Method for preparing aldehyde through butene hydroformylation
By dissolving rhodium catalysts and phosphite ligands in amide solvents, and utilizing their solubility differences with olefins and reaction products, a simplified process of hydroformylation reaction of mixed butenes and reduced production costs are achieved.
Patent Information
- Application Number
- CN202311806268.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-26
- Publication Date
- 2025-06-27
AI Technical Summary
In the prior art, the hydroformylation reaction of mixed butenes has problems such as complex process and high production cost. Especially in a homogeneous catalytic system, the catalyst and product are difficult to separate, and the produced valeraldehyde boiling point is high, resulting in rapid catalyst deactivation and hydrolysis of phosphite ligands, increasing process complexity and cost.
A strongly polar amide solvent is used as the solvent, and the rhodium catalyst and phosphite ligand are easily soluble in such solvents, while olefins and reaction products are hard to dissolve in amide solvents. The premix solution is maintained at a low temperature, added to a mixed atmosphere of hydrogen and carbon monoxide, heated and the reaction is heated, and the layer is automatically separated after the reaction is completed, and the product can be separated directly.
The process flow is simplified, the supplementary demand for phosphine ligands is reduced, the multiple problems of impurities caused by hydrolysis is avoided, the production cost is reduced, and the reaction activity is improved. It is suitable for reaction under low temperature and low pressure conditions.
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Abstract
Description
Technical Field
[0001] This application relates to an aldehyde synthesis process, and particularly to a hydroformylation reaction. Background Art
[0002] The preparation of aldehydes by hydroformylation reaction is one of the most widely used homogeneous catalytic reactions in industry. The product aldehydes are not only important chemical raw materials, but also their hydrogenation products, alcohols, are widely used solvents and raw materials for preparing plasticizers, surfactants, etc. In addition, aldehydes can be further converted into carboxylic acids, esters, amines, etc. The 2-propylheptanol obtained by hydrogenating 2-propylheptenal formed by bimolecular condensation of valeraldehyde prepared by hydroformylation of C4 olefins is a raw material for a new generation of plasticizers. The catalytic reaction of hydroformylation of 1-butene to valeraldehyde is relatively easy, but the raw material price is high. While mixed butenes, that is, a mixture of 1-butene and 2-butene, may also include some small molecule alkanes, which have the advantages of low price and wide sources. In addition to homogeneous catalytic hydroformylation to prepare valeraldehyde, the separation of the catalyst and the product can also be achieved by water-organic two-phase catalysis for the hydroformylation of 1-butene. However, the water-organic two-phase system cannot achieve the hydroformylation of mixed olefins. At present, the hydroformylation of mixed butenes mainly reacts in a homogeneous catalytic system. In order to achieve the hydroformylation of 2-butene in mixed butenes, a catalyst system composed of a phosphite ligand and rhodium must be used to achieve the double bond displacement of 2-butene and hydroformylation to produce valeraldehyde. However, in a homogeneous catalytic system, it is difficult to separate the catalyst and the product. Coupled with the relatively high boiling point of the generated valeraldehyde, the low-pressure drop membrane separation temperature used industrially is also relatively high. Long-term operation not only leads to rapid deactivation of the catalyst, but also the high separation temperature is likely to cause the phosphite ligand to easily react with trace moisture in the system and undergo hydrolysis. In order to maintain the normal production process, phosphine ligands must be continuously supplemented during the reaction to make up for the hydrolyzed phosphine ligands. In addition, the hydrolyzed phosphine ligands must be separated and removed through a complex water washing process. Therefore, the above technologies have problems such as complex processes and high production costs. Summary of the Invention
[0003] The embodiments of this application provide a method for preparing aldehydes by hydroformylation of butenes to solve the technical problems of complex process and high production cost existing in the hydroformylation reaction of mixed butenes.
