Catalyst composition for olefin hydroformylation reaction and use thereof

Abstract

The application belongs to the field of olefin hydroformylation, and discloses a catalyst composition and application of an olefin hydroformylation reaction. The catalyst composition comprises the following components: a transition metal active center, a first auxiliary agent, a second auxiliary agent and a third auxiliary agent; the transition metal active center is a carbonyl compound containing metal ruthenium and / or an ionic compound containing metal ruthenium; the first auxiliary agent is an aromatic carboxylic acid and / or an aromatic carboxylic acid derivative; the second auxiliary agent is a salt containing a halogen ion; and the third auxiliary agent is an aryl phosphine compound. The transition metal active center of the application is combined with the three auxiliary agents and applied to a propylene hydroformylation reaction, so that the normal-isomer ratio of a product can be reduced, and the yield of isobutyraldehyde is improved.

Description

Technical Field

[0001] This invention belongs to the field of olefin hydroformylation, and more specifically, relates to a catalyst composition for olefin hydroformylation reaction and its application. Background Technology

[0002] The olefin hydroformylation (carbonyl synthesis) reaction is a process in which olefins containing unsaturated double bonds react with syngas in the presence of a transition metal catalyst to produce an aldehyde with one more carbon atom. Since its discovery by German scientist Roelen in 1938, it has been widely used in the preparation of organic chemicals such as aldehydes and alcohols. The global annual production capacity has reached tens of millions of tons, and my country's carbonyl synthesis reaction equipment has a cumulative production capacity of nearly ten million tons.

[0003] After decades of development, the main carbonyl synthesis catalyst systems currently available include cobalt-based high-pressure catalysts, modified cobalt-based catalysts, rhodium-based low-pressure catalysts, and rhodium-based water-oil two-phase catalysts. In practical industrial applications, the hydroformylation of high-carbon olefins primarily utilizes traditional cobalt-based high-pressure catalyst systems due to catalyst separation issues. These systems require harsh reaction conditions, with pressures exceeding 30 MPa, resulting in high equipment investment and numerous byproducts. In the hydroformylation of low-carbon olefins, the rhodium / phosphine catalyst system has gradually replaced cobalt-based catalysts as the most widely used catalyst system due to its high reactivity and mild reaction conditions (temperature approximately 100℃, pressure 1-3 MPa). However, using rhodium as a catalyst is expensive, and the price of rhodium fluctuates greatly, posing a high risk. Therefore, an efficient precious metal recovery process is necessary to reduce production costs.

[0004] In my country, the carbonylation synthesis of butanol and octanol from propylene plays a crucial role in the carbonylation reaction industry, with domestic production capacity exceeding five million tons. However, the propylene hydroformylation reaction in this technology primarily uses a rhodium / phosphine complex catalyst as the active component, producing n-butyraldehyde at a relatively high N / I ratio. Due to market saturation and limitations related to plasticizer safety, health, and environmental concerns, this technology is likely to face conversion to other products. Isobutyraldehyde, originally a byproduct, can be used to produce high-value-added chemicals such as neopentyl glycol and dodecyl alcohol esters, and has received widespread attention in recent years. Research institutes and enterprises are continuously developing new catalyst systems to reduce the N / I ratio in the propylene hydroformylation reaction and achieve higher yields of isobutyraldehyde. However, current catalyst development still focuses on rhodium and cobalt catalysts, with slow progress on highly active catalyst systems with other metal centers. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by providing a catalyst composition and its application for the hydroformylation of olefins. The combination of the transition metal active center and three auxiliaries in this invention, applied to the hydroformylation of propylene, can reduce the positive-to-iso ratio of the product and increase the yield of isobutyraldehyde.

[0006] To achieve the above objectives, the present invention provides a catalyst composition for olefin hydroformylation reaction, the catalyst composition comprising the following components: a transition metal active center, a first promoter, a second promoter, and a third promoter;

[0007] The transition metal active center is a carbonyl compound containing ruthenium and / or an ionic compound containing ruthenium;

[0008] The first auxiliary agent is an aromatic carboxylic acid and / or an aromatic carboxylic acid derivative;

[0009] The second auxiliary agent is a salt containing halide ions;

[0010] The third adjuvant is an arylphosphine compound.

[0011] In a specific embodiment, the transition metal active center is Ru3(CO). 12 H4Ru4(CO) 12 At least one of Ru2Cl4(CO)6, RuCl3 and Ru(OAc)3.

