Olefin hydroformylation method and application

Abstract

According to the olefin hydroformylation method and application provided by the invention, the hydroformylation reaction is carried out by adopting a low-price non-noble metal cobalt-phosphine catalyst at lower pressure and lower proper temperature, so that the economic benefit of the process is remarkably improved; besides, in the system of the cobalt-phosphine catalyst solution, the mass ratio of the cobalt-phosphine catalyst solution to the olefin and the mass ratio of the cobalt to the olefin are adjusted, and the sum of the conversion rate of the raw materials and the selectivity of the alcohol and the aldehyde is increased at low temperature and pressure.

Description

Technical Field

[0001] The invention belongs to the field of hydroformylation reaction, and specifically relates to a method and application of olefin hydroformylation. Background Art

[0002] The olefin reacts with carbon monoxide and hydrogen in the presence of a catalyst to undergo a hydroformylation reaction. The hydroformylation method comprises contacting an olefinic unsaturated compound with carbon monoxide and hydrogen in the presence of a catalyst under reaction conditions. The catalyst used in the hydroformylation reaction in industrial production is generally a cobalt (Co)-based or rhodium (Rh)-based catalyst.

[0003] Compared with cobalt catalysts, Rh complexes have higher reaction activity and can react at milder temperatures and pressures. However, rhodium catalysts have poor high-temperature performance and are difficult to use for carbonylation of advanced olefins. Existing rhodium catalysts have good catalytic effects on terminal olefins, but poor activity on internal olefins. The catalyst is oil-soluble and product separation is also difficult, making post-processing more complicated. Rhodium, as a precious metal resource, is scarce and expensive, and its recovery and reuse cost is high.

[0004] EP2881173A4 discloses a catalyst composition and a method for hydroformylating olefins using the catalyst composition, wherein the catalyst composition uses a specific ligand of a transition metal catalyst and a ligand stabilizer in the hydroformylation process of olefins, thereby improving the stability of the catalyst to maintain the catalyst activity, reduce the amount of the ligand, and improve the selectivity for iso-aldehydes. Stability is a common problem of hydroformylation catalysts, and the activity of hydroformylation catalysts decreases significantly as the reaction time increases.

[0005] DE59704070D1 discloses a method for preparing alcohols having 7-18 carbon atoms, comprising hydroformylating the corresponding olefins with synthesis gas in the presence of an organic phase containing a cobalt catalyst at a temperature of 50-220°C and a pressure of 100-400 bar, followed by hydrogenating the aldehydes obtained thereby, wherein an aqueous solution of a cobalt salt is reacted with the synthesis gas in the presence of an organic solvent that is not miscible with water or only a small amount of water to form a cobalt catalyst, and the organic phase containing the cobalt catalyst is prepared by extracting the formed cobalt catalyst from the aqueous phase with an organic extractant that is not miscible with water or only a small amount of water. The formation of the cobalt catalyst, the extraction of the formed cobalt catalyst in the organic phase and the hydroformylation of the corresponding olefins are carried out in a one-step process. The oxo alcohol prepared by the method of the present invention is used to prepare carboxylic acid esters as plasticizers for plastics. The reaction time is generally more than 10 hours. Summary of the invention

[0006] The inventors have found in experiments that, in the prior art, the conversion rate of olefin hydroformylation reaction and the sum of the selectivity of alcohol and aldehyde in the obtained product are generally low when the cobalt-based catalyst is used at relatively low temperature and pressure.

[0007] In order to solve the problems existing in the prior art, the present invention provides a method for hydroformylation of olefins, which comprises:

[0008] (1) adding a cobalt-phosphine catalyst solution and synthesis gas into a pretreatment reactor for pretreatment to obtain a pretreated cobalt-phosphine catalyst solution;

[0009] (2) adding the pretreated cobalt-phosphine catalyst solution and olefin to a hydroformylation reactor in the presence of synthesis gas to carry out a hydroformylation reaction; wherein the mass ratio of the pretreated cobalt-phosphine catalyst solution to the olefin is (10 -6 ~1):1;

[0010] (3) After the reaction is completed, a portion of the alcohol, aldehyde, alkane and olefin raw materials are separated from the crude reaction product, and the remaining catalyst-containing solution is circulated to the pretreatment reactor for pretreatment.