[0004] The embodiments of this application provide a method for preparing aldehydes by hydroformylation of butenes, and the method for preparing aldehydes by hydroformylation of butenes includes the following steps:
[0005] Dissolve a rhodium catalyst, a phosphite ligand, and a butene raw material in an amide solvent to obtain a premixed solution, and keep the premixed solution below 0°C;
[0006] Add the premixed solution into a mixed atmosphere of hydrogen and carbon monoxide;
[0007] Heat the premixed solution to a predetermined temperature, and obtain a mixed solution after reacting for a predetermined time;
[0008] After the mixed solution is layered, the upper layer liquid is obtained by liquid separation to obtain an aldehyde product.
[0009] Among them, the butene raw material includes at least one butene among 1-butene and 2-butene.
[0010] In some embodiments of the present application, the rhodium catalyst includes at least one of HRh(CO)(PPh3)3, RhCl(CO)(TPPTS)2, RhCl3, RhCl(PPh3)3, HRh(CO)(TPPTS)3, Rh(CO)2(acac).
[0011] In some embodiments of the present application, the ligand includes at least one of L1, L2, L3, L4, and L1, L2, L3, L4 are molecules with the following chemical general formula:
[0012]
[0013] In some embodiments of the present application, the R1 is one of hydrogen, alkyl, halogen, trifluoromethyl, and methoxy; and / or,
[0014] The R2 is one of hydrogen, alkyl, halogen, trifluoromethyl, and methoxy.
[0015] In some embodiments of the present application, the rhodium catalyst includes Rh(CO)(acac)L4.
[0016] In some embodiments of the present application, the amide solvent is at least one of formamide, N-methylformamide, and N,N-dimethylformamide.
[0017] In some embodiments of the present application, the pressure of the mixed atmosphere is 0.5-9 MPa.
[0018] In some embodiments of the present application, in the mixed atmosphere, the ratio of the partial pressures of hydrogen and carbon monoxide is 0.5-5:1.
[0019] In some embodiments of the present application, the predetermined temperature is 50-120 °C; and / or,
[0020] The predetermined time is 2-6 h.
[0021] In some embodiments of the present application, the mixed butene further includes alkanes of C2-C5.
[0022] The above technical solutions provided by the embodiments of the present application have the following advantages compared with the prior art:
[0023] The method for producing aldehyde by hydroformylation of butene provided by the embodiment of the present application uses a strongly polar amide solvent as the solvent instead of water. The rhodium catalyst and phosphite ligands are easily soluble in the strongly polar solvent, while the olefin and the reaction product aldehyde are hardly soluble in such a solvent. During the reaction process, no ligand needs to be supplemented, and there is no problem of hydrolysis resulting in many impurities. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The accompanying drawings herein are incorporated into the specification and constitute a part of this specification, showing embodiments consistent with the present application, and are used together with the specification to explain the principles of the present application.
[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the accompanying drawings required for the description of the embodiments or the prior art. Obviously, for those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.
[0026] Figure 1 It is a schematic flow chart of a method for producing aldehyde by hydroformylation of butene provided by the embodiment of the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present application with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts belong to the scope of protection of the present application.
[0028] Unless otherwise specifically stated, the terms used herein should be understood as having the meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as the general understanding of those skilled in the art to which the present application belongs. In case of any contradiction, this specification shall prevail.
[0029] Unless otherwise specifically stated, various raw materials, reagents, instruments, and equipment used in the present application can be obtained through the market or prepared by existing methods.
[0030] There are technical problems in the existing hydroformylation reaction of mixed butenes, such as complex process and high production cost.
[0031] The technical solution provided by the embodiment of the present application to solve the above technical problems has the following general idea:
[0032] The embodiment of the present application provides a method for producing aldehyde by hydroformylation of butene. Please refer toFigure 1 , the method for preparing aldehyde by hydroformylation of butene comprises the following steps:
[0033] S1: Dissolve a rhodium catalyst, a phosphite ligand, and a butene raw material in an amide solvent to obtain a premixed solution, and keep the premixed solution below 0 °C;
[0034] S2: Add the premixed solution into a mixed atmosphere of hydrogen and carbon monoxide;
[0035] S3: Heat the premixed solution to a predetermined temperature, and obtain a mixed solution after reacting for a predetermined time;
[0036] S4: After the mixed solution is layered, separate the upper layer liquid by liquid separation to obtain an aldehyde product.