[0012] In a specific embodiment, the first auxiliary agent is substituted or unsubstituted benzoic acid and its salt, and / or carboxylic acid and its salt having a fused aromatic ring structure.

[0013] According to a preferred embodiment of the present invention, the first auxiliary agent is at least one selected from benzoic acid, 2,6-dichlorobenzoic acid, lithium benzoate, sodium benzoate, 9-anthracarboxylic acid, and 2,6-dimethoxybenzoic acid.

[0014] In a specific embodiment, the second auxiliary agent is an organic salt containing halide ions and / or an inorganic salt containing halide ions;

[0015] According to a preferred embodiment of the present invention, the halide anion in the halide-containing salt is Cl. - and / or F - .

[0016] According to a preferred embodiment of the present invention, the cation in the halide-containing salt is Li. + Na + K + and NH4 + At least one of them.

[0017] In a specific embodiment, the third adjuvant is selected from at least one of arylphosphine compounds containing heteroatoms on the benzene ring, arylphosphine oxide compounds containing heteroatoms on the benzene ring, substituted arylphosphine compounds, and substituted arylphosphine oxide compounds; preferably, the substituent is at least one of heteroatoms, 3-aminopropyl, and dimethylamino.

[0018] According to a preferred embodiment of the present invention, the third adjuvant is at least one of the compounds represented by structural formulas (1)-(7);

[0019]

[0020]

[0021] According to a preferred embodiment of the present invention, the molar ratio of the first auxiliary agent to the ruthenium element in the transition metal active center is (0.1-1000):1, preferably (1-100):1.

[0022] According to a preferred embodiment of the present invention, the molar ratio of the second auxiliary agent to the ruthenium element in the transition metal active center is (0.1-1000):1, preferably (1-200):1.

[0023] According to a preferred embodiment of the present invention, the molar ratio of the third auxiliary agent to the ruthenium element in the transition metal active center is (0.1-1000):1, preferably (1-50):1.

[0024] Another aspect of the present invention provides the application of the catalyst composition for the olefin hydroformylation reaction in the preparation of butyraldehyde by the propylene hydroformylation reaction.

[0025] In a specific embodiment, the total butyraldehyde yield of the propylene hydroformylation reaction is 65-90%, and the positive-to-iso ratio is 1-1.6.

[0026] In a specific embodiment, the propylene hydroformylation reaction is a reaction in which isobutyraldehyde and n-butyraldehyde are generated using CO, H2 and propylene as raw materials in the presence of the catalyst composition and solvent.

[0027] In this invention, an internal standard is added to the propylene hydroformylation reaction system to facilitate the determination of reaction yield by gas chromatography. However, the internal standard is not necessary in subsequent applications.

[0028] In this invention, the solvent used for the propylene hydroformylation reaction only needs to have good solubility for the reaction substrate, catalyst and auxiliaries. In the continuous production process, the product butyraldehyde / isobutyraldehyde can also be used as the solvent. As a preferred option, the solvent is N-methylpyrrolidone.

[0029] In a specific embodiment, the mass concentration of ruthenium in the catalyst composition in the propylene hydroformylation reaction solution composed of propylene, the catalyst composition and solvent is 0.001-5%, preferably 0.01-1%.

[0030] According to a preferred embodiment of the present invention, the molar ratio of CO to H2 is (0.1-10):1, preferably (0.5-1):(1-0.5).

[0031] According to a preferred embodiment of the present invention, the reaction pressure of the propylene hydroformylation reaction is 0.1-10 MPa, preferably 1-5 MPa.

[0032] According to a preferred embodiment of the present invention, the reaction temperature of the propylene hydroformylation reaction is 50-200°C, preferably 80-150°C.

[0033] In this invention, the propylene hydroformylation reaction can be carried out continuously, semi-continuously, or intermittently. According to a preferred embodiment of the invention, the reaction time for the propylene hydroformylation reaction is 2-7 hours.

[0034] In this invention, the catalyst active intermediate is generated in situ in the reaction system by adding a metal precursor, three auxiliaries, and syngas (carbon monoxide / hydrogen). Halogen ions and phosphine ligands can coordinate with the metal center to improve the selectivity of the hydroformylation reaction. In particular, the introduction of phosphine ligands can change the spatial structure of the active center and improve the selectivity of isoformaldehydes in the hydroformylation product. Carboxylic acids or carboxylate salts can provide hydrogen protons to the active intermediate or accelerate the transfer of hydrogen protons, thereby improving the activity of the propylene hydroformylation reaction. When this catalyst composition is applied to the propylene hydroformylation reaction, the total butyraldehyde yield is 65-90%, and the positive-to-iso ratio is 1-1.6.