[0011] The second object of the present invention is to provide the use of the above method in the preparation of alcohols and aldehydes by hydroformylation reaction.

[0012] In the olefin formylation reaction of the prior art, the mass ratio of the cobalt-phosphine catalyst solution to the olefin is usually greater than 1, and the sum of the selectivity of alcohols and aldehydes in the product of the cobalt-based catalyst is generally low at lower temperatures and pressures. The inventors of the present invention achieve a significant improvement in the conversion rate of the raw material and the sum of the selectivity of alcohols and aldehydes at lower temperatures and pressures by adjusting the mass ratios of the cobalt-phosphine catalyst solution to the olefin and cobalt to the olefin. The reaction rate can be significantly increased, and the olefin raw material processing capacity can be significantly improved. DETAILED DESCRIPTION

[0013] The following further exemplifies the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention belong to the scope of protection of the present invention. The specific process parameters and the like in the following examples are only examples in a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values ​​​​exemplified below.

[0014] The present invention provides a method for hydroformylation of olefins, characterized in that the method comprises:

[0015] (1) adding a cobalt-phosphine catalyst solution and synthesis gas into a pretreatment reactor for pretreatment to obtain a pretreated cobalt-phosphine catalyst solution;

[0016] (2) adding the pretreated cobalt-phosphine catalyst solution and olefin to a hydroformylation reactor in the presence of synthesis gas to carry out a hydroformylation reaction; wherein the mass ratio of the pretreated cobalt-phosphine catalyst solution to the olefin is (10 -6 ~1):1;

[0017] (3) After the reaction is completed, a portion of the alcohol, aldehyde, alkane and olefin raw materials are separated from the crude reaction product, and the remaining catalyst-containing solution is circulated to the pretreatment reactor for pretreatment.

[0018] In the hydroformylation reaction of the prior art, the mass ratio of the catalyst solution to the olefin is usually greater than 1, and at a relatively low temperature and pressure, the sum of the selectivity of alcohols and aldehydes in the product is generally low; however, in the technical scheme of the present invention, by adjusting the mass ratio of the cobalt-phosphine catalyst solution to the olefin after pretreatment and the mass ratio of cobalt to the olefin, the conversion rate of the raw material and the sum of the selectivity of alcohols and aldehydes in the product are improved at a relatively low temperature and pressure.

[0019] In addition, pretreatment of the catalyst solution is beneficial to the formation of active units of the cobalt-phosphine catalyst, reducing catalyst decomposition, improving the activity and stability of the catalyst, and extending the service life of the catalyst.

[0020] According to the method of the present invention, when the material containing the cobalt-phosphine complex catalyst is returned to the inlet of the hydroformylation reactor and / or the pretreatment reactor, a small amount of new catalyst can be added as needed.

[0021] According to a specific embodiment of the present invention, the mass ratio of the cobalt-phosphine catalyst solution to the olefin after pretreatment is (10 -6 ~1):1, preferably (10 -5 ~1):1, more preferably (0.0001~1):1, further preferably (0.001~1):1, most preferably (0.01~0.1):1.

[0022] According to one embodiment of the present invention, the pretreatment reactor may be an autoclave or a tubular reactor.

[0023] According to a specific embodiment of the present invention, the pretreatment conditions are:

[0024] The pretreatment temperature is 50°C to 210°C, preferably 70°C to 190°C, more preferably 70°C to 160°C, and most preferably 70°C to 100°C; the pretreatment pressure is 1Mpa to 12MPa, preferably 3MPa to 10MPa, and more preferably 5MPa to 8MPa; the pretreatment time is 0.1 to 1000 hours, preferably 1 to 100 hours, more preferably 1 to 50 hours, and most preferably 1 to 20 hours.

