CN109776294B - Olefin hydroformylation reaction method - Google Patents
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Abstract
The invention provides a method for hydroformylation reaction of olefin, which comprises the steps of hydroformylation reaction of olefin and synthesis gas to generate aldehyde through a first stage reaction and a second stage reaction in the presence of a rhodium complex catalyst, wherein the temperature of the first stage reaction is at least 5 ℃ lower than that of the second stage reaction. The invention adopts the sectional reaction, controls the temperature of the two-section reaction, and leads reactants to carry out the pre-reaction at lower temperature to improve the activity and the stability of the catalyst, thereby improving the performance of the catalyst and reducing the production cost.
Description
Technical Field
The invention belongs to the technical field of hydroformylation reaction, and particularly relates to an olefin hydroformylation reaction method beneficial to improving the stability and activity of a rhodium complex catalyst.
Background
The catalyst used in the hydroformylation reaction in industrial production is generally a cobalt (Co) based or rhodium (Rh) based catalyst, i.e., a catalyst having cobalt (Co) or rhodium (Rh) as a metal active center. However, most of the catalysts used in the hydroformylation reaction are rhodium-based catalysts due to various reasons such as severe reaction conditions, many side reactions, poor selectivity of reaction products, high reaction energy consumption, and complicated cobalt recovery process when using cobalt-based catalysts.
The activity of rhodium-based catalysts in hydroformylation processes and the selectivity to the product aldehyde depend on the combination of catalyst precursor and ligand and operating conditions. In the process of performing the olefin formylation reaction on the rhodium-based catalyst, as the complex catalyst formed by rhodium and other substances is very sensitive to the change of the state in the reaction process, the catalyst is easy to deactivate, thereby influencing the reaction conversion rate and the selectivity of products.
Chinese patent CN101293818 discloses a hydroformylation method, which comprises performing two-stage reaction on mixed butene hydroformylation, and feeding the unreacted raw material in the first stage reaction into the second stage reaction for continuous reaction, thereby solving the problem that the internal olefin can not react effectively, and improving the utilization rate of the olefin, but not relating to the improvement of the activity and stability of the catalyst. Chinese patent CN103814006 discloses a hydroformylation method with improved catalyst stability in the reaction, which adds a special α, β -unsaturated carbonyl compound to inhibit the decomposition of ligand and catalyst in the hydroformylation reaction, and this method increases the stability of catalyst to some extent, but also increases the reaction cost. Chinese patent CN102123978 in examples 8 to 14 uses a rhodium complex of calixarene bisphosphite as a catalyst to hydroformylate 1-octene by varying the partial pressure of carbon monoxide to give two or more aldehydes with target N/I ratios selectable in the range of 7-31, but this patent also does not address the problems of improvement in catalyst activity and stability, etc.
Disclosure of Invention
In order to improve the stability and the activity of a rhodium complex catalyst in a hydroformylation reaction, the invention provides a novel olefin hydroformylation reaction method, and the stability and the activity of the rhodium complex catalyst are improved by controlling different temperatures of two stages of reactions in a sectional reaction mode.
Specifically, the invention is carried out by adopting the following technical scheme:
a process for the hydroformylation of olefins comprising reacting an olefin and synthesis gas in the presence of a rhodium complex catalyst in a first stage and a second stage to form an aldehyde, wherein the first stage reaction temperature is at least 5 ℃ lower than the second stage reaction temperature, preferably the first stage reaction temperature is at least 10 ℃ lower than the second stage reaction temperature, more preferably the first stage reaction temperature is at least 15 ℃ lower than the second stage reaction temperature, and most preferably the first stage reaction temperature is 20 ℃ lower than the second stage reaction temperature.
According to a preferred embodiment of the invention, the temperature of the first stage reaction is between 50 and 135 ℃, preferably between 50 and 100 ℃, preferably between 60 and 80 ℃, more preferably between 70 and 80 ℃; and/or the pressure of the reaction is 0 to 8MPa, preferably 1 to 6MPa, more preferably 1 to 3 MPa; the reaction time is controlled within 50min, such as 1-40min, or 5-40min, or 6-30min, or 8-30min, preferably the first period reaction time is more than 5min, preferably 10-25min, more preferably 10-20min, most preferably 15-20 min.