[0035] The beneficial effects of the technical solution of the present invention are as follows:

[0036] This invention provides a catalyst composition with a transition metal as the active center. The transition metal active center of the catalyst composition for the olefin hydroformylation reaction of this invention is a carbonyl compound containing ruthenium and / or an ionic compound containing ruthenium, avoiding the use of expensive rhodium and offering advantages such as low cost and ease of industrialization.

[0037] The catalyst composition of the present invention can be used in the hydroformylation reaction of propylene to prepare aldehyde products with high catalytic activity and selectivity under relatively mild reaction conditions (reaction pressure of 0.1-10 MPa and reaction temperature of 50-200 °C).

[0038] The combination of the transition metal active center and three auxiliaries in this invention, applied to the hydroformylation reaction of propylene, can reduce the positive-to-negative ratio of the product and increase the yield of isobutyraldehyde.

[0039] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0040] Preferred embodiments of the invention will now be described in more detail. While preferred embodiments of the invention are described below, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that the invention will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

[0041] In the following embodiments and comparative examples:

[0042] All reagents used in the propylene hydroformylation reaction were of analytical grade.

[0043] Product Analysis: Qualitative and quantitative analysis of the product components was performed using micro-injection with an Agilent-6890 gas chromatograph. The quantification method employed was the internal standard method. Among other things:

[0044]

[0045] Where n is the amount of substance.

[0046] In this invention, since propylene is gaseous at room temperature and pressure, some unreacted propylene will volatilize from the system after the reaction is completed and the pressure is released, resulting in inaccurate evaluation results. Therefore, the reaction results of this invention do not give the conversion rate of propylene.

[0047] Example 1

[0048] This embodiment provides a catalyst composition for olefin hydroformylation reaction, the catalyst composition comprising the following components: a transition metal active center, a first promoter, a second promoter, and a third promoter;

[0049] The transition metal active center is Ru3(CO). 12 ;

[0050] The first auxiliary agent is 2,6-dichlorobenzoic acid; the molar ratio of the first auxiliary agent to ruthenium in the transition metal active center is 50:1;

[0051] The second auxiliary is LiCl; the molar ratio of the second auxiliary to the ruthenium element in the transition metal active center is 50:1;

[0052] The third adjuvant is diphenyl-2-pyridinephosphine; the molar ratio of the third adjuvant to ruthenium in the transition metal active center is 4:1.

[0053] The olefin hydroformylation reaction in this embodiment is a reaction to prepare isobutyraldehyde using CO, H2, and propylene as raw materials, under the conditions of the catalyst composition, internal standard, and solvent described in this embodiment. The specific operation is as follows:

[0054] Weigh the catalyst composition of this embodiment and place it in a 100 mL reactor. Then add 25 g of N-methylpyrrolidone as a solvent and 1 g of n-hexane as an internal standard, and mix them thoroughly. After installing the reactor, purge with 0.5 MPa of high-purity nitrogen and syngas (CO:H2 ≈ 1:1 molar ratio) to replace the air in the reactor (the ratio of high-purity nitrogen to syngas is not important; simply replacing the air in the reactor is sufficient). Repeat this process 3-5 times. Inject 2 g of propylene into a stainless steel pressure-resistant feed pipe and connect it to the feed end of the reactor. Start stirring and purge with syngas during stirring to pressurize the propylene into the reactor to a pressure of 2 MPa. Stop purging. Set the reaction temperature to 120 °C and start heating. Once the temperature reaches 120 °C, start recording the reaction time. During the reaction, continuously purge with syngas to maintain the pressure in the reactor at 2 MPa. After the reaction, turn off the heating and cool the reactor using an ice-water bath. Then depressurize and take the reactor liquid after the reaction for product analysis. The results are shown in Table 1.

[0055] In the olefin hydroformylation reaction of this embodiment:

[0056] The mass concentration of ruthenium in the catalyst composition in the olefin hydroformylation reaction solution consisting of propylene, the catalyst composition and solvent is 0.15%.

[0057] The reaction time is 3 hours.

[0058] Example 2

[0059] The only difference between this embodiment and Embodiment 1 is that the transition metal active center is Ru2Cl4(CO)6.