[0025] According to a specific embodiment of the present invention, the inventors of the present application unexpectedly discovered that when a cobalt-phosphine catalyst is added to a reaction system, a better reaction effect can be achieved by minimizing the introduction of solvent or even eliminating the introduction of solvent.

[0026] When the catalyst contains a solvent, the solvent may be various solvents known in the art, such as olefins, alkanes, aldehydes, alcohols, heavy substances produced in hydroformylation reactions, etc., preferably various types of C1-C20 aldehydes, alcohols, heavy substances produced in hydroformylation reactions. In addition, the solvent may contain products or raw materials.

[0027] Alternatively, no solvent may be used.

[0028] The solvent is preferably a strong soluble mixed solvent. The strong soluble mixed solvent may contain the following components: (1) C8-C16 high carbon alcohol, (2) at least two C9 compound condensation products. The use of a strong soluble mixed solvent can increase the catalyst concentration, reduce the reaction temperature, and increase the total yield of alcohol and aldehyde. Preferably, no solvent is added.

[0029] According to a specific embodiment of the present invention, in the cobalt-phosphine complex catalyst solution, the mass concentration of cobalt is 0.0001% to 10%, preferably 0.001% to 5%, more preferably 0.01% to 5%, and most preferably 0.1% to 2%.

[0030] According to a specific embodiment of the present invention, a small amount of water may be added to the hydroformylation reaction system, and the amount of water added accounts for 0.0001wt% to 10wt% of the total amount of the reaction solution, preferably 0.001% to 5%, more preferably 0.01wt% to 5wt%, and most preferably 0.01wt% to 1wt%.

[0031] According to a specific embodiment of the present invention, the raw materials for preparing the cobalt-phosphine complex catalyst include a cobalt-containing raw material and a phosphine ligand, wherein the mass ratio of cobalt to phosphorus in the cobalt-containing raw material and the phosphine ligand is 1:

[0032] (0.01~3), preferably 1:(0.1~2), more preferably 1:(0.3~1).

[0033] The cobalt-containing raw material can be a cobalt salt or a cobalt oxide, wherein the cobalt salt can be an inorganic acid cobalt or an organic acid cobalt, for example, one or more selected from the group consisting of cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt levulinate, cobalt formate, octacarbonyl dicobalt and cobalt cyclopentaneate.

[0034] The phosphine ligand may be various ligands known in the art, such as one or more of phosphites, triphenylphosphine, trialkylphosphine, di-(triphenylphosphine), alkylphenylphosphine, etc., preferably triphenylphosphine or trialkylphosphine.

[0035] The cobalt-phosphine complex catalyst solution can be prepared according to a known method, for example: dissolving a cobalt-containing raw material and a phosphine ligand in a solvent, introducing CO and H2 gases to a pressure of 1 to 6 MPa, preferably 2 to 4 MPa, and reacting at 80 to 180° C., preferably 100 to 150° C., for 0.5 to 24 hours, preferably 1 to 15 hours, more preferably 3 to 10 hours, to obtain a cobalt-phosphine catalyst solution.

[0036] According to a specific embodiment of the present invention, the olefin is a C1-C30 olefin, preferably a C6-C20 olefin, and the olefin may be a straight-chain olefin and / or a branched olefin, and the number of branches of the branched olefin may be ≥ 1. The present invention is particularly suitable for a C8 olefin mixture containing one or more of 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, etc. Due to the large steric hindrance, the difficulty of hydroformylation of trimethyl multi-branched olefins is higher than that of less branched olefins.

[0037] According to a specific embodiment of the present invention, the synthesis gas refers to a mixture of carbon monoxide and hydrogen or a mixture of carbon monoxide, hydrogen and other gases (such as methane, CO2, H2O, etc.), wherein the molar ratio of carbon monoxide to hydrogen is 100:1 to 1:100, preferably 10:1 to 1:10, more preferably 4:1 to 1:4, and most preferably 3:1 to 1:2.

