A cobalt phosphine complex catalyst, its preparation method and application

Abstract

This invention discloses a cobalt-phosphine complex catalyst, its preparation method, and its applications, belonging to the field of catalytic conversion technology in coal chemical and fine chemical industries. Addressing the problems of high cost, complex steps, and difficult catalyst recovery in existing hydroformylation-hydrogenation tandem systems (such as rhodium catalysis) and low activity and high energy consumption in cobalt catalysis, this invention provides a catalyst formed by in-situ coordination of cobalt salt and organophosphine ligands. This catalyst is suitable for the hydroformylation of C4-C22 coal-based Fischer-Tropsch olefins. Under a CO / H2 mixed atmosphere, at 40-200℃ and 1-10 MPa for 2-12 hours, it achieves the direct conversion of olefins to higher alcohols. The catalytic system exhibits excellent catalytic activity and thermal stability, operating stably even with low catalyst dosage. The process is simplified, energy consumption is low, and it possesses good industrial scale-up potential, making it suitable for the large-scale preparation of green alcohol chemicals.

Description

Technical Field

[0001] This invention belongs to the field of catalytic conversion technology in coal chemical and fine chemical industries, specifically relating to an integrated Fischer-Tropsch olefin hydroformylation-hydrogenation method for alcohol production using a cobalt phosphine complex as the core catalytic system. This technology exhibits superior catalytic activity compared to traditional cobalt catalytic systems and is suitable for the high-carbon alcoholization of coal-based olefins and the industrial-scale preparation of green alcohol chemicals. Background Technology

[0002] Hydroformylation is a fundamental organic reaction that converts olefins, CO, and H2 into aldehydes under the action of a catalyst. The aldehydes can then be hydrogenated to yield the corresponding alcohols. This reaction has significant industrial application value in the synthesis of surfactants, lubricants, plasticizers, and pharmaceutical intermediates, and is widely recognized as a key pathway for transforming low-value-added olefins into high-value-added chemicals.

[0003] Higher alcohols (C6 and above, especially C8-C16) are important raw materials for surfactants, lubricants, plasticizers, and pharmaceutical intermediates, with high market value and large technological demand. Directly converting low-cost olefin raw materials into higher alcohols can improve carbon atom utilization and significantly increase product added value, thus holding strategic significance in the upgrading of the chemical industry chain.

[0004] Coal-based Fischer-Tropsch (FT) olefins are a stable and cost-effective olefin feedstock, but they are a mixture of long and short-chain olefins with complex compositions and impurities. Producing higher alcohols from Fischer-Tropsch olefins in a one-step hydroformylation-hydrogenation tandem reaction can achieve high-value utilization of the feedstock, but several key technological bottlenecks remain in industrial application: these include catalyst cost and recyclability, selectivity control in complex mixed olefins, high N / I ratio, catalyst stability in media containing impurities, and continuous operation capability.

[0005] Existing high-efficiency hydroformylation catalysts are mostly rhodium-based. Although they exhibit excellent activity and selectivity, the high cost of precious metals and their sensitivity to impurities hinder large-scale applications. Cobalt-based catalysts offer cost advantages and industrial applicability potential, but during the reaction, they are prone to initiating side reactions such as olefin hydrogenation, aldol condensation, and polymer formation. Furthermore, cobalt species are susceptible to aggregation, carbonyl loss, or transformation into inactive cobalt metal particles under high temperature and pressure. In addition, traditional cobalt-based systems often exhibit low catalytic efficiency, high energy consumption due to demanding conditions, and increased product purification costs when processing long-chain or complex mixed olefins. Summary of the Invention

[0006] To address the problems of high cost, complex steps, and difficult catalyst recovery in existing hydroformylation-hydrogenation tandem systems, as well as low activity and high energy consumption in cobalt catalysis systems, this invention provides a non-precious metal cobalt phosphine complex catalyst system with a well-defined structure, high activity, and high thermal stability, enabling a green catalytic method for the one-step efficient preparation of higher alcohols from Fischer-Tropsch olefins.