According to a preferred embodiment of the invention, the temperature of the second stage reaction is between 55 and 140 ℃, preferably between 80 and 110 ℃, more preferably between 90 and 100 ℃; and/or the pressure of the reaction is 0 to 8MPa, preferably 1 to 6MPa, more preferably 1 to 3 MPa; and/or the reaction time is 1 to 8 hours, preferably 1 to 5 hours, more preferably 1 to 3 hours.
In the present invention, the temperature of the first stage reaction is maintained lower than the temperature of the second stage reaction, and the first stage reaction temperature is controlled to be at least 5 ℃ lower than the second stage reaction temperature, preferably at least 10 ℃ lower, preferably at least 15 ℃ lower than the second stage reaction temperature, more preferably at least 20 ℃ lower than the second stage reaction temperature. The difference between the first stage reaction temperature and the second stage temperature is controlled to be not more than 40 ℃ in general, and preferably, the difference between the first stage reaction temperature and the second stage temperature is not more than 30 ℃. For example, the temperature of the first stage reaction may be controlled to be 5-40 deg.C, or 5-30 deg.C, or 10-25 deg.C, or 10-20 deg.C, or 15-20 deg.C lower than the temperature of the second stage reaction. The first-stage reaction temperature is controlled to be lower than the second-stage reaction temperature, so that the stability of the catalyst is improved, and the activity of the catalyst is always kept at a higher level, probably because the combination between rhodium and a ligand in the rhodium complex catalyst used by the invention is easily influenced by reaction conditions to cause the breakage of a coordination bond between the ligand and the rhodium, so that the activity and the stability of the catalyst are influenced.
And preferably, for the reaction with higher reaction temperature in the second stage compared with the reaction with lower reaction temperature in the second stage, in order to improve the performance of the catalyst, the time of the reaction in the first stage should be increased appropriately to avoid the damage of the high reaction temperature to the performance of the catalyst.
In the present invention, the first-stage reaction and the second-stage reaction may be carried out in the same reactor, or may be carried out in two reactors connected in series. For convenience of operation, it is preferable to use the same reaction pressure in the first-stage reaction and the second-stage reaction.
According to a preferred embodiment of the present invention, the temperature is increased from the first reaction temperature to the second reaction temperature in a stepwise manner. Preferably, the temperature is increased from the first reaction temperature to the second reaction temperature at a rate of 3-6 deg.C/min.
According to a preferred embodiment of the invention, the olefin is C2-C12Olefin, preferably C5-C12Olefin, preferably C6-C12Olefin, more preferably C6-C10The alkene, in one embodiment of the present invention, is octene.
According to a preferred embodiment of the present invention, the rhodium complex catalyst is represented by the formula (I):
Rh(L1)x(L2)y(L3)zformula (I)
Wherein L is1Selected from the group consisting of carbonyl, acetylacetone, diphenylphosphine, cyclooctadiene, norbornene and triphenylphosphine, L2And L3The same or different, each independently selected from hydrogen, carbonyl, chlorine, bromine, acetylacetone, diphenylphosphine, cyclooctadiene, norbornene and triphenylphosphine;
x is an integer of 1-3, y and z are each independently selected from integers of 0-4, and x + y + z is ≤ 5.
According to a preferred embodiment of the present invention, the rhodium complex catalyst is an organophosphine-modified rhodium complex catalyst, including a rhodium complex catalyst and an organophosphorus compound. The catalyst using the rhodium complex modified with the organophosphine has a better effect, and the probable reason is that the organophosphine compound can form a complex with rhodium, so that the separation of the complex and the rhodium in the rhodium complex catalyst can be prevented, the rhodium complex can be stabilized, and the stability of the catalyst can be improved.
According to a preferred embodiment of the present invention, the organic phosphine compound is a phenyl group-containing organic phosphine compound selected from the group consisting of substituted or unsubstituted triphenylphosphine oxide, substituted or unsubstituted triphenylphosphine and substituted or unsubstituted diphenylphosphine, preferably substituted or unsubstituted triphenylphosphine or substituted or unsubstituted diphenylphosphine.