[0060] Example 3

[0061] The only difference between this embodiment and Embodiment 1 is that:

[0062] The active center of the transition metal is H4Ru4(CO). 12 ;

[0063] The first auxiliary agent is 2,6-dimethoxybenzoic acid;

[0064] The third adjuvant is 4-(dimethylamino)triphenylphosphine.

[0065] Example 4

[0066] The only difference between this embodiment and Embodiment 1 is that:

[0067] The transition metal active center is Ru2Cl4(CO)6;

[0068] The first auxiliary agent is 2,6-dimethoxybenzoic acid.

[0069] Example 5

[0070] The only difference between this embodiment and Embodiment 1 is that:

[0071] The transition metal active center is Ru2Cl4(CO)6;

[0072] The first auxiliary agent is 2,6-dimethoxybenzoic acid;

[0073] The reaction time is 6 hours.

[0074] Example 6

[0075] The only difference between this embodiment and Embodiment 1 is that the transition metal active center is RuCl3.

[0076] Example 7

[0077] The only difference between this embodiment and Embodiment 1 is that the transition metal active center is Ru(OAc)3.

[0078] Comparative Example 1

[0079] The only difference between this comparative example and Example 1 is that the catalyst composition of Example 1 is replaced with Ru3(CO). 12 ,Ru3(CO) 12 The mass concentration of ruthenium in the olefin hydroformylation reaction solution, which consists of propylene, a catalyst composition, and a solvent, is 0.15%.

[0080] Comparative Example 2

[0081] The only difference between this comparative example and Example 1 is that the catalyst composition includes the following components: a transition metal active center and a first promoter, but does not include the second and third promoters;

[0082] The transition metal active center is Ru3(CO). 12 ;

[0083] The first auxiliary agent is 2,6-dichlorobenzoic acid; the molar ratio of the first auxiliary agent to ruthenium in the transition metal active center is 50:1;

[0084] The mass concentration of ruthenium in the catalyst composition is 0.15% in the olefin hydroformylation reaction solution composed of propylene, the catalyst composition, and a solvent.

[0085] Comparative Example 3

[0086] The only difference between this comparative example and Example 1 is that the catalyst composition includes the following components: a transition metal active center and a second promoter, but does not include the first promoter and the third promoter.

[0087] The transition metal active center is Ru3(CO). 12 ;

[0088] The second auxiliary is LiCl; the molar ratio of the second auxiliary to the ruthenium element in the transition metal active center is 50:1;

[0089] The mass concentration of ruthenium in the catalyst composition is 0.15% in the olefin hydroformylation reaction solution composed of propylene, the catalyst composition, and a solvent.

[0090] Comparative Example 4

[0091] The only difference between this comparative example and Example 1 is that the catalyst composition includes the following components: a transition metal active center and a third promoter, but does not include the first promoter and the second promoter.

[0092] The transition metal active center is Ru3(CO). 12 ;

[0093] The third adjuvant is diphenyl-2-pyridinium phosphine; the molar ratio of the third adjuvant to the ruthenium element in the transition metal active center is 4:1;

[0094] The mass concentration of ruthenium in the catalyst composition is 0.15% in the olefin hydroformylation reaction solution composed of propylene, the catalyst composition, and a solvent.

[0095] Comparative Example 5

[0096] The only difference between this comparative example and Example 1 is that the catalyst composition includes the following components: a transition metal active center, a first promoter, a second promoter, but does not include a third promoter;

[0097] The transition metal active center is Ru3(CO). 12 ;

[0098] The first auxiliary agent is 2,6-dichlorobenzoic acid; the molar ratio of the first auxiliary agent to ruthenium in the transition metal active center is 50:1;

[0099] The second auxiliary is LiCl; the molar ratio of the second auxiliary to the ruthenium element in the transition metal active center is 50:1;

[0100] The mass concentration of ruthenium in the catalyst composition is 0.15% in the olefin hydroformylation reaction solution composed of propylene, the catalyst composition, and a solvent.

[0101] Table 1

[0102]

[0103] The results in Table 1 show that:

[0104] Comparative Example 1 shows that the hydroformylation of olefins exhibits very low activity under conditions where only a ruthenium catalyst is used.

[0105] Furthermore, in Comparative Examples 2-4, the combined use of a single auxiliary agent and a ruthenium catalyst had limited effect on improving the yield of butyraldehyde in the olefin hydroformylation reaction system; in Comparative Example 5, the combined use of auxiliary agent one and auxiliary agent two with the ruthenium catalyst could significantly improve the activity of the propylene hydroformylation reaction (i.e., improve the yield of butyraldehyde in the reaction system), but the proportion of n-butyraldehyde in the product was much greater than that of isobutyraldehyde.