[0007] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a cobalt-phosphine complex catalyst, wherein the catalyst is formed by coordination of a cobalt compound and a phosphine ligand.

[0009] The cobalt compounds are selected from Co2(CO)8, Co(acac)2, CoCl2, CoBr2, CoI2 and their modified complexes. The modification methods include anion exchange, ligand pre-complexation, support loading (activated carbon, SiO2, Al2O3, etc.) or in-situ generation.

[0010] The general structural formula of phosphine ligands is as follows:

[0011]

[0012] Where R 1 R 2 R 3 R 4 R 5 R 6 The alkyl group is independently selected from C1 to C20, the haloalkyl group is selected from C1 to C20, the alkoxy group is selected from C1 to C20, and the aryl group or substituted aryl group is selected from C6 to C24.

[0013] The substituents in the substituted aryl group are C1-C12 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, halogen, nitro, cyano, C1-C12 haloalkyl, and C6-C18 aryl.

[0014] The nitrogen-containing substituent is —NR 3 R 4 , where R 3 R 4 The alkyl group is independently selected from C1 to C20, C1 to C20 haloalkyl group, C1 to C20 alkoxy group, C6 to C24 aryl group or substituted aryl group, wherein the substituent in the substituted aryl group is C1 to C12 alkyl group, C1 to C6 alkoxy group, C1 to C6 alkylamino group, halogen group, nitro group, cyano group, C1 to C12 haloalkyl group, C6 to C18 aryl group;

[0015] The silicon substituent is -SiR 2 R 3 R4 , where R 2 R 3 R 4 The alkyl group is independently selected from C1 to C20, C1 to C20 haloalkyl group, C1 to C20 alkoxy group, C6 to C24 aryl group or substituted aryl group, wherein the substituent in the substituted aryl group is C1 to C12 alkyl group, C1 to C6 alkoxy group, C1 to C6 alkylamino group, halogen group, nitro group, cyano group, C1 to C12 haloalkyl group, C6 to C18 aryl group.

[0016] Furthermore, the molar ratio of phosphine ligand to cobalt in the complex is from 0.5:1 to 3:1.

[0017] Preferably, Co(acac)2 is mixed with an appropriate amount of anionic precursor in an inert solvent and dried to prepare a mother liquor or impregnated catalyst.

[0018] Phosphine ligands are preferably synthesized using industrially scalable synthetic routes, such as the Grignard reagent method: starting with haloalkanes / haloaromatics or halosilanes, R–MgX Grignard reagents are prepared with magnesium in dry tetrahydrofuran under inert gas protection, and then reacted with phosphine chlorides to obtain monophosphine ligands; or polymorphic methods such as silanization followed by the introduction of phosphine groups are used to prepare phosphine ligands with special skeletons.

[0019] The substituents of the ligand can be phenyl, substituted phenyl, methyl, ethyl, octyl, biphenyl, etc., to adjust the electronic and steric properties.

[0020] Secondly, the present invention provides a one-step method for preparing higher alcohols from coal-based Fischer-Tropsch olefins. In a CO / H2 mixed atmosphere, a C4-C22 coal-based Fischer-Tropsch olefin substrate is contacted with a cobalt phosphine complex catalyst and reacted at 40°C-200°C and 1 MPa-10 MPa for 2-12 hours to obtain the corresponding higher alcohol.

[0021] The overall chemical reaction formula is as follows:

[0022]

[0023]

[0024] 1-(Di-tert-butylphosphaneyl)-2-(2-methoxyphenyl)-1H-indole (L12). ¹HNMR (500 MHz, CDCl3): δ 8.10–8.25 (d, J = 8.0 Hz, 1H), 7.70–7.85 (d, J = 8.0Hz, 1H), 7.30–7.50 (m, 4H), 7.00–7.20 (m, 3H), 6.70–6.85 (d, J = 8.5 Hz, 1H),3.80–3.95 (s, 3H), 1.30–1.50 (d, J = 10.0 Hz, 18H).

