Method for hydroformylation of multi-branched olefin
By using a cobalt-phosphine catalyst solution for the hydroformylation of multi-branched olefins, the problems of poor activity and low reactor utilization in the hydroformylation of multi-branched high-carbon-number olefins have been solved. This has improved the stability and activity of the catalyst, reduced reaction pressure and equipment investment, simplified process operation, and lowered processing costs.
Patent Information
- Application Number
- CN202411623891.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-14
- Publication Date
- 2026-05-15
AI Technical Summary
Existing technologies suffer from poor hydroformylation activity and low reactor utilization in multi-branched high-carbon-number olefins.
The hydroformylation of multi-branched olefins was carried out using a cobalt-phosphine catalyst solution. The mass concentration of cobalt in the cobalt-phosphine catalyst solution was 0.01wt%-2.0wt%, the mass ratio of α-triisobutylene to β-triisobutylene was 1:1-2, and the mass ratio of cobalt-phosphine catalyst solution to olefin material was 0.1-0.8:1. The catalyst performance was optimized through pretreatment and contact reaction, and the reaction pressure and catalyst-to-oil ratio were reduced.
This approach improves catalyst stability and activity, reduces reaction pressure and equipment investment, increases reactor utilization, simplifies process operation, and lowers processing costs.
Abstract
Description
Technical Field
[0001] This invention relates to the field of hydroformylation reactions, and more specifically to a method for the hydroformylation of multi-branched olefins. Background Technology
[0002] The hydroformylation reaction of olefins can effectively convert inexpensive and readily available basic chemical raw materials, such as olefins, into a variety of important chemical products such as aldehydes and alcohols. In industrial production, the catalysts used in the hydroformylation reaction are generally cobalt (Co)-based or rhodium (Rh)-based catalysts.
[0003] For example, WO0222696A1 discloses a method for the continuous hydroformylation of polyolefins having 30-700 carbon atoms. The method includes: i) preparing a cobalt carbonyl catalyst active for hydroformylation from a catalyst precursor dissolved in an aqueous phase in the absence of polyolefin; ii) hydroformylating the polyolefin with syngas in a reaction zone in the presence of the cobalt carbonyl catalyst; iii) separating the cobalt carbonyl catalyst from the effluent of the reaction zone while at least partially regenerating the catalyst precursor, and recycling the catalyst precursor to the next step.
[0004] CN1257140A discloses a continuous method for hydroformylation of olefins having 6-20 carbon atoms, comprising: a) fully contacting an aqueous solution of cobalt(II) salt with hydrogen and carbon monoxide to form a hydroformylation active cobalt catalyst, and fully contacting an aqueous phase containing the cobalt catalyst with the olefin and optionally an organic solvent, as well as hydrogen and carbon monoxide, in at least one reaction zone; b) treating the effluent from the reaction zone with oxygen in the presence of an acidic aqueous solution of cobalt(II) salt, wherein the cobalt catalyst decomposes to form cobalt(II) salt and these substances are back-extracted into the aqueous phase; and subsequently separating the phases; c) recycling the aqueous solution of cobalt(II) salt in an unchanged form to step a), wherein the concentration of the aqueous solution of cobalt(II) salt, calculated as cobalt, is 1.1-1.7% by weight, and is continuously operated under conditions not exceeding the solubility limit of cobalt(II) formate in water.
[0005] Rh catalysts have higher reactivity than cobalt catalysts and can react under milder temperatures and pressures. However, the catalysts are oil-soluble and product separation is difficult, making post-processing more complex. Rhodium is a rare and expensive precious metal, and its recycling and reuse costs are high.
[0006] CN116063155A discloses a method for preparing alcohols by hydroformylation of olefins, the method comprising: (1) in the presence of a cobalt-phosphine complex catalyst, reacting C8-C... 30Olefins and syngas are introduced into a first reactor for a first contact reaction to obtain a first mixture; (2) syngas and the first mixture are introduced into a second reactor for a second contact reaction to obtain a second mixture; the volume of the second reactor is smaller than that of the first reactor; (3) the second mixture is separated to obtain light and heavy components respectively; (4) the heavy components are recycled. This method has a simple process flow, high olefin conversion rate, and high target product yield. However, this prior art is applied to high carbon number olefins with large steric hindrance, resulting in low hydroformylation activity. Furthermore, the agent-to-oil ratio in this prior art is too high, leading to low reactor utilization and difficult product separation. Summary of the Invention
[0007] The purpose of this invention is to provide a solution that overcomes the problems of poor hydroformylation activity and low reactor utilization in the prior art for multi-branched high-carbon-number olefins.