[0037] Wherein, the butene raw material comprises at least one of 1-butene and 2-butene.
[0038] Butene has a low boiling point and is easy to volatilize. To reduce the volatilization of the butene phase, the premixed solution needs to be kept at a low temperature before the reaction.
[0039] It is easy to understand that mixed butene is a common chemical product in the market, generally including a mixture of 1-butene and 2-butene, and may also include some small molecule alkanes. In some embodiments, the mixed butene described in the present application, in addition to including at least one of 1-butene and 2-butene, also includes some alkanes with 2 to 5 carbon atoms (i.e., C2 to C5).
[0040] In the present application, a strongly polar amide solvent is used as the solvent instead of water. The rhodium catalyst and the phosphite ligand are easily soluble in the strongly polar solvent, while the olefin and the reaction product aldehyde are hardly soluble in such a solvent. During the reaction process, there is no need to supplement the ligand, and there is no problem of a large amount of impurities caused by hydrolysis.
[0041] In addition, the present application also has the following advantages:
[0042] 1. The amide solvent is used as the solvent throughout the process, and there is no need to add other additives midway, and the process is simple;
[0043] 2. The reaction product aldehyde is hardly soluble in the amide solvent. After the reaction is completed, it automatically layers, and the product can be separated directly by liquid separation, and the process is simple;
[0044] 3. The olefin and the reaction product aldehyde are hardly soluble in the amide solvent, while the rhodium catalyst and the phosphite ligand are easily soluble in the amide solvent. The catalyst is enriched in the amide solvent, is easy to separate, and is easy to recycle;
[0045] 4. Compared with the existing solutions using water as a solvent, the present application uses an amide solvent as the solvent. Although the solubility of butene in the amide solvent is very low, it is higher than that in water. Therefore, the reaction activity of the present application is much higher than that of the existing solutions. At the same time, due to its high reaction activity, this reaction can also be carried out under low temperature and low pressure, reducing the requirements for equipment and the process energy consumption.
[0046] In some embodiments of the present application, the rhodium catalyst includes at least one of HRh(CO)(PPh3)3, RhCl(CO)(TPPTS)2, RhCl3, RhCl(PPh3)3, HRh(CO)(TPPTS)3, Rh(CO)2(acac).
[0047] The above substances are common rhodium catalysts.
[0048] In some embodiments of the present application, the ligand includes at least one of L1, L2, L3, L4, and L1, L2, L3, L4 are molecules with the following chemical general formula:
[0049]
[0050] In some embodiments of the present application, the R1 is one of hydrogen, alkyl, halogen, trifluoromethyl, and methoxy.
[0051] In some embodiments of the present application, the R2 is one of hydrogen, alkyl, halogen, trifluoromethyl, and methoxy.
[0052] In some embodiments of the present application, the rhodium catalyst includes Rh(CO)(acac)L4.
[0053] It should be noted that L4 in Rh(CO)(acac)L4 is the ligand L4.
[0054] On the premise that the ligand includes at least one of L1, L2, L3, L4, the rhodium catalyst may include at least one of HRh(CO)(PPh3)3, RhCl(CO)(TPPTS)2, RhCl3, RhCl(PPh3)3, HRh(CO)(TPPTS)3, Rh(CO)2(acac), and Rh(CO)(acac)L4.
[0055] In some embodiments of the present application, the pressure of the mixed gas is 0.5 - 9 MPa.
[0056] The pressure of the mixed gas is the pressure at which the reaction proceeds.
[0057] As an example, the pressure of the mixed atmosphere can be 0.5 MPa, 1 MPa, 3 MPa, 6 MPa, 9 MPa.
