10 or 9 and then transported to the two-phase separation device 3. In one embodiment, the concentration of the extractant aqueous solution is, for example, 0.05-0.3 mol / L. The extractant aqueous solution is considered as extractant, the reaction system is considered as organophosphorus ligand, and the molar ratio between the reaction system and the extractant aqueous solution is 1:3 to 1:8.

[0088] In one embodiment, the olefin hydroformylation reaction system of the present invention further includes a coalescence separation device 4. The coalescence separation device 4 is connected to the reaction device 1 and the two-phase separation device 3 to dehydrate the oil phase and then transport it to the reaction device 1. In one embodiment, a circulation pump 8 is installed on the pipeline connecting the coalescence separation device 4 and the reaction device 1 to circulate the oil phase after removing impurities back to the reaction device 1.

[0089] In one embodiment, the two-phase separation device 3 is connected to the waste liquid tank 5 to transport the liquid phase separated by the two-phase separation device 3 to the waste liquid tank 5.

[0090] In one embodiment, the reaction device 1 of the present invention is provided with a ligand replenishment port for periodically replenishing catalyst ligands.

[0091] The present invention also provides a method for olefin hydroformylation, using the above-described olefin hydroformylation reaction system, comprising the following steps:

[0092] Step 1: Olefins and syngas undergo hydroformylation under the catalysis of a rhodium phosphine complex catalyst;

[0093] Step 2: Extract part or all of the reaction mixture from Step 1 using an aqueous extractant solution to obtain an oil phase and an aqueous phase;

[0094] The oil phase is used for cyclic catalysis to carry out the hydroformylation reaction of olefins.

[0095] In one embodiment, the olefin hydroformylation method is a continuous reaction; the continuous reaction system is periodically replenished with ligands for the rhodium phosphine complex catalyst.

[0096] In one specific embodiment, the olefin hydroformylation method of the present invention using the above-mentioned olefin hydroformylation reaction system is as follows:

[0097] The olefin hydroformylation reaction system is purged and replaced with inert gas, and the olefins and syngas react in reaction unit 1. A 0.125 mol / L extractant aqueous solution is prepared and added to the extractant storage tank 2. A portion of the reaction liquid is extracted from the evaporator 7 and injected into the two-phase separation unit 3 in a certain proportion with the extractant via a metering pump. The flow rate of the extracted reaction liquid is 10-15% of the circulating mass of the system, or 10-15% of the total mass of the reaction system. The circulating mass of the system refers to the amount of the reaction system minus the amount discharged as product. The hourly circulation rate of the system is 5-10% of the total mass of the system materials. The molar ratio of organophosphorus ligands to extractant in the extracted reaction liquid is 1:3 to 1:8. The reaction solution, consisting of the light component, enters from the bottom of the two-phase separator 3, while the extractant solution, consisting of the heavy component, enters from the top of the two-phase separator 3. After thorough mixing, extraction, and separation in the two-phase separator 3, the materials enter the coalescence separator 4 for drying at a rate of 1 BV / h. The water content of the material exiting the coalescence separator 4 is <15 ppm. The dried material is returned to the reaction unit 1 to continue participating in the reaction. The aqueous phase enters the waste liquid tank 5. Due to a certain degree of loss of organophosphorus ligands, 5% of the initially added organophosphorus ligands needs to be replenished to the reaction unit 1 every 72 hours.

[0098] Therefore, the method of the present invention has the following effects:

[0099] (1) Low cost. Pyridine compounds are inexpensive and readily available, making the synthesis of water-soluble pyridine extractants economically feasible; the amount required is small, and a 1 wt% aqueous solution of the extractant is sufficient to meet the needs; a small amount of ligand is added to the reaction system every 72 hours, and phosphine ligands are inexpensive.

[0100] (2) Good regeneration effect. The catalyst activity did not decrease significantly after the unit ran continuously for 7 days.