[0025]

[0026] 1,3-Diisopropyl-2-phenyl-1,3,2-diazaphosphepane (L13). ¹H NMR (500MHz, CDCl3): δ 7.30–7.50 (m, 5H), 3.80–4.20 (m, 2H), 3.20–3.60 (m, 4H), 1.80–2.20 (m, 4H), 1.20–1.40 (d, J = 6.5 Hz, 12H).

[0027]

[0028] (5-Methylthiophen-2-yl)bis((trimethylsilyl)methyl)phosphane (L14). ¹HNMR (500 MHz, CDCl3): δ 6.60–6.75 (m, 2H), 2.40–2.60 (m, 4H), 2.20–2.35 (s,3H), 0.00–0.20 (s, 18H).

[0029]

[0030] Phenylbis((trimethoxysilyl)methyl)phosphane (L15). ¹H NMR (500 MHz,CDCl3): δ 7.30–7.50 (m, 5H), 3.50–3.60 (s, 18H), 2.40–2.70 (m, 4H).

[0031]

[0032] 1,3-Bis(2-methoxyphenyl)-5-phenyl-1,3,5-diazaphosphinane (L16). ¹HNMR (500 MHz, CDCl3): δ 7.20–7.50 (m, 9H), 6.80–7.00 (m, 4H), 3.80–4.00 (s,6H), 3.50–3.80 (m, 4H), 2.50–2.80 (m, 2H).

[0033]

[0034] 1,1-Di-tert-butyl-N-(2-methoxyphenyl)phosphanamine (L17). ¹H NMR (500MHz, CDCl3): δ 7.00–7.30 (m, 4H), 3.80–3.95 (s, 3H), 1.20–1.40 (d, J = 10.5Hz, 18H).

[0035]

[0036] Bis(3-methoxyphenyl)(2-((trimethylsilyl)oxy)phenyl)phosphane (L18). ¹H NMR (500 MHz, CDCl3): δ 7.10–7.50 (m, 11H), 6.70–6.90 (m, 2H), 3.75–3.85(s, 6H), 0.20–0.35 (s, 9H).

[0037]

[0038] N-(2,6-Diisopropylphenyl)-1,1,1-trimethylsilanamine (L19). ¹H NMR(500 MHz, CDCl3): δ 7.10–7.25 (m, 3H), 3.20–3.40 (m, 2H), 1.20–1.35 (d, J =6.8 Hz, 12H), 0.00–0.15 (s, 9H).

[0039]

[0040] 1-(Diisopropylphosphaneyl)-3-methyl-1,3-dihydro-2H-benzo[d]imidazol-2-imine (L20). ¹H NMR (500 MHz, CDCl3): δ 7.10–7.40 (m, 4H), 3.80–4.20 (m,2H), 3.30–3.60 (s, 3H), 1.20–1.50 (m, 12H).

[0041]

[0042] (2-(1,1-Dimethyl-2-((perfluorophenyl)methyl)disilaneyl)phenyl)diphenylphosphane (L21). ¹H NMR (500 MHz, C6D6): δ 7.00–7.60 (m, 14H), 2.80–3.10 (m, 2H), 0.80–1.10 (m, 2H), 0.20–0.50 (s, 6H).

[0043]

[0044] 1-(Diphenylphosphaneyl)-2-(4-methoxybenzyl)piperazine (L22). ¹H NMR(500 MHz, CDCl3): δ 7.20–7.50 (m, 10H), 6.80–7.00 (d, J = 8.5 Hz, 2H), 3.70–3.85 (s, 3H), 3.40–3.70 (m, 2H), 2.60–3.00 (m, 8H), 2.40–2.60 (m, 2H).