[0058] In some embodiments of the present application, in the mixed atmosphere, the ratio of the partial pressures of hydrogen and carbon monoxide is 0.5 to 5:1.
[0059] The aldehyde can be further hydrogenated to form an alcohol. In the present application, the ratio of the partial pressures of hydrogen and carbon monoxide can be adjusted within the above range according to actual needs.
[0060] As an example, the ratio of the partial pressures of hydrogen and carbon monoxide can be 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1.
[0061] In some embodiments of the present application, the predetermined temperature is 50 to 120 °C.
[0062] As an example, the predetermined temperature can be 50 °C, 70 °C, 90 °C, 100 °C, 120 °C.
[0063] In some embodiments of the present application, the predetermined time is 2 to 6 h.
[0064] As an example, the predetermined time can be 2 h, 3 h, 4 h, 5 h, 6 h.
[0065] In some embodiments of the present application, the mixed butene further includes alkanes with C2 to C5.
[0066] The present application will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present application and not to limit the scope of the present application. The experimental methods without specific conditions in the following embodiments are usually determined according to industry standards. If there is no corresponding industry standard, they are carried out according to general international standards, conventional conditions, or the conditions recommended by the manufacturer.
[0067] Example 1
[0068] 0.022 g of rhodium catalyst HRh(CO)(PPh3)3, 0.05 g of ligand L1 (where R1 and R2 are both H atoms), 6 mL of formamide and 2.5 mL of 2-butene were separately added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. The butene was in liquid state, the temperature was -5 °C, and the temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 70 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed solution inside the autoclave was taken out. After the mixed solution was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 2-butene was 92.3%, and the selectivity of pentanal was 97.8%, among which the selectivity of linear aldehyde was 98.5%.
[0069] Example 2
[0070] 0.022 g of rhodium catalyst RhCl(CO)(TPPTS)2, 0.10 g of ligand L1 (where R1 and R2 are both H atoms), 12 mL of formamide and 3.5 mL of 2-butene were separately added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. The butene was in liquid state, the temperature was -5 °C, and the temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 2.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 60 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 3 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed solution inside the autoclave was taken out. After the mixed solution was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 2-butene was 94.8%, and the selectivity of pentanal was 98.3%, among which the selectivity of linear aldehyde was 99.2%.
[0071] Example 3
[0072] 0.022 g of rhodium catalyst HRh(CO)(PPh3)3, 0.5 g of ligand L1 (where R1 is an H atom and R2 is an F atom), 6 mL of formamide, and 2.5 mL of 2-butene were separately added to a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. The butene was in liquid state, the temperature was -5 °C, and the temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 9.0 MPa. The syngas consisted of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 50 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed solution inside the autoclave was taken out. After the mixed solution was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 2-butene was 85.7%, and the selectivity of pentanal was 98.8%, among which the selectivity of linear aldehyde was 97.5%.
[0073] Example 4
[0074] 0.022 g of rhodium catalyst RhCl3, 1.2 g of ligand L1 (where R1 is -OCH3 and R2 is -C2H5), 15 mL of formamide, and 2.5 mL of 2-butene were separately added to a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. The butene was in liquid state, the temperature was -5 °C, and the temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 0.50 MPa. The syngas consisted of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 120 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 1000 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed solution inside the autoclave was taken out. After the mixed solution was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 2-butene was 89.1%, and the selectivity of pentanal was 92.6%, among which the selectivity of linear aldehyde was 95.5%.
[0075] Example 5
[0076] 0.022 g of rhodium catalyst RhCl(PPh3)3, 0.06 g of ligand L1 (where R1 is an H atom and R2 is -CF3), 6 mL of formamide and 2.5 mL of 1-butene were respectively added to a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. The butene was in liquid state and the temperature was -5 °C. The temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 5.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 70 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 100 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed solution inside the autoclave was taken out. After the mixed solution was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 1-butene was 93.4%, and the selectivity of pentanal was 98.8%, among which the selectivity of linear aldehyde was 98.1%.