[0038] According to a specific embodiment of the present invention, the formylation reactor is a tubular reactor.

[0039] According to a specific embodiment of the present invention, the mass ratio of cobalt to olefin is 1*10 -6 ~1, preferably 1*10 -5 ~10 -2 , more preferably 1*10 -4 ~5*10 -3 .

[0040] In the present invention, cobalt in the mass ratio of cobalt / olefin represents the cobalt element.

[0041] According to a specific embodiment of the present invention, the conditions of the formylation reaction are: the hydroformylation reaction temperature is 70°C to 200°C, preferably 100°C to 190°C, more preferably 110°C to 180°C; the reaction pressure is 1MPa to 12MPa, preferably 2MPa to 8Mpa, more preferably 3MPa to 6Mpa; the reaction time is 0.1 to 60 hours, preferably 1 to 40 hours, more preferably 3 to 20 hours, and most preferably 4 to 10 hours.

[0042] According to a specific embodiment of the present invention, the molar ratio of synthesis gas to olefin is (1-12):1, preferably (2-6):1, and more preferably (3-6):1.

[0043] According to a specific embodiment of the present invention, in the step (3), the crude product separation can be performed by first performing gas-liquid separation and then performing distillation separation.

[0044] The gas-liquid separation can be performed in a gas-liquid separation tank under the condition of lowering the temperature without lowering the pressure. The gas-liquid separation temperature is 0°C to 100°C, preferably 20°C to 80°C, and more preferably 20°C to 40°C.

[0045] The gas phase flow obtained after gas-liquid separation is basically synthesis gas. After condensation and / or absorption, the remaining synthesis gas can be circulated to the pre-reactor and / or the reactor inlet for repeated use.

[0046] The liquid phase flow after gas-liquid separation can be distilled and separated by a distillation device, and the top output is alkane, aldehyde, and alcohol, and the bottom obtains a heavy material containing a cobalt-phosphine complex catalyst.

[0047] The second object of the present invention is to provide the use of the above method in preparing alcohols by hydroformylation reaction.

[0048] The present invention has at least the following advantages:

[0049] 1. In the technical solution of the present invention, a low cobalt / olefin mass ratio is used, such as 2×10 -4 Compared with the prior art, the amount of catalyst used is reduced and the catalyst utilization rate is significantly improved.

[0050] 2. The technical solution of the present invention improves the conversion rate of the raw material and the sum of the selectivity of alcohol and aldehyde in the product by adjusting the mass ratio of the cobalt-phosphine catalyst solution to the olefin.

[0051] 3. The technical solution of the present invention adopts a low-cost non-precious metal cobalt-phosphine catalyst to carry out the hydroformylation reaction at a relatively low pressure and a relatively low suitable temperature, thereby significantly improving the economic benefits of the process.

[0052] 4. The technical solution of the present invention significantly improves the reaction speed, significantly increases the raw material processing capacity, and improves the utilization rate of the reaction device.

[0053] 5. The present invention is applicable to a wide range of olefin raw materials, and is particularly suitable for the hydroformylation reaction of multi-branched olefins with large steric hindrance.

[0054] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, the raw materials used are all common commercially available raw materials.

[0055] Catalyst Preparation Example 1

[0056] In a reaction kettle, cobalt cyclohexanecarboxylate and triphenylphosphine were dissolved in isononanol in such amounts that the cobalt content in the obtained solution was 1.5wt% and the phosphorus content was 0.87wt%. The air was replaced with synthesis gas, and the synthesis gas was filled in to a pressure of 3MPa. The mixture was stirred at 400rpm and 110°C for 6h to obtain a cobalt-phosphine complex solution, which was recorded as catalyst solution A1.