[0008] To achieve the above objectives, the present invention provides a method for hydroformylation of multi-branched olefins, the method comprising:
[0009] In the presence of a cobalt-phosphine catalyst solution, olefin materials containing triisobutylene and syngas are introduced into the reactor for contact reaction.
[0010] The mass concentration of cobalt in the cobalt-phosphine catalyst solution is 0.01wt%-2.0wt%, preferably 0.02wt%-1.0wt%.
[0011] The triisobutylene is α-triisobutylene and β-triisobutylene in a mass ratio of 1:1-2;
[0012] The mass ratio of the cobalt-phosphine catalyst solution to the olefin material is 0.1-0.8:1.
[0013] The solution provided by this invention has at least the following advantages:
[0014] 1. The method of the present invention enables continuous production. Without the addition of cobalt-phosphine catalyst, it can react continuously for 250 hours, and the catalyst activity is more stable, which is convenient for industrial application.
[0015] 2. In the method of the present invention, the agent-to-oil ratio is low, which overcomes the defect of high agent-to-oil ratio in traditional hydroformylation reaction and significantly improves the utilization rate of reactor.
[0016] 3. The method of the present invention is particularly suitable for the formylation reaction of multi-branched olefins with large steric hindrance, and has the advantages of lower reaction pressure, lower equipment investment and significantly reduced processing costs.
[0017] 4. In the method of the present invention, the same synthesis gas as that used in the contact reaction can be used when preparing the catalyst and pretreating the catalyst, without the need for high CO concentration or even pure CO gas, which reduces investment and simplifies process operation. Detailed Implementation
[0018] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0019] As described above, the present invention provides a method for hydroformylation of multi-branched olefins, the method comprising:
[0020] In the presence of a cobalt-phosphine catalyst solution, olefin materials containing triisobutylene and syngas are introduced into the reactor for contact reaction.
[0021] The mass concentration of cobalt in the cobalt-phosphine catalyst solution is 0.01wt%-2.0wt%, preferably 0.02wt%-1.0wt%.
[0022] The triisobutylene is α-triisobutylene and β-triisobutylene in a mass ratio of 1:1-2;
[0023] The mass ratio of the cobalt-phosphine catalyst solution to the olefin material is 0.1-0.8:1.
[0024] Preferably, the method further includes: pretreating the cobalt-phosphine catalyst solution prior to the contact reaction;
[0025] The pretreatment method includes introducing syngas into a preprocessor to allow the syngas to react with the cobalt-phosphine catalyst solution to obtain a pretreated cobalt-phosphine catalyst solution. The inventors of this invention have found that, in this preferred embodiment, it facilitates the formation of active units in the cobalt-phosphine catalyst, reduces catalyst decomposition, improves catalyst activity and stability, and extends catalyst lifespan.
[0026] Preferably, the preprocessor is an autoclave or a tubular reactor.
[0027] In a preferred embodiment, the pretreatment conditions include: a temperature of 50℃-200℃, preferably 75℃-150℃, more preferably 90℃-120℃; a pressure of 1MPa-12MPa, preferably 3MPa-10MPa, more preferably 3MPa-6MPa; and a time of 0.1h-10h, preferably 1h-3h.
[0028] Preferably, the pretreatment conditions further include: a rotation speed of 100-1000 rpm, more preferably 400-700 rpm.
[0029] Preferably, the conditions for the contact reaction include: a temperature of 60℃-250℃, more preferably 100℃-220℃, and even more preferably 150℃-200℃; and a pressure of 1MPa-10MPa, more preferably 2MPa-8MPa, and even more preferably 3MPa-5MPa.
[0030] Preferably, when the reactor is a batch reactor, the contact reaction time is 1-40 hours, more preferably 3-20 hours, and even more preferably 5-10 hours.