[0077] Example 6
[0078] 0.022 g of rhodium catalyst HRh(CO)(PPh3)3, 0.055 g of ligand L2 (where R1 is an H atom and R2 is -CH3), 6 mL of formamide and 2.5 mL of 1-butene were respectively added to a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. The butene was in liquid state and the temperature was -5 °C. The temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 70 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed solution inside the autoclave was taken out. After the mixed solution was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 1-butene was 94.3%, and the selectivity of pentanal was 98.4%, among which the selectivity of linear aldehyde was 97.3%.
[0079] Example 7
[0080] 0.03 g of rhodium catalyst HRh(CO)(TPPTS)3, 0.055 g of ligand L3 (wherein R1 and R2 are both H atoms), 6 mL of formamide and 2.5 mL of 2-butene were respectively added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. The butene was in liquid state and the temperature was -5 °C. The temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 70 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed solution inside the autoclave was taken out. After the mixed solution was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 2-butene was 91.3%, and the selectivity of pentanal was 97.8%, among which the selectivity of linear aldehyde was 99.0%.
[0081] Example 8
[0082] 0.03 g of rhodium catalyst Rh(CO)(acac)L4, 0.30 g of ligand L4 (wherein R1 and R2 are both H atoms), 6 mL of formamide and 5.0 mL of 2-butene were respectively added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. The butene was in liquid state and the temperature was -5 °C. The temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 70 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 3 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed solution inside the autoclave was taken out. After the mixed solution was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 2-butene was 90.9%, and the selectivity of pentanal was 98.0%, among which the selectivity of linear aldehyde was 98.5%.
[0083] Example 9
[0084] 0.03 g of rhodium catalyst Rh(CO)(acac)L4, 1.5 g of ligand L4 (wherein both R1 and R2 are H atoms), 15 mL of formamide and 7.5 mL of 2-butene were respectively added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. The butene was in liquid state and the temperature was -5°C. The temperature inside the stainless-steel autoclave was controlled at -5°C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 3.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 80°C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 6 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed liquid inside the autoclave was taken out. After the mixed liquid was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 2-butene was 99.0%, and the selectivity of pentanal was 97.8%, among which the selectivity of linear aldehyde was 98.9%.
[0085] Example 10
[0086] 0.020 g of rhodium catalyst Rh(CO)2(acac), 0.08 g of ligand L4 (wherein R1 is H atom and R2 is -CH3), 6 mL of formamide and 2.5 mL of mixed butene were respectively added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. In terms of the volume ratio of the mixed butene, the mixed butene included 50% of 1-butene and 50% of 2-butene. The mixed butene was in liquid state and the temperature was -5°C. The temperature inside the stainless-steel autoclave was controlled at -5°C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 70°C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed liquid inside the autoclave was taken out. After the mixed liquid was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of the mixed butene was 94.4%, and the selectivity of pentanal was 98.2%, among which the selectivity of linear aldehyde was 97.7%.
[0087] Example 11
[0088] 0.03 g of rhodium catalyst Rh(CO)(acac)L4, 0.06 g of ligand L4 (where R1 is -C2H5 and R2 is -OCH3), 6 mL of formamide and 2.5 mL of mixed butenes were respectively added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. Among them, based on the volume ratio of the mixed butenes, the mixed butenes included 20% 1-butene and 80% 2-butene. The mixed butenes were in a liquid state, the temperature was -5 °C, and the temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 90 °C, and then it was reacted at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed liquid inside the autoclave was taken out. After the mixed liquid was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 2-butene was 96.6%, and the selectivity of pentanal was 97.3%, among which the selectivity of linear aldehyde was 98.1%.