According to a preferred embodiment of the present invention, the substituted triphenylphosphine refers to triphenylphosphine having a substituent on the benzene ring in triphenylphosphine, wherein the substituent may substitute any hydrogen of any benzene ring, preferably, the substituted triphenylphosphine is represented by formula (II):
wherein R is1、R2And R3Each independently selected from C1-C5Alkyl or alkoxy, preferably, R1、R2And R3Each independently selected from methyl, ethyl, n-propyl, isopropyl or C1-C5An alkoxy group;
according to a preferred embodiment of the present invention, the substituted diphenylphosphine refers to a diphenylphosphine compound having a substituent on the phenyl ring in the diphenylphosphine, wherein the substituent may be substituted for any one hydrogen of any one of the phenyl rings, and preferably, the substituted diphenylphosphine is represented by formula (III):
wherein R is4Selected from cyclohexane or cycloheptane;
R5and R6Each independently selected from C1-C5Alkyl or alkoxy, preferably, R5And R6Each independently selected from methyl, ethyl, n-propyl, isopropyl or C1-C5An alkoxy group.
According to a preferred embodiment of the present invention, the molar ratio of the organophosphinic compound to rhodium in the rhodium complex catalyst is (0.5-200):1, preferably (12-200):1, more preferably (40-150): 1.
According to a preferred embodiment of the present invention, the molar ratio of the olefin to the rhodium complex catalyst in the hydroformylation reaction is (500-.
According to a preferred embodiment of the invention, the molar ratio of hydrogen to carbon monoxide in the synthesis gas is (0.1-20): 1, preferably, the molar ratio of hydrogen to carbon monoxide in the synthesis gas is (1-10): 1, more preferably 1: 1.
according to a preferred embodiment of the invention, the hydroformylation reaction is carried out in a solvent, preferably an organic solvent, preferably selected from C4-C10Aldehyde, C4-C10Ketone (b), C4-C10And one or more of alkanes, aromatics, and substituted aromatics. The hydroformylation solvent may be exemplified by one or more of butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, caprylic aldehyde, nonanal, methyl isobutyl ketone, acetophenone, toluene, xylene, chlorobenzene, and heptaldehyde.
According to a preferred embodiment of the invention, the olefin is premixed with the catalyst before contacting the olefin with the synthesis gas in the hydroformylation reaction, preferably for a premixing time of less than 10min, such as from 0.1 to 10min, preferably less than 5min, such as from 0.1 to 5min, more preferably from 1 to 3 min.
The invention sets two stages of different reaction temperatures in the hydroformylation reaction, controls the reaction temperature of the first stage to be lower than that of the second stage by at least 5 ℃, and improves the activity and stability of the catalyst by using the method, thereby improving the use efficiency of the rhodium catalyst and reducing the production cost.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
In the examples of the present invention, the chromatographic analysis: agilent 7890A and nitrogen as carrier gas.
31PNMR analysis: bruker AV400D in CDCl3Is a solvent.
Example 1
In a glove box under an inert atmosphere, 12.14mL of 1-octene was measured and dissolved in 12.86mL of toluene at a molar ratio of 1-octene to rhodium in the rhodium complex catalyst of 4000:1 and added to a glass syringe. 17.50mg of tris (triphenylphosphine) carbonylrhodium hydride (catalyst of the structure of formula I, where L is1Is H, L2Is CO, L3Is triphenylphosphine, x ═ y ═ 1, z ═ 3, and 630mg triphenylphosphine (a compound of the structure of formula II, where R is1、R2And R3All hydrogen) was dissolved in 10mL of toluene (triphenylphosphine to rhodium molar ratio 126:1), added to another glass syringe, and the syringe was sealed and removed from the glove box.
The hydroformylation reaction apparatus was a 50mL autoclave reaction apparatus. Heating the autoclave to 80 deg.C, evacuating, and introducing synthesis gas (CO: H)21:1) were replaced several times, the vent valve was opened, and then a toluene solution of the catalyst ((triphenylphosphine) rhodium carbonyl hydride and a toluene solution of triphenylphosphine) was quickly added to the reaction vessel, and then a toluene solution of 1-octene was added to the reaction vessel. Closing the vent valve, premixing and stirring for 2min at a set pressure of 2MPa, and introducing synthesis gas (CO: H)21:1) for 20min, and then heating the autoclave to 100 ℃ at a rate of 5 ℃/min and continuing the reaction for 100 min. After the reaction is completed, the reaction liquid is collected and the catalyst is separated and recovered. The liquid phase product from which the catalyst was removed was chromatographed, and the results are shown in Table 1 (fresh catalyst).