[0031] In a preferred embodiment, when the reactor is a tubular reactor, the contact reaction time is 1-50 hours, preferably 20-40 hours, and more preferably 25-40 hours. The inventors have found that, under this preferred embodiment, the cobalt-phosphine catalyst solution during the reaction process is more stable and less prone to decomposition.
[0032] While it is generally understood that high pressure is beneficial to the reaction, excessively high pressure will significantly increase equipment investment, power consumption, and operating costs. The inventors of this invention unexpectedly discovered during experiments that, using the cobalt-phosphine catalyst solution of this invention, the reaction pressure can be reduced to no more than 6 MPa; this reduces the required equipment investment and power consumption, thereby significantly lowering production costs.
[0033] Preferably, the conditions for the contact reaction further include a rotation speed of 100-1000 rpm, more preferably 400-700 rpm.
[0034] In a preferred embodiment, the syngas participating in the contact reaction and the syngas participating in the pretreatment reaction are the same or different;
[0035] Preferably, the syngas participating in the contact reaction and the syngas participating in the pretreatment reaction are both mixed gases containing CO and H2;
[0036] In the mixed gas, the molar ratio of CO to H2 is 4:1 to 1:4; preferably 3:1 to 1:3; more preferably 2:1 to 1:2.
[0037] In a preferred embodiment, the olefin material is obtained by polymerizing C4 olefins.
[0038] Preferably, the C4 olefin is at least one of the following: C4 produced by a refinery catalytic cracking unit, C4 produced by cracking to produce ethylene, and C4 produced as a byproduct of methanol-to-olefins production.
[0039] According to a particularly preferred embodiment, the cobalt-phosphine catalyst solution is a recycled cobalt-phosphine catalyst solution. The inventors of this invention have discovered that using a recycled cobalt-phosphine catalyst solution can improve feedstock conversion and C13 alcohol selectivity.
[0040] It should be noted that the recycled cobalt-phosphine catalyst solution in this invention is obtained by separating the products obtained from the contact reaction.
[0041] The present invention does not impose any particular requirements on the separation method, and those skilled in the art can choose according to their needs.
[0042] According to a preferred embodiment, the method further includes preparing the cobalt-phosphine catalyst solution using an operation comprising the following steps:
[0043] (1) In the presence of a solvent, cobalt-containing raw materials and phosphine ligands are mixed to obtain mixture I;
[0044] (2) In the presence of syngas, the mixture I is mixed and reacted to obtain a cobalt-phosphine catalyst solution.
[0045] Preferably, the syngas participating in the mixed reaction is the same as the syngas participating in the hydroformylation of multi-branched high-carbon olefins.
[0046] In a preferred embodiment, in step (1), the phosphine ligand is selected from at least one of phosphites, triarylphosphine, trialkylphosphine, and alkylarylphosphine.
[0047] According to a particularly preferred embodiment, the phosphine ligand is trioctylphosphine.
[0048] Preferably, in step (1), the cobalt-containing raw material is selected from at least one of cobalt carbonate, cobalt formate, cobalt acetate, cobalt stearate, cobalt oxide, cobalt metal, cobalt octacarbonyl, and cobalt isooctanoate.
[0049] Preferably, the solvent is selected from toluene, xylene, benzene, methanol, ethanol, and C4-C4 solvents. 10 At least one of the alcohols.
[0050] Preferably, the solvent is isononol.
[0051] In a preferred embodiment, in step (2), the conditions for the mixing reaction include: a temperature of 80-180℃, preferably 100℃-150℃; a pressure of 1MPa-6MPa, preferably 2MPa-4MPa; and a time of 0.5h-24h, preferably 1h-15h, more preferably 3h-10h.
[0052] The present invention will be described in detail below through examples. Unless otherwise specified, the instruments, reagents, and materials involved in the following examples are all conventional instruments, reagents, and materials, which can be obtained through legitimate commercial channels. Unless otherwise stated, all reagents used are commercially available analytical grade products.
[0053] Olefin material: Composed of 44wt% α-triisobutylene, 49wt% β-triisobutylene, and the remainder being other multi-branched olefins with ≥12 carbon atoms, which are common commercial products.
[0054] Cobalt isooctanoate, trioctylphosphine, and isononol are all commercially available products.