[0089] Example 12
[0090] 0.03 g of rhodium catalyst Rh(CO)(acac)L4, 0.10 g of ligand L4 (where R1 is -CH3 and R2 is -CF3), 6 mL of formamide and 2.5 mL of mixed butenes were respectively added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. Among them, based on the volume ratio of the mixed butenes, the mixed butenes included 10% 1-butene, 50% 2-butene, and 40% mixed alkanes of C2-C5. The mixed butenes were in a liquid state, the temperature was -5 °C, and the temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 80 °C, and then it was reacted at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed liquid inside the autoclave was taken out. After the mixed liquid was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of the mixed butenes was 95.0%, and the selectivity of pentanal was 97.2%, among which the selectivity of linear aldehyde was 97.1%.
[0091] Example 13
[0092] 0.03 g of rhodium catalyst Rh(CO)(acac)L4, 0.06 g of ligand L4 (where R1 is -Cl and R2 is -F), 6 mL of formamide and 2.5 mL of mixed butenes were respectively added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. Among them, based on the volume ratio of the mixed butenes, the mixed butenes included 10% 1-butene, 50% 2-butene, and 40% mixed alkanes of C2-C5. The mixed butenes were in a liquid state at a temperature of -5 °C, and the temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 80 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed liquid inside the autoclave was taken out. After the mixed liquid was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of the mixed butenes was 92.6%, and the selectivity for pentanal was 97.5%, among which the selectivity for linear aldehydes was 97.9%.
[0093] Example 14
[0094] 0.03 g of rhodium catalyst Rh(CO)(acac)L4, 0.03 g of ligand L4 (where R1 is -CF3 and R2 is -OCH3), 6 mL of formamide and 2.5 mL of mixed butenes were respectively added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. Among them, based on the volume ratio of the mixed butenes, the mixed butenes included 10% 1-butene, 50% 2-butene, and 40% mixed alkanes of C2-C5. The mixed butenes were in a liquid state at a temperature of -5 °C, and the temperature inside the stainless-steel autoclave was controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel autoclave was raised to 80 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed liquid inside the autoclave was taken out. After the mixed liquid was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of the mixed butenes was 92.5%, and the selectivity for pentanal was 97.4%, among which the selectivity for linear aldehydes was 94.2%.
[0095] Example 15
[0096] 0.03 g of rhodium catalyst Rh(CO)(acac)L4, 0.06 g of ligand L4 (wherein R1 and R2 are both H atoms), 6 mL of formamide and 2.5 mL of mixed butenes were respectively added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. Among them, based on the volume ratio of the mixed butenes, the mixed butenes include 10% 1-butene, 50% 2-butene, and 40% mixed alkanes of C2-C5. The mixed butenes are in a liquid state, the temperature is -5 °C, and the temperature inside the stainless-steel autoclave is controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas consists of hydrogen and carbon monoxide, and the partial pressure ratio of hydrogen to carbon monoxide is 2:1. The temperature inside the stainless-steel autoclave was raised to 70 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed liquid inside the autoclave was taken out. After the mixed liquid was taken out, it was divided into upper and lower layers. The reactants and products are both located in the upper layer, and the catalyst is located in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 2-butene is 91.9%, and the selectivity of pentanal is 95.0%, among which the selectivity of straight-chain aldehyde is 98.2%, and the selectivity of pentanol is 2.3%.
[0097] Example 16
[0098] 0.03 g of rhodium catalyst Rh(CO)(acac)L4, 0.08 g of ligand L4 (wherein R1 and R2 are both H atoms), 6 mL of formamide and 2.5 mL of mixed butenes were respectively added into a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. Among them, based on the volume ratio of the mixed butenes, the mixed butenes include 10% 1-butene, 50% 2-butene, and 40% mixed alkanes of C2-C5. The mixed butenes are in a liquid state, the temperature is -5 °C, and the temperature inside the stainless-steel autoclave is controlled at -5 °C. Then, syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, and this was repeated 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas consists of hydrogen and carbon monoxide, and the partial pressure ratio of hydrogen to carbon monoxide is 5:1. The temperature inside the stainless-steel autoclave was raised to 70 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed liquid inside the autoclave was taken out. After the mixed liquid was taken out, it was divided into upper and lower layers. The reactants and products are both located in the upper layer, and the catalyst is located in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of 2-butene is 87.9%, and the selectivity of pentanal is 90.5%, among which the selectivity of straight-chain aldehyde is 98.0%, and the selectivity of pentanol is 7.7%.