[0101] (3) High stability. Key technical indicators such as reaction temperature, pressure, product conversion rate, yield, and product normal-to-isotropic ratio remain highly stable throughout the reaction cycle.

[0102] (4) The process is simple and easy to scale up.

[0103] The present invention will be described in detail below through specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention, and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art will understand that modifications that do not depart from the spirit and concept of the present invention fall within the scope of protection of the present invention. Unless otherwise specified, the reagents and instruments used in the following embodiments are all commercially available products.

[0104] In Comparative Examples 1, Examples 1-6, and 13-18, the metal precursor of catalytic system A was [Rh(CO)₂Cl]₂, and the organophosphine ligand had the following structure 1. In Examples 7-12 and 19-24, the metal precursor of catalytic system B was Rh(NO₃)₃, and the organophosphine ligand had the following structure 2. In Examples 1-12, the pyridine extractant A had the following structure 3. In Examples 13-24, the pyridine extractant B had the following structure 4.

[0105]

[0106] Comparative Example 1

[0107] In a pilot-scale experiment for the production of pentanal by the hydroformylation of mixed C4, the syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 ml / h, the reaction temperature was 100℃, the pressure was 2 MPa, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The reaction was carried out continuously for 7 days. The data on ligand content, free phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 1 (phosphorus content is obtained by...). 31 pNMR determination):

[0108] Table 1

[0109] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 2.4 2.25 2.1 1.96 1.72 Free phosphate concentration (wt%) 0 0.12 0.26 0.38 0.65 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[0.93×10 5 ]]> <![CDATA[0.85×10 5 ]]> <![CDATA[0.77×10 5 ]]> <![CDATA[0.72×10 5 ]]> Conversion rate % 0 98 95 86 82 Product positive and negative ratio 0 32 28 26 22

[0110] Example 1

[0111] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 ml / h, the reaction temperature was 100℃, the pressure was 2 MPa, the catalyst was catalyst A, and the reaction solution was pentanal. The system contained 400 wppm rhodium (6.5 g) and 2.4 wt% organophosphorus ligands (390 g). The flow rate of the extraction reaction solution was 200 ml / h, and the flow rate of the extractant aqueous solution was 12 ml / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 2 (the phosphorus content is obtained by...). 31 (P NMR determination):

[0112] Table 2

[0113] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 2.4 2.38 2.37 2.36 2.33 Free phosphate concentration (wt%) 0 0 0 0 0.03 Pyridine phosphate concentration (wt%) 0 0 0 0.05 0.05 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[0.95×10 5 ]]> <![CDATA[0.9×10 5 ]]> <![CDATA[0.87×10 5 ]]> Conversion rate % 0 98 98 96 93 Product positive and negative ratio 0 32 30 30 28

[0114] Example 2

[0115] In a pilot-scale experiment for the production of pentanal via the hydration of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 Wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 mL / h, and the flow rate of the extractant aqueous solution was 20 mL / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 3 (phosphorus content is obtained by...). 31 (P NMR determination):

[0116] Table 3

[0117]

[0118]

[0119] Example 3

[0120] In a pilot-scale experiment for the production of pentanal via the hydration of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 Wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 mL / h, and the flow rate of the extractant aqueous solution was 32 mL / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 4 (phosphorus content is obtained by...). 31 (P NMR determination):

[0121] Table 4

[0122] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 2.4 2.38 2.37 2.36 2.35 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.05 0.06 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[0.95×10 5 ]]> <![CDATA[0.93×10 5 ]]> <![CDATA[0.9×10 5 ]]> Conversion rate % 0 98 98 96 96 Product positive and negative ratio 0 32 30 30 30

[0123] Example 4

[0124] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 ml / h, the reaction temperature was 100℃, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 ml / h, the flow rate of the extractant aqueous solution was 12 ml / h, and 19.5 g of phosphine ligand was added to the system every 72 hours. After 7 days of continuous reaction, the ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 5 (phosphorus content is obtained by...). 31 (P NMR determination):