The color of the toluene solution of the recovered catalyst did not change significantly from that before the reaction, indicating that rhodium was not oxidized. At the same time pass31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the structure of the catalyst is not destroyed. The recovered catalyst was used for the above reaction again without further treatment, and after the reaction was completed, the reaction solution was collected for chromatography, and the results are shown in table 1.
Example 2
The same as in example 1, except that the amount of triphenylphosphine added was changed to 450mg (molar ratio of organophosphine compound to rhodium: 90: 1). The test results are shown in Table 1.
The color of the toluene solution of the recovered catalyst did not change significantly from that before the reaction, indicating that rhodium was not oxidized. At the same time pass31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the structure of the catalyst is not destroyed. The recovered catalyst was used to conduct the above reaction again without further treatment, and after completion of the reaction, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 3
The same as in example 1, except that the amount of triphenylphosphine added was changed to 200mg (molar ratio of organophosphine compound to rhodium: 40: 1). The test results are shown in Table 1.
The toluene solution of the recovered catalyst was slightly darker in color than before the reaction, indicating that a small amount of rhodium was oxidized. At the same time pass31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the structure of the catalyst is not destroyed. The recovered catalyst was used to conduct the above reaction again without further treatment, and after completion of the reaction, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 4
The same as example 1, except that the organic phosphine compound was replaced with triphenylphosphine oxide in an equimolar amount (molar ratio of organic phosphine compound to rhodium: 126:1), the other experimental conditions were unchanged, and the test results are shown in Table 1.
The color of the toluene solution of the recovered catalyst did not change significantly from that before the reaction, indicating that rhodium was not oxidized. At the same time pass31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the structure of the catalyst is not destroyed. The recovered catalyst was used to conduct the above reaction again without further treatment, and after completion of the reaction, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 5
The difference from example 1 is that the rhodium complex catalyst used is triphenylphosphine rhodium acetylacetonate. The test results are shown in Table 1.
The color of the toluene solution of the recovered catalyst did not change significantly from that before the reaction, indicating that rhodium was not oxidized. At the same time pass31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the structure of the catalyst is not destroyed. The recovered catalyst was used to conduct the above reaction again without further treatment, and after completion of the reaction, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 6
The same as example 1 except that the temperature in the first stage reaction was 95 ℃ and the temperature in the second stage reaction was 100 ℃. The test results are shown in Table 1.
The toluene solution of the recovered catalyst was slightly darker in color than before the reaction, indicating that a small amount of rhodium was oxidized. By passing31PNMR analysis shows that the peak position of P after reaction is not changed obviously when the chemical environment of P atom in the ligand combined with rhodium is changed, which indicates that the phosphine ligand combined with the catalyst is not separated,the catalyst structure was not destroyed. The recovered catalyst was used to conduct the above reaction again without further treatment, and after completion of the reaction, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 7
The difference from example 1 is that the temperature in the first stage of the reaction was 90 ℃ and the temperature in the second stage of the reaction was 100 ℃. The test results are shown in Table 1.
The toluene solution of the recovered catalyst was slightly darker in color than before the reaction, indicating that a small amount of rhodium was oxidized. By passing31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the catalyst structure is not destroyed. The recovered catalyst was used for the above reaction again without further treatment, and after the reaction was completed, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 8
The difference from example 1 is that the temperature in the first stage reaction was 85 ℃ and the temperature in the second stage reaction was 100 ℃. The test results are shown in Table 1.
The toluene solution of the recovered catalyst was slightly darker in color than before the reaction, indicating that a small amount of rhodium was oxidized. By passing31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the catalyst structure is not destroyed. The recovered catalyst was used for the above reaction again without further treatment, and after the reaction was completed, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 9
The difference from example 1 is that the temperature in the first stage reaction was 70 ℃ and the temperature in the second stage reaction was 100 ℃. The test results are shown in Table 1.
The toluene solution of the recovered catalyst showed no significant change in color, indicating that the rhodium was not oxidized. By passing31PNMR analysis of the change in the chemical environment of the P atom in the rhodium-bound ligand revealedThe chemical environment of the catalyst is not obviously changed after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the catalyst structure is not damaged. The recovered catalyst was used for the above reaction again without further treatment, and after the reaction was completed, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 10
The difference from example 1 is that the temperature in the first stage reaction was 60 ℃ and the temperature in the second stage reaction was 100 ℃. The test results are shown in Table 1.