[0045]

[0046] 1-(Bis(4-methoxyphenyl)phosphaneyl)-4-((trimethylsilyl)methyl)piperazine (L23). ¹H NMR (500 MHz, CDCl3): δ 7.10–7.40 (m, 4H), 6.80–7.00(m, 4H), 3.75–3.85 (s, 6H), 3.00–3.40 (m, 8H), 2.20–2.50 (m, 2H), 0.00–0.20(s, 9H).

[0047]

[0048] (4-Methoxybenzyl)bis(4-methoxyphenyl)phosphane (L24). ¹H NMR (500MHz, CDCl3): δ 7.10–7.40 (m, 6H), 6.80–7.00 (m, 6H), 3.75–3.85 (s, 9H), 3.10–3.40 (m, 2H).

[0049]

[0050] N-tert-Butyl-N-(4-methoxybenzyl)-1,1-diphenylphosphanamine (L25). ¹HNMR (500 MHz, CDCl3): δ 7.20–7.60 (m, 10H), 6.80–7.00 (d, J = 8.5 Hz, 2H), 3.75–3.85 (s, 3H), 3.50–3.80 (m, 2H), 1.20–1.40 (s, 9H).

[0051] The substrate is an industrial Fischer-Tropsch olefin. After the reaction is complete, the reaction solution is directly subjected to vacuum distillation to obtain the target product, a higher alcohol.

[0052] Furthermore, the molar ratio of CO / H2 is 1:1 to 1:5.

[0053] Furthermore, the amount of the cobalt phosphine complex catalyst is 0.01% to 1.0% of the molar amount of the olefin substrate, calculated as cobalt; wherein the molar ratio of the phosphine ligand to the substrate is 0.05% to 5.0%.

[0054] Furthermore, the reaction can be carried out in the presence or without a solvent, wherein the solvent is toluene, xylene, tetrahydrofuran or other inert organic solvents.

[0055] Thirdly, the present invention provides an application of a cobalt phosphine complex catalyst in the hydroformylation reaction of olefins.

[0056] Fourthly, the present invention provides an application of a cobalt phosphine complex catalyst in the preparation of higher alcohols.

[0057] The mechanism of this invention is as follows: First, the metal catalyst Co and its ligands form a catalytic precursor A during pre-activation. A coordinates with the double bond of the substrate olefin to form intermediate B, followed by the migration and insertion of H atoms to generate intermediate C. C then coordinates with a molecule of carbon monoxide to form intermediate D, followed by carbonyl insertion to form intermediate E. E coordinates with hydrogen and undergoes cleavage to generate the final product of hydroformylation, aldehyde F. Finally, aldehyde F is further reduced to generate the final product, higher alcohol G.

[0058] .

[0059] Compared with the prior art, the present invention has the following advantages:

[0060] This invention uses non-precious metal cobalt as the core, significantly reducing the cost of the catalytic system; the catalyst can be formed in situ and recycled in the reaction system, simplifying process steps and reducing separation processes; the reaction can be carried out in a solvent-free system with no by-product pollutant emissions, exhibiting excellent environmental friendliness; by adjusting the phosphine ligand structure, it can maintain near-rhodium catalytic system activity over a wide range of olefins, with yields reaching over 94%; the process is short and the operating conditions are mild, making it suitable for industrial scale-up applications.

[0061] This invention eliminates the need to separate intermediate products and allows for the direct synthesis of the target product from simple raw materials, simplifying the process, reducing energy consumption, minimizing waste solution emissions, and reducing environmental pollution. The yield of high carbon alcohols can reach up to 97%.