[0125] Table 5

[0126] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 2.4 2.38 2.4 2.39 2.4 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.05 0.05 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> Conversion rate % 0 98 98 98 96 Product positive and negative ratio 0 32 30 30 28

[0127] Example 5

[0128] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 mL / h, the flow rate of the extractant aqueous solution was 20 mL / h, and 19.5 g of phosphine ligand was added to the system every 72 hours. After 7 days of continuous reaction, the data on ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 6 (phosphorus content is obtained by...). 31 (P NMR determination):

[0129] Table 6

[0130] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 2.4 2.37 2.4 2.39 2.38 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.05 0.06 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> Conversion rate % 0 98 98 98 98 Product positive and negative ratio 0 32 32 32 32

[0131] Example 6

[0132] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 ml / h, the reaction temperature was 100℃, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 ml / h, the flow rate of the extractant aqueous solution was 32 ml / h, and 19.5 g of phosphine ligand was added to the system every 72 hours. After 7 days of continuous reaction, the data on ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 7 (phosphorus content is obtained by...). 31 (P NMR determination):

[0133] Table 7

[0134] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 2.4 2.38 2.4 2.4 2.39 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.06 0.06 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> Conversion rate % 0 98 98 98 98 Product positive and negative ratio 0 32 32 32 32

[0135] Example 7

[0136] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added. Catalyst B was used, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 ml / h, the reaction temperature was 100℃, the pressure was 2 MPa, the catalyst was catalyst B, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 1 wt% (156 g). The flow rate of the extraction reaction solution was 200 ml / h, and the flow rate of the extractant aqueous solution was 12 ml / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 2 (phosphorus content is obtained by...). 31 (P NMR determination):

[0137] Table 8

[0138]

[0139]

[0140] Example 8

[0141] In a pilot-scale experiment for the production of pentanal via the hydration of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst B, the reaction solution was pentanal, the rhodium content in the system was 400 Wppm (6.5 g), and the organophosphorus ligand content was 1 wt% (156 g). The flow rate of the extraction reaction solution was 200 mL / h, and the flow rate of the extractant aqueous solution was 20 mL / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 3 (phosphorus content is obtained by...). 31 (P NMR determination):

[0142] Table 9

[0143] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 1 0.98 0.98 0.96 0.94 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.02 0.02 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[0.96×10 5 ]]> <![CDATA[0.92×10 5 ]]> <![CDATA[0.9×10 5 ]]> Conversion rate % 0 98 98 96 94 Product positive and negative ratio 0 32 32 30 29

[0144] Example 9

[0145] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst B, the reaction solution was pentanal, the rhodium content in the system was 400 Wppm (6.5 g), and the organophosphorus ligand content was 1 wt% (156 g). The flow rate of the extraction reaction solution was 200 mL / h, and the flow rate of the extractant aqueous solution was 32 mL / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 4 (phosphorus content is obtained by...). 31 (P NMR determination):

[0146] Table 10

[0147] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 1 1 0.98 0.98 0.96 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.02 0.03 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[0.98×10 5 ]]> <![CDATA[0.98×10 5 ]]> <![CDATA[0.95×10 5 ]]> Conversion rate % 0 98 98 96 95 Product positive and negative ratio 0 32 32 30 30

[0148] Example 10

[0149] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst B, the reaction solution was pentanal, the rhodium content in the system was 400 Wppm (6.5 g), and the organophosphorus ligand content was 1 wt% (156 g). The flow rate of the extraction reaction solution was 200 mL / h, the flow rate of the extractant aqueous solution was 12 mL / h, and 7.8 g of phosphine ligand was added to the system every 72 hours. After 7 days of continuous reaction, the data on ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 5 (phosphorus content is obtained by...). 31 (P NMR determination):

[0150] Table 11

[0151]

[0152]