[0106] The various embodiments demonstrate the use of three additives in combination with a ruthenium catalyst, which significantly improves the activity of propylene hydroformylation, increases the yield of butyraldehyde, and reduces the positive-to-negative ratio in the product to below 2 or even 1.5. Example 5 shows that extending the reaction time allows unreacted propylene in the system to continue converting to butyraldehyde.

[0107] As can be seen from the comparison of Examples 1, 6 and 7, carbonyl compounds containing ruthenium have higher catalytic activity than ionic compounds containing ruthenium. This is because ruthenium carbonyl compounds are more easily converted into active intermediates in the system, thus resulting in a higher product yield under the same reaction time.

[0108] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A catalyst composition for the hydroformylation of olefins, characterized in that, The catalyst composition comprises the following components: a transition metal active center, a first promoter, a second promoter, and a third promoter; The transition metal active center is a carbonyl compound containing ruthenium and / or an ionic compound containing ruthenium; The first auxiliary agent is an aromatic carboxylic acid and / or an aromatic carboxylic acid derivative; The second auxiliary agent is a salt containing halide ions; The third adjuvant is an arylphosphine compound.

2. The catalyst composition for the hydroformylation of olefins according to claim 1, wherein, The transition metal active center is Ru3(CO). 12 H4Ru4(CO) 12 At least one of Ru2Cl4(CO)6, RuCl3, and Ru(OAc)3; The first auxiliary agent is substituted or unsubstituted benzoic acid and its salt, and / or, carboxylic acid and its salt having a fused aromatic ring structure; The second auxiliary agent is an organic salt containing halide ions and / or an inorganic salt containing halide ions; The third auxiliary is selected from at least one of arylphosphine compounds containing heteroatoms on the benzene ring, arylphosphine oxide compounds containing heteroatoms on the benzene ring, substituted arylphosphine compounds, and substituted arylphosphine oxide compounds; preferably, the substituent is at least one of heteroatoms, 3-aminopropyl, and dimethylamino.

3. The catalyst composition for the hydroformylation of olefins according to claim 2, wherein, The first auxiliary agent is at least one selected from benzoic acid, 2,6-dichlorobenzoic acid, lithium benzoate, sodium benzoate, 9-anthracarboxylic acid, and 2,6-dimethoxybenzoic acid.

4. The catalyst composition for the hydroformylation of olefins according to claim 2, wherein, The halide anion in the halide-containing salt is Cl. - and / or F - ; The cation in the halide-containing salt is Li + Na + K + and NH4 + At least one of them.

5. The catalyst composition for the hydroformylation of olefins according to claim 2, wherein, The third adjuvant is at least one of the compounds represented by structural formulas (1)-(7); 6. The catalyst composition for the hydroformylation of olefins according to any one of claims 1-5, wherein, The molar ratio of the first auxiliary agent to the ruthenium element in the transition metal active center is (0.1-1000):1, preferably (1-100):1; The molar ratio of the second auxiliary agent to the ruthenium element in the transition metal active center is (0.1-1000):1, preferably (1-200):1; The molar ratio of the third auxiliary agent to the ruthenium element in the transition metal active center is (0.1-1000):1, preferably (1-50):

1.

7. The use of the catalyst composition for olefin hydroformylation according to any one of claims 1-6 in the preparation of butyraldehyde by propylene hydroformylation; Preferably, the total butyraldehyde yield of the propylene hydroformylation reaction is 65-90%, and the positive-to-iso ratio is 1-1.

6.

8. The application according to claim 7, wherein, The propylene hydroformylation reaction is a reaction in which isobutyraldehyde and n-butyraldehyde are generated using CO, H2 and propylene as raw materials in the presence of the catalyst composition and solvent.

9. The application according to claim 8, wherein, The mass concentration of ruthenium in the catalyst composition in the propylene hydroformylation reaction solution composed of propylene, the catalyst composition and solvent is 0.001-5%, preferably 0.01-1%.

10. The application according to claim 8, wherein, The molar ratio of CO to H2 is (0.1-10):1, preferably (0.5-1):(1-0.5); The reaction pressure for the propylene hydroformylation reaction is 0.1-10 MPa, preferably 1-5 MPa; The reaction temperature for the propylene hydroformylation reaction is 50-200℃, preferably 80-150℃; The reaction time for the propylene hydroformylation reaction is 2-7 hours.

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