[0062] This invention overcomes the bottlenecks of low catalytic efficiency, difficult separation, and poor catalyst thermal stability in traditional multi-metal tandem systems by achieving synergistic hydroformylation and hydrogenation reactions in a single catalytic system. This provides a new pathway for the efficient conversion of coal-based Fischer-Tropsch olefins into high-value-added chemicals. This technology has broad application prospects and significant industrial value in coal chemical industry, syngas utilization, and the production of green alcohol chemicals. Attached Figure Description

[0063] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0064] Figure 1 This is a schematic diagram of the general structural formula of phosphine ligands;

[0065] Figure 2 This is a schematic diagram of the overall chemical reaction of the present invention;

[0066] Figure 3 A schematic diagram of the mechanism of this invention. Detailed Implementation

[0067] To gain a deeper understanding of this invention, we will provide a comprehensive and detailed description. However, this invention has various implementations and is not limited to the specific examples listed herein. These examples are presented to enhance a full understanding of the disclosure of this invention.

[0068] Example 1

[0069] Using 5 mL of a mixed olefin (composition: C10 alkanes 12.5%; C10 olefins 12.5%; C11 alkanes 12.5%; C11 olefins 12.5%; C12 alkanes 12.5%; C12 olefins 12.5%; C13 alkanes 12.5%; C13 olefins 12.5%) as the substrate, 14.34 mg (0.056 mmol) of cobalt(II) acetylacetonate was used as the metal catalyst, and 77.84 mg (0.28 mmol) of L... 12 As a ligand, it was placed in a high-temperature and high-pressure reactor at 170°C and stirred for 4 hours in a CO / H2 (4MPa / 3.5MPa) mixed gas.

[0070] After the reaction, the olefin fraction in the mixed substrate was converted to 99.8%, of which 5.2% was converted to the corresponding alkanes, 2.6% to isoolefins, and 92% to the corresponding C4 olefins. n+1 Higher alcohols, with a positive-to-isomer ratio of 98.2:1.8.

[0071] Example 2

[0072] Using 5 mL of a mixed olefin (composition: C10 alkanes 12.5%; C10 olefins 12.5%; C11 alkanes 12.5%; C11 olefins 12.5%; C12 alkanes 12.5%; C12 olefins 12.5%; C13 alkanes 12.5%; C13 olefins 12.5%) as the substrate, 17.20 mg (0.067 mmol) of cobalt(II) acetylacetonate was used as the metal catalyst, and 93.41 mg (0.34 mmol) of L... 12 As a ligand, it was placed in a high-temperature and high-pressure reactor at 170°C and stirred for 4 hours in a CO / H2 (3.5MPa / 3.5MPa) mixed gas.

[0073] After the reaction, the olefin fraction in the mixed substrate was converted to 99.7%, of which 7.4% was converted to the corresponding alkanes, 3.2% to isoolefins, and 89.1% to the corresponding C4 ... n+1 Higher alcohols, with a positive-to-isomer ratio of 98.4:1.6.

[0074] Example 3

[0075] Using 5 mL of a mixed olefin (composition: C10 alkanes 12.5%; C10 olefins 12.5%; C11 alkanes 12.5%; C11 olefins 12.5%; C12 alkanes 12.5%; C12 olefins 12.5%; C13 alkanes 12.5%; C13 olefins 12.5%) as the substrate, 22.94 mg (0.090 mmol) of cobalt(II) acetylacetonate was used as the metal catalyst, and 124.54 mg (0.448 mmol) of L... 12 As a ligand, it was placed in a high-temperature and high-pressure reactor at 170°C and stirred for 4 hours in a CO / H2 (3.5MPa / 3.5MPa) mixed gas.

[0076] After the reaction, the olefin fraction in the mixed substrate was converted to 98.6%, of which 5.7% was converted to the corresponding alkanes, 4.8% to isoolefins, and 88.1% to the corresponding C4444445 ... n+1 Higher alcohols, with a positive-to-isomer ratio of 97.3:2.7.

[0077] Example 4

[0078] Using 20 mL of a mixed olefin (composition: C10 alkanes 12.5%; C10 olefins 12.5%; C11 alkanes 12.5%; C11 olefins 12.5%; C12 alkanes 12.5%; C12 olefins 12.5%; C13 alkanes 12.5%; C13 olefins 12.5%) as the substrate, 20.10 mg (0.078 mmol) of cobalt(II) acetylacetonate was used as the metal catalyst, and 108.9 mg (0.39 mmol) of L... 13 As a ligand, it was placed in a high-temperature and high-pressure reactor at 170°C and stirred for 4 hours in a CO / H2 (3.5MPa / 3.5MPa) mixed gas.