[0057] Catalyst Preparation Example 2

[0058] In a reaction kettle, cobalt cyclohexanecarboxylate and triphenylphosphine are dissolved in isononanol in such amounts that the cobalt content in the obtained solution is 0.67wt% and the phosphorus content is 0.39wt%. The air is replaced with synthesis gas, and the synthesis gas is filled in to a pressure of 3MPa. Under stirring at 400rpm and 110°C for 6h, a cobalt-phosphine complex solution is obtained, which is recorded as catalyst solution A2.

[0059] Catalyst Preparation Example 3

[0060] In a reaction kettle, cobalt cyclohexanecarboxylate and triphenylphosphine are dissolved in isononanol in such amounts that the cobalt content in the obtained solution is 0.26wt%, and the phosphorus content is 0.20wt%. The air is replaced with synthesis gas, and the synthesis gas is filled in to a pressure of 4MPa. Under stirring at 400rpm and 120°C, a cobalt-phosphine complex solution is obtained after reacting for 6h, which is recorded as catalyst solution A3.

[0061] The olefin raw material in the example is a commercially available C8 olefin, and the composition is: 75.1 wt % of 2,4,4-trimethyl-1-pentene, 21.2 wt % of 2,4,4-trimethyl-2-pentene, and the rest are multi-branched olefins.

[0062] The following formula for calculating the raw material conversion rate is: [1-(the mass of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene in the reaction product) / (the mass of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene in the raw material)]×100%

[0063] Example 1

[0064] The catalyst solution A1 and the synthesis gas (CO / H2 molar ratio of 1:2) were added to the pretreatment reactor. The temperature of the pretreatment reactor was 100 °C and the pressure was 6 MPa. The pretreatment was carried out for 1 h. After the pretreatment, the catalyst solution and the C8 olefin were introduced into the hydroformylation reactor at a ratio of 5.2 g:180 g. The mass ratio of cobalt to C8 olefin was 4.3×10 -4, synthesis gas (CO / H2 molar ratio of 1:2) was added, the reaction pressure was 6 MPa, the reaction temperature was 180°C, the reaction was carried out for 5 hours, and the product was analyzed by chromatography. The raw material conversion rate was 94.2wt%, and the product contained 22.6wt% of 2.4.4-trimethylpentane, 14.4wt% of isononanal, 54.9wt% of isononanol, and 8.2wt% of heavy matter.

[0065] Example 2

[0066] The catalyst solution A2 and the synthesis gas (CO / H2 molar ratio of 1:2) were added to the pretreatment reactor. The temperature of the pretreatment reactor was 100 °C and the pressure was 6 MPa. The pretreatment was carried out for 1 h. After the pretreatment, the catalyst solution and the C8 olefin were introduced into the hydroformylation reactor at a ratio of 9.1 g:180 g. The mass ratio of cobalt to C8 olefin was 3.3×10 -4 , synthesis gas (CO / H2 molar ratio of 1:2) was added, the reaction pressure was 6 MPa, the reaction temperature was 180°C, the reaction was carried out for 5 hours, and the product was analyzed by chromatography. The raw material conversion rate was 95.1wt%, and the product contained 22.9wt% of 2.4.4-trimethylpentane, 8.6wt% of isononanal, 61.4wt% of isononanol, and 7.1wt% of heavy matter.

[0067] Example 3

[0068] The catalyst solution A2 and the synthesis gas (CO / H2 molar ratio of 1:2) were added to the pretreatment reactor. The temperature of the pretreatment reactor was 100 °C and the pressure was 6 MPa. The pretreatment was carried out for 1 h. After the pretreatment, the catalyst solution and the C8 olefin were introduced into the hydroformylation reactor at a ratio of 9.1 g:180 g. The mass ratio of cobalt to C8 olefin was 3.3×10 -4 , 1.59wt% of water and synthesis gas (CO / H2 molar ratio is 1:2) were added, the reaction pressure was 6MPa, the reaction temperature was 180℃, the reaction was carried out for 6h, and the product was analyzed by chromatography. The raw material conversion rate was 90.8wt%, and the product contained 23.1wt% of 2.4.4-trimethylpentane, 12.8wt% of isononanal, 58.5wt% of isononanol, and 5.62wt% of heavy matter.