The toluene solution of the recovered catalyst showed no significant change in color, indicating that the rhodium was not oxidized. By passing31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the catalyst structure is not destroyed. The recovered catalyst was used for the above reaction again without further treatment, and after the reaction was completed, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 11
The difference from example 1 is that the temperature in the first stage reaction was 70 ℃ and the temperature in the second stage reaction was 90 ℃. The test results are shown in Table 1.
The color of the toluene solution of the recovered catalyst did not change significantly from that before the reaction, indicating that rhodium was not oxidized. At the same time pass31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the structure of the catalyst is not destroyed. The recovered catalyst was used to conduct the above reaction again without further treatment, and after completion of the reaction, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 12
The difference from example 1 is that the temperature in the first stage reaction was 60 ℃ and the temperature in the second stage reaction was 80 ℃. The test results are shown in Table 1.
The toluene solution of the recovered catalyst showed no significant change in color, indicating rhodiumNot oxidized. By passing31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the catalyst structure is not destroyed. The recovered catalyst was used for the above reaction again without further treatment, and after the reaction was completed, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 13
The difference from example 1 is that the temperature in the first stage reaction was 90 ℃ and the temperature in the second stage reaction was 110 ℃. The test results are shown in Table 1.
The toluene solution of the recovered catalyst was slightly darker in color than before the reaction, indicating that a small amount of rhodium was oxidized. By passing31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the catalyst structure is not destroyed. The recovered catalyst was used for the above reaction again without further treatment, and after the reaction was completed, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 14
The difference from example 1 is that the reaction time in the first stage is 5min and the reaction time in the second stage is 115 min. The test results are shown in Table 1.
The toluene solution of the recovered catalyst was slightly darker in color than before the reaction, indicating that a small amount of rhodium was oxidized. By passing31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the catalyst structure is not destroyed. The recovered catalyst was used for the above reaction again without further treatment, and after the reaction was completed, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 15
The difference from example 1 is that the reaction time in the first stage is 10min, and the reaction time in the second stage is 110 min. The test results are shown in Table 1.
The toluene solution of the recovered catalyst was slightly darker in color than before the reaction, indicating that a small amount of rhodium was oxidized. By passing31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the catalyst structure is not destroyed. The recovered catalyst was used for the above reaction again without further treatment, and after the reaction was completed, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 16
The difference from example 1 is that the reaction time in the first stage is 15min and the reaction time in the second stage is 105 min. The test results are shown in Table 1.
The toluene solution of the recovered catalyst showed no significant change in color, indicating that the rhodium was not oxidized. By passing31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the catalyst structure is not destroyed. The recovered catalyst was used for the above reaction again without further treatment, and after the reaction was completed, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 17
The difference from example 1 is that the reaction time in the first stage was 40min and the reaction time in the second stage was 80 min. The test results are shown in Table 1.
The color of the toluene solution of the recovered catalyst did not change significantly from that before the reaction, indicating that rhodium was not oxidized. At the same time pass31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the structure of the catalyst is not destroyed. The recovered catalyst was used to conduct the above reaction again without further treatment, and after completion of the reaction, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 18
The same as in example 1, except that the molar ratio of 1-octene to rhodium in the rhodium complex catalyst was 2000: 1. the test results are shown in Table 1.
The color of the toluene solution of the recovered catalyst did not change significantly from that before the reaction, indicating that rhodium was not oxidized. At the same time pass31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the structure of the catalyst is not destroyed. The recovered catalyst was used to conduct the above reaction again without further treatment, and after completion of the reaction, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 19
The difference from example 1 is that the molar ratio of 1-octene to rhodium complex catalyst is 8000: 1. the test results are shown in Table 1.
The color of the toluene solution of the recovered catalyst did not change significantly from that before the reaction, indicating that rhodium was not oxidized. At the same time pass31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the structure of the catalyst is not destroyed. The recovered catalyst was used to conduct the above reaction again without further treatment, and after completion of the reaction, the reaction solution was collected and subjected to chromatographic analysis, and the results are shown in table 1.
Example 20
The same as in example 1, except that the molar ratio of 1-octene to rhodium complex catalyst was 10000: 1. the test results are shown in Table 1.