[0079] Example 5

[0080] Using 20 mL of a mixed olefin mixture (composition: C10 alkanes 12.5%; C10 olefins 12.5%; C11 alkanes 12.5%; C11 olefins 12.5%; C12 alkanes 12.5%; C12 olefins 12.5%; C13 alkanes 12.5%; C13 olefins 12.5%) as the substrate, 11.64 mg (0.089 mmol) of cobalt chloride as the metal catalyst, and 135.3 mg (0.45 mmol) of L... 14 As a ligand, it was placed in a high-temperature and high-pressure reactor at 200°C and stirred for 2 hours in a CO / H2 (4MPa / 4MPa) mixed gas.

[0081] After the reaction, the olefin fraction in the mixed substrate was converted to 95.2%, of which 8.1% was converted to the corresponding alkanes, 13.4% to isoolefins, and 73.7% to the corresponding C4 olefins. n+1 Higher alcohols, with a normal-to-isomeric ratio of 92:8.

[0082] Example 6

[0083] Using 20 mL of a mixed olefin mixture (composition: C10 alkanes 12.5%; C10 olefins 12.5%; C11 alkanes 12.5%; C11 olefins 12.5%; C12 alkanes 12.5%; C12 olefins 12.5%; C13 alkanes 12.5%; C13 olefins 12.5%) as the substrate, 10.2 mg (0.078 mmol) of cobalt chloride as the metal catalyst, and 148.2 mg (0.39 mmol) of L... 15 As a ligand, it was placed in a high-temperature and high-pressure reactor at 200°C and stirred for 2 hours in a CO / H2 (4MPa / 4MPa) mixed gas.

[0084] After the reaction, the olefin fraction in the mixed substrate was converted to 99.8%, of which 2.1% was converted to the corresponding alkanes, 0.7% to isoolefins, and 97% to the corresponding C4 olefins. n+1 Higher alcohols, with a normal-to-isomeric ratio of 55:45.

[0085] Example 7

[0086] Using 100 mL of a mixed olefin (composition: C10 alkanes 12.5%; C10 olefins 12.5%; C11 alkanes 12.5%; C11 olefins 12.5%; C12 alkanes 12.5%; C12 olefins 12.5%; C13 alkanes 12.5%; C13 olefins 12.5%) as the substrate, 11.65 mg (0.089 mmol) of cobalt chloride as the metal catalyst, and 175.6 mg (0.45 mmol) of L... 16 As a ligand, it was placed in a high-temperature and high-pressure reactor at 200°C and stirred for 2 hours in a CO / H2 (4MPa / 4MPa) mixed gas.

[0087] After the reaction, the olefin fraction in the mixed substrate was converted to 97.7%, of which 2.5% was converted to the corresponding alkanes, 10.3% to isoolefins, and 84.9% to the corresponding C44.9%. n+1 Higher alcohols, with a positive-to-isomeric ratio of 95.4:4.6.

[0088] Example 8

[0089] Using 200 mL of a mixed olefin mixture (composition: C10 alkanes 12.5%; C10 olefins 12.5%; C11 alkanes 12.5%; C11 olefins 12.5%; C12 alkanes 12.5%; C12 olefins 12.5%; C13 alkanes 12.5%; C13 olefins 12.5%) as the substrate, 13.1 mg (0.1 mmol) of cobalt chloride as the metal catalyst, and 134.6 mg (0.504 mmol) of L... 17 As a ligand, it was placed in a high-temperature and high-pressure reactor at 200°C and stirred for 2 hours in a CO / H2 (4MPa / 4MPa) mixed gas.