[0069] Example 4

[0070] The catalyst solution A2 and the syngas with the composition of CH4:CO:H2 (molar ratio) 1:3:6 and 25 ppm CO2 were added to the pretreatment reactor. The temperature of the pretreatment reactor was 100 ° C and the pressure was 8 MPa. The pretreatment was carried out for 1 hour. After the pretreatment, the catalyst solution and the C8 olefin were introduced into the hydroformylation reactor at a ratio of 36.6 g:60.4 g. The mass ratio of cobalt to C8 olefin was 4.0×10 -3The synthesis gas composition is CH4:CO:H2 (molar ratio) 1:3:6 and contains 25PPmCO2, the reaction pressure is 8MPa, the reaction temperature is 160℃, the reaction time is 6.7h, and the product is subjected to chromatographic analysis. The raw material conversion rate is 96.0wt%, and the product contains 28.1wt% of 2.4.4-trimethylpentane, 1.0wt% of isononanal, 65.2wt% of isononanol, and 5.5wt% of heavy matter.

[0071] Example 5

[0072] The catalyst solution A2 and the synthesis gas (CO / H2 molar ratio of 1:2) were added to the pretreatment reactor. The temperature of the pretreatment reactor was 100 °C and the pressure was 6 MPa. The pretreatment was carried out for 1 h. After the pretreatment, the catalyst solution and the C8 olefin were introduced into the hydroformylation reactor at a ratio of 5 g:180.7 g. The mass ratio of cobalt to C8 olefin was 1.8×10 -4 , synthesis gas (CO / H2 molar ratio is 1:2), reaction pressure 6MPa, reaction temperature 180℃, reaction time 5h, chromatographic analysis of the product, raw material conversion rate 98.3wt%, 2.4.4-trimethylpentane 21wt%, isononanal 14.9wt%, isononanol 55.0wt%, and heavy matter 8.6wt% in the product.

[0073] It can be seen from Example 5 that under the condition of low mass ratio of cobalt-phosphine catalyst solution to olefin, at reaction temperature of 180°C and high olefin conversion, a relatively high content of aldehyde can still be obtained in the product. However, in the prior art, at high olefin conversion (e.g., greater than 90wt%), the aldehyde content in the product is greatly reduced (e.g., less than 5wt%), and the alkane content is greatly increased.

[0074] Comparative Example 1

[0075] The catalyst solution A3 and the syngas with the composition of CH4:CO:H2 (molar ratio) 1:3:6 and 25 ppm CO2 were added to the pretreatment reactor. The temperature of the pretreatment reactor was 100 °C and the pressure was 8 MPa. The pretreatment was carried out for 1 h. After the pretreatment, the catalyst solution and the C8 olefin were introduced into the hydroformylation reactor at a ratio of 110 g:60.2 g. The mass ratio of cobalt to C8 olefin was 4.7×10 -3 The synthesis gas composition is CH4:CO:H2 (molar ratio) 1:3:6 and contains 25PPmCO2, the reaction pressure is 8MPa, the reaction temperature is 160℃, the reaction time is 6.7h, and the product is subjected to chromatographic analysis. The raw material conversion rate is 87.7wt%, and the product contains 27.3wt% of 2.4.4-trimethylpentane, 4.7wt% of isononanal, 53.7wt% of isononanol, and 14.4wt% of heavy matter.

[0076] Table 1

[0077]

[0078] It can be seen from the comparison between Comparative Example 1 and the embodiments that according to the method of the present application, a higher conversion rate and a higher selectivity of isononanol and isononanal can be obtained under the condition of a lower mass ratio of cobalt to C8 olefins.