[0153] Example 11

[0154] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst B, the reaction solution was pentanal, the rhodium content in the system was 400 Wppm (6.5 g), and the organophosphorus ligand content was 1 wt% (156 g). The flow rate of the extraction reaction solution was 200 mL / h, the flow rate of the extractant aqueous solution was 20 mL / h, and 7.8 g of ligand was added to the system every 72 hours. After 7 days of continuous reaction, the ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 6 (phosphorus content is obtained by...). 31 (P NMR determination):

[0155] Table 12

[0156] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 1 1 1 0.99 1 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.03 0.04 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> Conversion rate % 0 98 98 98 97 Product positive and negative ratio 0 32 32 32 31

[0157] Example 12

[0158] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant A with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 ml / h, the reaction temperature was 100℃, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 ml / h, the flow rate of the extractant aqueous solution was 32 ml / h, and 19.5 g of phosphine ligand was added to the system every 72 hours. After 7 days of continuous reaction, the data on ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 7 (phosphorus content is obtained by...). 31 (P NMR determination):

[0159] Table 13

[0160] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 1 1 1 0.99 1 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.04 0.04 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> Conversion rate % 0 98 98 98 98 Product positive and negative ratio 0 32 32 32 32

[0161] Example 13

[0162] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 ml / h, the reaction temperature was 100℃, the pressure was 2 MPa, the catalyst was catalyst A, and the reaction solution was pentanal. The system contained 400 wppm rhodium (6.5 g) and 2.4 wt% organophosphorus ligands (390 g). The flow rate of the extraction reaction solution was 200 ml / h, and the flow rate of the extractant aqueous solution was 12 ml / h. After 7 days of continuous reaction, the data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 2 (the phosphorus content is obtained by...). 31 (P NMR determination):

[0163] Table 14

[0164] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 2.4 2.37 2.37 2.36 2.34 Free phosphate concentration (wt%) 0 0 0 0 0.03 Pyridine phosphate concentration (wt%) 0 0 0 0.05 0.05 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[0.95×10 5 ]]> <![CDATA[0.9×10 5 ]]> <![CDATA[0.88×10 5 ]]> Conversion rate % 0 98 98 96 93 Product positive and negative ratio 0 32 30 30 29

[0165] Example 14

[0166] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 Wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 mL / h, and the flow rate of the extractant aqueous solution was 20 mL / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 3 (phosphorus content is obtained by...). 31 (P NMR determination):

[0167] Table 15

[0168] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 2.4 2.38 2.37 2.36 2.33 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.05 0.05 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[0.95×10 5 ]]> <![CDATA[0.9×10 5 ]]> <![CDATA[0.89×10 5 ]]> Conversion rate % 0 98 98 96 95 Product positive and negative ratio 0 32 30 30 28

[0169] Example 15

[0170] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 ml / h, the reaction temperature was 100℃, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 ml / h, and the flow rate of the extractant aqueous solution was 32 ml / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 4 (phosphorus content is obtained by...). 31 (P NMR determination):

[0171] Table 16

[0172]

[0173]

[0174] Example 16

[0175] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 mL / h, the flow rate of the extractant aqueous solution was 12 mL / h, and 19.5 g of phosphine ligand was added to the system every 72 hours. After 7 days of continuous reaction, the data on ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 5 (phosphorus content is obtained by...). 31 (P NMR determination):

[0176] Table 17

[0177] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 2.4 2.38 2.4 2.39 2.4 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.05 0.05 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> Conversion rate % 0 98 98 98 96 Product positive and negative ratio 0 32 30 30 28

[0178] Example 17

[0179] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 mL / h, the flow rate of the extractant aqueous solution was 20 mL / h, and 19.5 g of phosphine ligand was added to the system every 72 hours. After 7 days of continuous reaction, the data on ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 6 (phosphorus content is obtained by...). 31 (P NMR determination):