[0090] After the reaction, the olefin fraction in the mixed substrate was converted to 98.8%, of which 7.9% was converted to the corresponding alkanes, 5.4% to isoolefins, and 85.5% to the corresponding C4 ... n+1 Higher alcohols, with a positive-to-isomeric ratio of 91.7:8.3.

[0091] Example 9

[0092] Using 5 mL of 1-octene as the substrate, 33.15 mg (0.25 mmol) of cobalt chloride as the metal catalyst, and 354 mg (1.28 mmol) of L... 12 As a ligand, it was placed in a high-temperature and high-pressure reactor at 200°C and stirred for 2 hours in a CO / H2 (4.5MPa / 4.5MPa) mixed gas.

[0093] After the reaction, the olefin fraction in the mixed substrate was converted to 95.8%, of which 4.9% was converted to the corresponding alkanes, 8.4% to isoolefins, and 86.5% to the corresponding Cn+1 higher alcohols, with a normal-to-isomeric ratio of 93.7:6.3.

[0094] Example 10

[0095] Using 5 mL of 1-decene as the substrate, 20.6 mg (0.16 mmol) of cobalt chloride as the metal catalyst, and 220.4 mg (0.79 mmol) of L... 12 As a ligand, it was placed in a high-temperature and high-pressure reactor at 200°C and stirred for 2 hours in a CO / H2 (4MPa / 4MPa) mixed gas.

[0096] After the reaction, the conversion rate of the olefin fraction in the mixed substrate was 96.6%, of which 4.6% was converted to the corresponding alkanes, 6.4% to isoolefins, and 85.6% to the corresponding Cn+1 higher alcohols, with a normal-to-isomeric ratio of 92.8:7.2.

[0097] Example 11

[0098] Using 5 mL of 1-dodecene as the substrate, 23.46 mg (0.18 mmol) of cobalt chloride as the metal catalyst, and 250.86 mg (0.90 mmol) of L... 12 As a ligand, it was placed in a high-temperature and high-pressure reactor at 200°C and stirred for 2 hours in a CO / H2 (5MPa / 5MPa) mixed gas.

[0099] After the reaction, the olefin fraction in the mixed substrate was converted to 95.4%, of which 3.6% was converted to the corresponding alkanes, 4.4% to isoolefins, and 87.4% to the corresponding Cn+1 higher alcohols, with a normal-to-isomeric ratio of 91.7:8.3.

[0100] Example 12

[0101] Using 5 mL of 1-tetradecene as the substrate, 23.13 mg (0.18 mmol) of cobalt chloride as the metal catalyst, and 247.32 g (0.89 mmol) of L... 12 As a ligand, it was placed in a high-temperature and high-pressure reactor at 200°C and stirred for 2 hours in a CO / H2 (4MPa / 4MPa) mixed gas.

[0102] After the reaction, the olefin fraction in the mixed substrate was converted to 94.4%, of which 4.6% was converted to the corresponding alkanes, 3.4% to isoolefins, and 86.4% to the corresponding Cn+1 higher alcohols, with a normal-to-isomeric ratio of 92.6:7.4.

[0103] In summary, Examples 1-3 demonstrate that this catalyst system can maintain extremely high olefin conversion and high-carbon alcohol selectivity in coal-based Fischer-Tropsch olefin fractions with different compositions, and exhibits excellent straight-chain alcohol selectivity (>97%).

[0104] Examples 3-8 systematically demonstrate that by changing the phosphine ligand structure (from L8 to L13), the normal-to-isomeric ratio of the higher alcohol products can be controlled within a wide range from 97.3:2.7 to 55:45 while maintaining high activity. This fully demonstrates the ability of this invention to control product selectivity through ligand design.

[0105] Examples 4 to 8 demonstrate that the catalyst system can maintain high activity and stability when the reaction scale is increased from 20 mL to 200 mL, verifying its potential for industrial scale-up.

[0106] Examples 9 to 12 demonstrate different long-chain α-olefin substrates ranging from octene to tetradecene. The catalysts all exhibited excellent reactivity and product selectivity, confirming the broad substrate applicability of this catalytic system.