The toluene solution of the recovered catalyst slightly changed in color from before the reaction, indicating that a small amount of rhodium was oxidized. At the same time pass31The PNMR analysis shows that the chemical environment of the P atom in the ligand combined with rhodium is not changed obviously after the reaction, which indicates that the phosphine ligand combined with the catalyst is not separated and the structure of the catalyst is not destroyed. The recovered catalyst is not required to be treated again, the recovered catalyst is used for carrying out the reaction again, and after the reaction is finished, reaction liquid is collected and fed into the reactorThe results of the line chromatography are shown in Table 1.
Comparative example 1
The same as example 1, except that the autoclave was directly heated to 100 ℃ for 120min, the remaining experimental conditions were unchanged, and the test results are shown in Table 1.
The toluene solution of the recovered catalyst changed in color from pale yellow before the reaction to brown, and the catalyst was oxidized. By passing31The PNMR analysis shows that the peak position of P after reaction is obviously changed when the chemical environment of the P atom in the ligand combined with rhodium is changed, which indicates that the catalyst structure is destroyed.
Comparative example 2
The same as example 4, except that the autoclave was directly heated to 100 ℃ for 120min, the remaining experimental conditions were unchanged, and the test results are shown in Table 1.
The toluene solution of the recovered catalyst changed in color from pale yellow before the reaction to brown, and the catalyst was oxidized. By passing31The PNMR analysis shows that the peak position of P after reaction is obviously changed when the chemical environment of the P atom in the ligand combined with rhodium is changed, which indicates that the catalyst structure is destroyed.
Comparative example 3
The same as example 1, except that 1-octene was not added in the stage 1 reaction for 0.5h, and 1-octene was added in the stage 2 reaction for 120min, and the rest of the experimental conditions were unchanged, the test results are shown in Table 1.
TABLE 1
"- - -" indicates no detection.
As can be seen from the data in table 1, by setting the reaction temperatures in the two stages to be different, the conversion of the starting material and the yield of the product are significantly improved compared to the reaction at a single temperature. As can be seen from comparison of comparative example 1 and comparative example 2 and example 4, the catalyst activity and selectivity are low when the catalyst is used to directly react at high temperature. As can be seen from the comparison of comparative example 3 and example 1, the catalyst activity and selectivity were low when the catalyst system was pre-reacted alone.
By using the method provided by the invention, the catalyst still has good catalytic effect when being recycled, and the conversion rate of the obtained octenes and the selectivity of the nonanal are kept at a higher level.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (29)
1. A method for hydroformylation of olefins comprises reacting olefins and synthesis gas in the presence of a rhodium complex catalyst to produce aldehydes in a first stage reaction and a second stage reaction, wherein the temperature of the first stage reaction is 50-135 ℃; and/or the pressure of the reaction is 0-8 MPa; and/or the reaction time is within 50min, and the temperature of the second-stage reaction is 55-140 ℃; and/or the pressure of the reaction is 0-8 MPa; and/or the reaction time is 1-8h, and the temperature of the first stage reaction is lower than the temperature of the second stage reaction by at least 5 ℃.
2. The process of claim 1, wherein the temperature of the first stage reaction is at least 10 ℃ lower than the temperature of the second stage reaction.
3. The process of claim 1 or 2, wherein the temperature of the first stage reaction is at least 15 ℃ lower than the temperature of the second stage reaction.
4. The method according to claim 1 or 2, wherein the temperature of the first stage reaction is 60-80 ℃; and/or the pressure of the reaction is 1-6 MPa; and/or the reaction time is 10-25 min.
5. The method according to claim 1 or 2, wherein the temperature of the first stage reaction is 70-80 ℃; and/or the pressure of the reaction is 1-3 MPa; and/or the reaction time is 10-20 min.
6. The method of claim 1 or 2, wherein the temperature of the second stage reaction is 80-110 ℃; and/or the pressure of the reaction is 1-6 MPa; and/or the reaction time is 1-5 h.
7. The method according to claim 1 or 2, wherein the temperature of the second stage reaction is 90-100 ℃; and/or the pressure of the reaction is 1-3 MPa; and/or the reaction time is 1-3 h.