[0079] Unless otherwise defined, the terms used in the present invention have the meanings commonly understood by those skilled in the art.

[0080] The embodiments described in the present invention are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Those skilled in the art may make various other substitutions, changes and improvements within the scope of the present invention. Therefore, the present invention is not limited to the above embodiments, but is only limited by the claims.

Claims

1. A method for hydroformylation of olefins, characterized in that: The method includes: (1) adding a cobalt-phosphine catalyst solution and synthesis gas into a pretreatment reactor for pretreatment to obtain a pretreated cobalt-phosphine catalyst solution; (2) adding the pretreated cobalt-phosphine catalyst solution and olefin to a hydroformylation reactor in the presence of synthesis gas to carry out a hydroformylation reaction; wherein the mass ratio of the pretreated cobalt-phosphine catalyst solution to the olefin is (10 -6 ~1):1; (3) After the reaction is completed, a portion of the alcohol, aldehyde, alkane and olefin raw materials are separated from the crude reaction product, and the remaining catalyst-containing solution is circulated to the pretreatment reactor for pretreatment.

2. The method according to claim 1, characterized in that: The mass ratio of the cobalt-phosphine catalyst solution to the olefin after pretreatment is (10 -5 ~1):1, more preferably (0.0001~1):1, further preferably (0.001~1):1, most preferably (0.01~0.1):

1.

3. The method according to claim 1, characterized in that The mass ratio of cobalt to olefin is 1*10 -6 ~1, preferably 1*10 -5 ~10 -2 , more preferably 1*10 -4 ~5*10 -3 .

4. The method according to claim 1, characterized in that The pretreatment conditions are as follows: pretreatment temperature is 50°C to 210°C, preferably 70°C to 190°C, more preferably 70°C to 160°C, and most preferably 70°C to 100°C; pretreatment pressure is 1Mpa to 12MPa, preferably 3MPa to 10MPa, and more preferably 5MPa to 8MPa; pretreatment time is 0.1 to 1000 hours, preferably 1 to 100 hours, more preferably 1 to 50 hours, and most preferably 1 to 20 hours.

5. The method according to claim 1, characterized in that The cobalt-phosphine catalyst solution is a catalyst solution dissolved in a solvent or a catalyst containing no solvent.

6. The method according to claim 1, characterized in that In the cobalt-phosphine catalyst solution, the mass concentration of cobalt is 0.0001% to 10%, preferably 0.001% to 5%, more preferably 0.01% to 5%, and most preferably 0.1% to 2%.

7. The method according to claim 1, characterized in that A small amount of water is added to the hydroformylation reaction system, and the amount of water added accounts for 0.0001wt% to 10wt% of the total amount of the reaction solution, preferably 0.001wt% to 5%, more preferably 0.01wt% to 5wt%, and most preferably 0.01wt% to 1wt%.

8. The method according to claim 1, characterized in that The raw materials for preparing the cobalt-phosphine catalyst include a cobalt-containing raw material and a phosphine ligand, wherein the mass ratio of cobalt and phosphorus of the cobalt-containing raw material to the phosphine ligand is 1:(0.01-3), preferably 1:(0.1-2), and more preferably 1:(0.3-1).

9. The method according to claim 1, characterized in that: The conditions of the formylation reaction are: The conditions of the formylation reaction are: the hydroformylation reaction temperature is 70°C to 200°C, preferably 100°C to 190°C, more preferably 110°C to 180°C; the reaction pressure is 1MPa to 12MPa, preferably 2MPa to 8MPa; the reaction time is 0.1 to 60 hours, preferably 1 to 40 hours, more preferably 3 to 20 hours, and most preferably 4 to 10 hours.

10. The method according to claim 1, characterized in that The molar ratio of the synthesis gas to olefin is (1-12):1, preferably (2-6):1, and more preferably (3-6):

1.

11. Use of the method according to any one of claims 1 to 10 in the preparation of alcohols and aldehydes by hydroformylation reaction.

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