[0180] Table 18

[0181] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 2.4 2.37 2.4 2.39 2.38 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.05 0.06 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> Conversion rate % 0 98 98 98 98 Product positive and negative ratio 0 32 32 32 32

[0182] Example 18

[0183] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 mL / h, the flow rate of the extractant aqueous solution was 32 mL / h, and 19.5 g of phosphine ligand was added to the system every 72 hours. After 7 days of continuous reaction, the data on ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 7 (phosphorus content is obtained by...). 31 (P NMR determination):

[0184] Table 19

[0185]

[0186]

[0187] Example 19

[0188] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added. Catalyst B was used, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 ml / h, the reaction temperature was 100℃, the pressure was 2 MPa, the catalyst was catalyst B, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 1 wt% (156 g). The flow rate of the extraction reaction solution was 200 ml / h, and the flow rate of the extractant aqueous solution was 12 ml / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 2 (phosphorus content is obtained by...). 31 (P NMR determination):

[0189] Table 20

[0190] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 1 0.98 0.98 0.96 0.96 Free phosphate concentration (wt%) 0 0 0 0 0.02 Pyridine phosphate concentration (wt%) 0 0 0 0.02 0.02 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[0.96×10 5 ]]> <![CDATA[0.93×10 5 ]]> <![CDATA[0.89×10 5 ]]> Conversion rate % 0 98 96 96 93 Product positive and negative ratio 0 34 32 30 28

[0191] Example 20

[0192] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst B, the reaction solution was pentanal, the rhodium content in the system was 400 Wppm (6.5 g), and the organophosphorus ligand content was 1 wt% (156 g). The flow rate of the extraction reaction solution was 200 mL / h, and the flow rate of the extractant aqueous solution was 20 mL / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 3 (phosphorus content is obtained by...). 31 (P NMR determination):

[0193] Table 21

[0194] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 1 0.98 0.98 0.96 0.94 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.02 0.02 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[0.96×10 5 ]]> <![CDATA[0.92×10 5 ]]> <![CDATA[0.9×10 5 ]]> Conversion rate % 0 98 98 96 94 Product positive and negative ratio 0 32 32 30 29

[0195] Example 21

[0196] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst B, the reaction solution was pentanal, the rhodium content in the system was 400 Wppm (6.5 g), and the organophosphorus ligand content was 1 wt% (156 g). The flow rate of the extraction reaction solution was 200 mL / h, and the flow rate of the extractant aqueous solution was 32 mL / h. The reaction was carried out continuously for 7 days. The data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 4 (phosphorus content is obtained by...). 31 (P NMR determination):

[0197] Table 22

[0198] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 1 1 0.98 0.98 0.96 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.02 0.03 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[0.98×10 5 ]]> <![CDATA[0.98×10 5 ]]> <![CDATA[0.95×10 5 ]]> Conversion rate % 0 98 98 96 95 Product positive and negative ratio 0 32 32 30 30

[0199] Example 22

[0200] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst B, the reaction solution was pentanal, the rhodium content in the system was 400 Wppm (6.5 g), and the organophosphorus ligand content was 1 wt% (156 g). The flow rate of the extraction reaction solution was 200 mL / h, the flow rate of the extractant aqueous solution was 12 mL / h, and 7.8 g of phosphine ligand was added to the system every 72 hours. After 7 days of continuous reaction, the data on ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 5 (phosphorus content is obtained by...). 31 (P NMR determination):

[0201] Table 23

[0202] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 1 0.98 1 0.99 1 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.03 0.03 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> Conversion rate % 0 98 98 97 97 Product positive and negative ratio 0 32 32 32 30

[0203] Example 23

[0204] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst B, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 1 wt% (156 g). The flow rate of the extraction reaction solution was 200 mL / h, the flow rate of the extractant aqueous solution was 20 mL / h, and 7.8 g of ligand was added to the system every 72 hours. After 7 days of continuous reaction, the data on the content of ligands, free phosphate esters, pyridine phosphates, catalyst activity, and key technical indicators at each time point are shown in Table 6 (phosphorus content is obtained by...). 31 (P NMR determination):