[0099] Example 17
[0100] 0.03 g of rhodium catalyst Rh(CO)(acac)L4, 0.08 g of ligand L4 (wherein both R1 and R2 are H atoms), 6 mL of formamide and 2.5 mL of mixed butenes were respectively added to a stainless-steel autoclave equipped with a magnetic stirrer and a temperature controller. Among them, based on the volume ratio of the mixed butenes, the mixed butenes included 10% 1-butene, 50% 2-butene, and 40% mixed alkanes of C2-C5. The mixed butenes were in a liquid state, the temperature was -5 °C, the temperature inside the stainless-steel autoclave was controlled at -5 °C, and then syngas was introduced into the stainless-steel autoclave to displace the air inside the autoclave, repeating 3 times. Then, syngas was charged until the pressure inside the autoclave reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressure ratio of hydrogen to carbon monoxide was 0.5:1. The temperature inside the stainless-steel autoclave was raised to 70 °C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel autoclave was cooled to room temperature, the pressure was released, and the mixed liquid inside the autoclave was taken out. After the mixed liquid was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. After calculation, the conversion rate of the mixed butenes was 83.8%, the selectivity of pentanal was 98.5%, and the selectivity of linear aldehyde was 98.1%.
[0101] Example 18
[0102] The lower-layer formamide solution of Example 9 was separated out, re-added to the high-pressure reactor, and then 2.5 mL of mixed butenes was added. In terms of the volume ratio of the mixed butenes, the mixed butenes included 50% 1-butene and 50% 2-butene. The mixed butenes were in a liquid state, at a temperature of -5°C, and the temperature inside the stainless-steel high-pressure reactor was controlled at -5°C. Then, syngas was introduced into the stainless-steel high-pressure reactor to displace the air inside the reactor, and this was repeated 3 times. Then, syngas was charged until the pressure inside the reactor reached 1.0 MPa. The syngas was composed of hydrogen and carbon monoxide, and the partial pressures of hydrogen and carbon monoxide were equal. The temperature inside the stainless-steel high-pressure reactor was raised to 70°C, and then the reaction was carried out at a constant temperature and pressure with a stirring speed of 500 rpm for 2 hours. Subsequently, after the stainless-steel high-pressure reactor was cooled to room temperature, the pressure was released, and the mixed liquid inside the reactor was taken out. After the mixed liquid was taken out, it was divided into upper and lower layers. The reactants and products were both in the upper layer, and the catalyst was in the lower layer. The composition of the upper layer was analyzed by gas chromatography. The above operations were repeated 20 times, and the conversion rates of the mixed butenes were 96.8%, 97.6%, 97.1%, 97.3%, 97.2%, 96.9%, 96.9%, 96.8%, 96.9%, 96.7%, 96.3%, 97.2%, 96.5%, 96.4%, 96.5%, 96.3%, 96.1%, 97.3%, 96.0%, 96.9% respectively; the selectivities of pentanal were 97.6%, 96.8%, 97.8%, 98.1%, 98.3%, 97.2%, 97.3%, 98.2%, 97.5%, 97.5%, 97.6%, 97.2%, 97.4%, 97.6%, 97.8%, 97.9%, 98.2%, 97.9%, 97.7%, 98.3% respectively; and the selectivities of linear aldehydes were 98.1%, 98.2%, 98.6%, 98.2%, 97.8%, 98.2%, 98.0%, 98.1%, 97.9%, 97.8%, 98.4%, 98.3%, 97.5%, 98.5%, 98.2%, 98.0%, 97.9%, 98.3%, 97.7%, 98.1% respectively.