[0107] The method described in this invention is simple, and the products can be separated by conventional vacuum distillation after the reaction. The catalyst system can be recycled, resulting in significant economic and environmental benefits.

[0108] Contents not described in detail in this specification are prior art known to those skilled in the art. Although illustrative specific embodiments of the invention have been described above to facilitate understanding by those skilled in the art, it should be understood that the invention is not limited to the scope of the specific embodiments. Various modifications are readily apparent to those skilled in the art as long as they fall within the spirit and scope of the invention as defined and determined by the appended claims, and all inventions utilizing the concept of this invention are protected.

Claims

1. A cobalt phosphine complex catalyst, characterized in that: The catalyst is formed by coordination of a cobalt compound and a phosphine ligand. The cobalt compound is selected from Co2(CO)8, Co(acac)2, CoCl2, CoBr2, CoI2 and their modified complexes, and the modification methods include anion exchange, ligand pre-complexation, support loading or in-situ generation; The general structural formula of the phosphine ligand is as follows: ； Where R 1 R 2 R 3 R 4 R 5 R 6 The alkyl group is independently selected from C1 to C20, the haloalkyl group is selected from C1 to C20, the alkoxy group is selected from C1 to C20, and the aryl group or substituted aryl group is selected from C6 to C24. The substituents in the substituted aryl group are C1-C12 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, halogen, nitro, cyano, C1-C12 haloalkyl, and C6-C18 aryl. The nitrogen-containing substituent is —NR 3 R 4 , where R 3 R 4 The alkyl group is independently selected from C1 to C20, C1 to C20 haloalkyl group, C1 to C20 alkoxy group, C6 to C24 aryl group or substituted aryl group, wherein the substituent in the substituted aryl group is C1 to C12 alkyl group, C1 to C6 alkoxy group, C1 to C6 alkylamino group, halogen group, nitro group, cyano group, C1 to C12 haloalkyl group, C6 to C18 aryl group; The silicon-containing substituent is —SiR2R3R4, wherein R2, R3, and R4 are independently selected from C1 to C20 alkyl, C1 to C20 haloalkyl, C1 to C20 alkoxy, C6 to C24 aryl or substituted aryl, and the substituent in the substituted aryl is C1 to C12 alkyl, C1 to C6 alkoxy, C1 to C6 alkylamino, halogen, nitro, cyano, C1 to C12 haloalkyl, or C6 to C18 aryl.

2. The cobalt phosphine complex catalyst according to claim 1, characterized in that: The molar ratio of phosphine ligand to cobalt in the complex is from 0.5:1 to 3:

1.

3. A one-step method for preparing higher alcohols from coal-based Fischer-Tropsch olefins, characterized in that: Under a CO / H2 mixed atmosphere, C4-C22 coal-based Fischer-Tropsch olefin substrates are contacted with the cobalt phosphine complex catalyst described in claim 1 or 2 and reacted at 40°C-200°C and 1 MPa-10 MPa for 2-12 hours to obtain the corresponding higher alcohols.

4. The method according to claim 3, characterized in that: The molar ratio of CO / H2 is 1:1 to 1:

5.

5. The method according to claim 3, characterized in that: The amount of the cobalt phosphine complex catalyst is 0.01% to 1.0% of the molar amount of the olefin substrate, calculated as cobalt; wherein the molar ratio of phosphine ligand to substrate is 0.05% to 5.0%.

6. The method according to claim 3, characterized in that: The reaction can be carried out in the presence or without a solvent, wherein the solvent is toluene, xylene, tetrahydrofuran or other inert organic solvents.

7. The application of the cobalt phosphine complex catalyst according to any one of claims 1 or 2 in the hydroformylation reaction of olefins.

8. The use of the cobalt phosphine complex catalyst according to any one of claims 1 or 2 in the preparation of higher alcohols.

Images