[0205] Table 24

[0206]

[0207]

[0208] Example 24

[0209] In a pilot-scale experiment for the production of pentanal via the hydroformylation of mixed C4, an online catalyst regeneration system was added, and an aqueous solution of extractant B with a concentration of 0.125 mol / L was prepared. The syngas feed rate was 15 L / h, the mixed C4 feed rate was 300 mL / h, the reaction temperature was 100 °C, the pressure was 2 MPa, the catalyst was catalyst A, the reaction solution was pentanal, the rhodium content in the system was 400 wppm (6.5 g), and the organophosphorus ligand content was 2.4 wt% (390 g). The flow rate of the extraction reaction solution was 200 mL / h, the flow rate of the extractant aqueous solution was 32 mL / h, and 19.5 g of phosphine ligand was added to the system every 72 hours. After 7 days of continuous reaction, the data on ligand, free phosphate, pyridine phosphate content, catalyst activity, and key technical indicators at each time point are shown in Table 7 (phosphorus content is obtained by...). 31 (P NMR determination):

[0210] Table 25

[0211] Reaction time (days) 0 1 3 5 7 Phosphite ligand concentration (wt%) 1 1 1 0.99 1 Free phosphate concentration (wt%) 0 0 0 0 0 Pyridine phosphate concentration (wt%) 0 0 0 0.04 0.04 <![CDATA[Catalyst activity g / molRh.h -1 > <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> <![CDATA[1×10 5 ]]> Conversion rate % 0 98 98 98 98 Product positive and negative ratio 0 32 32 32 32

[0212] As shown in the comparative examples and embodiments, in the pilot-scale experiment of producing pentanal by mixed C4 hydroformylation, with the extension of reaction time, the phosphite ligands in the catalyst system deteriorate to produce free phosphate esters, the amount of organophosphorus ligands decreases, phosphate ester impurities accumulate, and the catalyst activity and product N / A ratio decrease significantly, severely affecting reaction stability and product performance. Adding an online catalyst regeneration system and using pyridine extractants to extract the reaction system reduces the content of free phosphate esters, increases catalyst stability and product N / A ratio, and periodically replenishing the reaction system with a certain amount of phosphite ligands maintains essentially unchanged catalyst activity and product N / A ratio over long-term operation.

[0213] In summary, the online regeneration method provided by this invention can significantly improve the stability and product performance of the continuous hydroformylation reaction of olefins, greatly increase the utilization rate of the precious metal rhodium catalyst, and the extractant used is inexpensive and readily available, and the regeneration process is simple, making it highly economical and practical.

[0214] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for online regeneration of a rhodium-phosphine complex catalyst, characterized in that, The reaction system containing the rhodium phosphine complex catalyst was extracted using an aqueous extractant solution, and then the oil phase and aqueous phase were separated. The regenerated rhodium phosphine complex catalyst was present in the oil phase. The extractant aqueous solution is a solution obtained by mixing the extractant with water, and the extractant has the following structure: R1, R2, R3, and R4 may be the same or different, and are independently selected from one of hydrogen, halogen, trihalomethyl, hydroxyl, nitro, sulfonic acid, and cyano groups.

2. The method for online regeneration of the rhodium-phosphine complex catalyst according to claim 1, characterized in that, R1, R2, R3, and R4 are independently selected from hydrogen, halogens, and trihalomethyl; the extractant is a water-soluble compound.