[0103] The various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and the individual values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as the individual numbers within that range, such as 1, 2, 3, 4, 5, and 6, and this applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.
[0104] In this application, unless otherwise specified, the orientation terms such as "upper" and "lower" specifically refer to the drawing directions in the attached drawings. Additionally, in the description of the specification of this application, the terms "include", "comprise", etc. mean "include but not limited to". Moreover, the term "include", "comprise" or any other variant thereof is intended to cover non-exclusive inclusion, such that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device. Without further limitation, the elements defined by the statement "include..." do not preclude the existence of additional identical elements in the process, method, article or device comprising the said elements. In this text, relative terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. In this text, "and / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist simultaneously, or B exists alone. For the association relationship of more than three associated objects described by "and / or", it means that these three associated objects can exist alone for any one of them, or any at least two of them exist simultaneously. For example, for A, and / or B, and / or C, it can mean that any one of A, B, and C exists alone, or any two of them exist simultaneously, or all three of them exist simultaneously. In this text, "at least one" means one or more, and "multiple" means two or more. "At least one kind", "at least one item (piece) below" or similar expressions refer to any combination of these items, including any combination of single item (piece) or plural items (pieces). For example, "at least one item (piece) of a, b, or c", or, "at least one item (piece) of a, b, and c" can both mean: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.
[0105] The above are only specific embodiments of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application will not be limited to these embodiments shown herein, but rather to the broadest scope consistent with the principles and novel features claimed herein.
Claims
1. A method for preparing aldehyde by hydroformylation of butene, characterized in that, The method for preparing aldehyde by hydroformylation of butene comprises the following steps: Dissolve a rhodium catalyst, a phosphite ligand, and a butene raw material in an amide solvent to obtain a premixed solution, and keep the premixed solution below 0 °C; Add the premixed solution into a mixed atmosphere of hydrogen and carbon monoxide; Heat the premixed solution to a predetermined temperature, and obtain a mixed solution after reacting for a predetermined time; After the mixed solution is layered, separate the upper layer liquid by liquid separation to obtain an aldehyde product. Wherein, the butene raw material comprises at least one butene among 1-butene and 2-butene.
2. The method for preparing aldehyde by hydroformylation of butene according to claim 1, wherein The rhodium catalyst comprises at least one of HRh(CO)(PPh3)3, RhCl(CO)(TPPTS)2, RhCl3, RhCl(PPh3)3, HRh(CO)(TPPTS)3, Rh(CO)2(acac).
3. The method for preparing aldehyde by hydroformylation of butene according to claim 1, characterized in that, The ligand comprises at least one of L1, L2, L3, L4, and L1, L2, L3, L4 are molecules with the following general chemical formula:
4. The method for producing aldehyde by hydroformylation of butene according to claim 3, characterized in that, R1 is one of hydrogen, alkyl, halogen, trifluoromethyl, and methoxy; and / or, R2 is one of hydrogen, alkyl, halogen, trifluoromethyl, and methoxy.
5. The method for preparing aldehyde by hydroformylation of butene according to claim 3, wherein, The rhodium catalyst comprises Rh(CO)(acac)L4.
6. The method for preparing aldehyde by hydroformylation of butene according to claim 1, characterized in that, The amide solvent is at least one of formamide, N-methylformamide, and N,N-dimethylformamide.
7. The method for producing aldehyde by hydroformylation of butene according to claim 1, wherein The pressure of the mixed atmosphere is 0.5 - 9 MPa.
8. The method for preparing aldehyde by hydroformylation of butene according to claim 1, characterized in that, In the mixed atmosphere, the ratio of the partial pressures of hydrogen and carbon monoxide is 0.5 - 5:
1.
9. The method for preparing aldehyde by hydroformylation of butene according to claim 1, characterized in that, The predetermined temperature is 50 - 120 °C; and / or, The predetermined time is 2 - 6 h.
10. The method for preparing aldehyde by hydroformylation of butene according to claim 1, wherein, The mixed butene further comprises alkanes with C2 - C5.