8. The process according to claim 1 or 2, characterized in that the olefin is C2-C12An olefin.
9. The process according to claim 1 or 2, characterized in that the olefin is C5-C12An olefin.
10. The process according to claim 1 or 2, characterized in that the olefin is C6-C10An olefin.
11. The process of claim 1 or 2, wherein the rhodium complex catalyst is of formula (I):
Rh(L1)x(L2)y(L3)zformula (I)
Wherein L is1Selected from the group consisting of carbonyl, acetylacetone, diphenylphosphine, cyclooctadiene, norbornene and triphenylphosphine, L2And L3The same or different, each independently selected from hydrogen, carbonyl, chlorine, bromine, acetylacetone, diphenylphosphine, cyclooctadiene, norbornene and triphenylphosphine;
x is an integer of 1-3, y and z are each independently selected from integers of 0-4, and x + y + z is ≤ 5.
12. The process of claim 1 or 2, wherein the rhodium complex catalyst is a rhodium complex catalyst modified with an organophosphinic compound.
13. The method according to claim 12, wherein the organophosphinic compound is a phenyl-containing organophosphinic compound.
14. The method of claim 12, wherein the organic phosphine compound is selected from the group consisting of substituted or unsubstituted triphenylphosphine oxide, substituted or unsubstituted triphenylphosphine, and substituted or unsubstituted diphenylphosphine.
15. The method of claim 14,
the substituted triphenylphosphine is represented by formula (II):
wherein R is1、R2And R3Each independently selected from C1-C5Alkyl or alkoxy.
16. The method of claim 15, wherein R is1、R2And R3Each independently selected from methyl, ethyl, n-propyl, isopropyl or C1-C5An alkoxy group.
17. The method of claim 14,
the substituted diphenylphosphine is represented by formula (III):
wherein R is4Selected from cyclohexane or cycloheptane;
R5and R6Each independently selected from C1-C5Alkyl or alkoxy.
18. The method of claim 17,
R5and R6Each independently selected from methyl, ethyl, n-propyl, isopropyl or C1-C5An alkoxy group.
19. The process of claim 12, wherein the molar ratio of the organophosphinic compound to rhodium in the rhodium complex catalyst is (0.5-200): 1.
20. The process of claim 12, wherein the molar ratio of organophosphinic compound to rhodium in the rhodium complex catalyst is (12-200): 1.
21. The process of claim 12, wherein the molar ratio of organophosphinic compound to rhodium in the rhodium complex catalyst is (40-150): 1.
22. The process as claimed in claim 1 or 2, characterized in that the molar ratio of the olefin to rhodium in the rhodium complex catalyst is (500-; and/or the molar ratio of hydrogen to carbon monoxide in the synthesis gas is (0.1-20): 1.
23. the process as claimed in claim 1 or 2, characterized in that the molar ratio of the olefin to rhodium in the rhodium complex catalyst is (1000-; and/or the molar ratio of hydrogen to carbon monoxide in the synthesis gas is (1-10): 1.
24. the process as claimed in claim 23, wherein the molar ratio of the olefin to rhodium in the rhodium complex catalyst is (2000- > 8000): 1.
25. The process according to claim 1 or 2, characterized in that the hydroformylation reaction is carried out in a solvent, which is an organic solvent.
26. The method of claim 25, wherein the organic solvent is selected from C4-C10Aldehyde, C4-C10Ketone (b), C4-C10At least one of alkane, acetophenone, toluene, xylene and chlorobenzene.
27. The process according to claim 1 or 2, characterized in that in the hydroformylation reaction the olefin is premixed with the catalyst for less than 10min before contacting the olefin with the synthesis gas.
28. The method of claim 27, wherein the premixing time is less than 5 min.
29. The method of claim 27, wherein the premixing time is less than 1-3 min.
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| CN113698281B (en) * | 2020-05-21 | 2023-10-10 | 中国石油化工股份有限公司 | Method for hydroformylation |
| CN112679327B (en) * | 2021-01-12 | 2022-01-04 | 四川大学 | Method for preparing aldehyde compound by olefin two-phase hydroformylation |
| CN115010586B (en) * | 2021-03-05 | 2024-10-11 | 中国石油化工股份有限公司 | Hydroformylation reaction method and system |
| CN115701418B (en) * | 2021-08-02 | 2024-05-17 | 中国石油化工股份有限公司 | Aldol composition and preparation method thereof, and method for continuously preparing aldehyde and alcohol |
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