3. The method for online regeneration of the rhodium-phosphine complex catalyst according to claim 2, characterized in that, The extractant is at least one of compounds L1 to L10, wherein R1, R2, R3, and R4 in compounds L1 to L10 are respectively: L1: R1 = hydrogen, R2 = hydrogen, R3 = hydrogen, R4 = hydrogen; L2: R1 = hydrogen, R2 = hydrogen, R3 = chlorine, R4 = chlorine; L3: R1 = hydrogen, R2 = chlorine, R3 = chlorine, R4 = hydrogen; L4: R1 = chlorine, R2 = chlorine, R3 = chlorine, R4 = hydrogen; L5: R1 = chlorine, R2 = chlorine, R3 = chlorine, R4 = chlorine; L6: R1 = hydrogen, R2 = chlorine, R3 = chlorine, R4 = chlorine; L7: R1 = hydrogen, R2 = trichloromethyl, R3 = chlorine, R4 = chlorine; L8: R1 = hydrogen, R2 = trifluoromethyl, R3 = chlorine, R4 = chlorine; L9: R1 = hydrogen, R2 is trichloromethyl, R3 = hydrogen, R4 is chlorine; L10: R1 = hydrogen, R2 is trifluoromethyl, R3 = hydrogen, R4 is chlorine.

4. The method for online regeneration of the rhodium-phosphine complex catalyst according to claim 1, characterized in that, The reaction system is an olefin hydroformylation reaction system; the rhodium phosphine complex catalyst is a catalyst system formed by complexing a carbonyl rhodium precursor with an organophosphine ligand containing a phosphite structure; the extractant aqueous solution is used to extract 10-15% by weight of the reaction system containing the rhodium phosphine complex catalyst.

5. The method for online regeneration of the rhodium-phosphine complex catalyst according to claim 4, characterized in that, After adding an organophosphorus ligand with a phosphite structure to the oil phase, the resulting oil phase is reused to catalyze the hydroformylation of olefins.

6. An olefin hydroformylation reaction system, characterized in that, include: A reaction apparatus used for the hydroformylation of olefins; Extractant storage tank, used for preparing or storing extractant solutions; The two-phase separation device is connected to the reaction device and the extractant storage tank respectively, so as to transport the reaction system and the extractant solution to the two-phase separation device for extraction and phase separation to obtain the oil phase and the water phase. The two-phase separation device is connected to the reaction device to circulate the oil phase back to the reaction device; the extractant aqueous solution is a solution obtained by mixing the extractant with water, and the extractant has the following structure: R1, R2, R3, and R4 may be the same or different, and are independently selected from one of hydrogen, halogen, trihalomethyl, hydroxyl, nitro, sulfonic acid, and cyano groups.

7. The olefin hydroformylation reaction system according to claim 6, characterized in that, Also includes: An evaporation device is connected to the reaction device and the two-phase separation device to evaporate a portion of the reaction system and then transport it to the two-phase separation device, while the remaining reaction system is discharged as a reaction product.

8. The olefin hydroformylation reaction system according to claim 6, characterized in that, Also includes: A coalescence separation device is connected to the reaction device and the two-phase separation device to dehydrate the oil phase and then transport it to the reaction device.

9. The olefin hydroformylation reaction system according to claim 6, characterized in that, The reaction apparatus is equipped with a ligand replenishment port for periodically replenishing the catalyst ligand.

10. A method for hydroformylation of olefins, characterized in that, The olefin hydroformylation method includes the following steps: Step 1: Olefins and syngas undergo hydroformylation under the catalysis of a rhodium phosphine complex catalyst; Step 2: Extract part or all of the reaction mixture from Step 1 using an aqueous extractant solution to obtain an oil phase and an aqueous phase; The oil phase is used for the hydroformylation of olefins via cyclic catalysis; the extractant aqueous solution is a solution obtained by mixing the extractant with water, and the extractant has the following structure: R1, R2, R3, and R4 may be the same or different, and are independently selected from one of hydrogen, halogen, trihalomethyl, hydroxyl, nitro, sulfonic acid, and cyano groups.

11. The olefin hydroformylation method according to claim 10, characterized in that, The olefin hydroformylation method is a continuous reaction; the continuous reaction system is periodically replenished with ligands for the rhodium phosphine complex catalyst.

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