[0055] α-Triisobutylene conversion rate: (mass of α-triisobutylene in feed - mass of α-triisobutylene in product) / (mass of α-triisobutylene in feed) × 100%
[0056] The following preparation examples and comparative preparation examples are used to illustrate the preparation of cobalt-phosphine catalyst solutions.
[0057] Preparation Example 1
[0058] (1) Cobalt isooctanoate and trioctylphosphine are dissolved in isononol to obtain mixture I, wherein the amount of cobalt isooctanoate and trioctylphosphine is controlled so that the cobalt content in mixture I is 0.40 wt% and the phosphorus content is 0.24 wt%.
[0059] (2) Replace the air with syngas H2 / CO (molar ratio 2:1), and fill with CO and H2 gas (molar ratio of CO and H2 is 1:2) to a pressure of 3MPa. Under stirring at 400rpm, the mixture I is mixed and reacted at 110℃ for 20h to obtain cobalt-phosphine catalyst solution A1.
[0060] Preparation Example 2
[0061] (1) Cobalt isooctanoate and trioctylphosphine are dissolved in isononol to obtain mixture I, wherein the amount of cobalt isooctanoate and trioctylphosphine is controlled so that the cobalt content in mixture I is 0.78 wt% and the phosphorus content is 0.47 wt%.
[0062] (2) Replace the air with syngas H2 / CO (molar ratio 2:1), and fill with CO and H2 gas (molar ratio of CO and H2 is 1:2) to a pressure of 5MPa. Under stirring at 400rpm, the mixture I is mixed and reacted at 120℃ for 12h to obtain cobalt-phosphine catalyst solution A2.
[0063] Example 1
[0064] Cobalt-phosphine catalyst solution A1 and syngas (CO / H2 molar ratio 1:2) were added to a pretreatment reactor. The pretreatment temperature was 100℃, the pressure was 6MPa, the stirring speed was 600rpm, and the pretreatment time was 1h. The pretreated catalyst solution A1 and olefin material were added to a batch reactor at a mass ratio of 18.9g:150g. Syngas (CO / H2 molar ratio 1:2) was introduced, and a contact reaction was carried out at 180℃, the pressure was 8MPa, the stirring speed was 600rpm, and the reaction time was 12h. Chromatographic analysis of the reaction products showed that the conversion rate of α-triisobutene was 90.7wt%, the products contained 28.8wt% pentamethyl-heptane, 70.2wt% pentamethyl-heptanol, and other products <1wt%.
[0065] Example 2
[0066] Catalyst solution A1 and syngas (CO / H2 molar ratio 1:2) were added to a pretreatment reactor. The pretreatment temperature was 101℃, the pressure was 6MPa, the stirring speed was 600rpm, and the pretreatment time was 1h. The pretreated catalyst solution A1 and olefin feedstock were added to a batch reactor at a mass ratio of 40g:60g. Syngas (CO / H2 molar ratio 1:2) was introduced, and a contact reaction was carried out at 180℃, the pressure was 8MPa, the stirring speed was 600rpm, and the reaction time was 10h. Chromatographic analysis of the reaction products showed that the conversion rate of α-triisobutene was 92.6wt%, and the products contained 35.2wt% pentamethyl-heptane and 63.9wt% pentamethyl-heptanol.
[0067] Example 3 (Continuous tubular reaction)
[0068] A cobalt-phosphine catalyst solution and syngas (CO / H2 molar ratio of 1:2) were added to a pretreatment reactor. The pretreatment reactor was maintained at 100℃ and 8MPa for 1 hour. After pretreatment, the catalyst solution and olefin material were introduced into a tubular reactor at a mass ratio of 15g:38g. Syngas (CO / H2 molar ratio of 1:2) was introduced to carry out a contact reaction at 172℃ and 8MPa for 30 hours. Chromatographic analysis of the reaction products showed that the conversion rate of α-triisobutene was 95.3wt%, and the products contained 29.6wt% pentamethyl-heptane and 67.6wt% C13 alcohol.
[0069] Example 4 (Continuous tubular reaction)
[0070] A cobalt-phosphine catalyst solution and syngas (CO / H2 molar ratio of 1:2) were added to a pretreatment reactor. The pretreatment reactor was heated to 100℃ and the pressure was 8MPa for 1 hour. The pretreated cobalt-phosphine catalyst solution and olefin material were then introduced into a tubular reactor at a mass ratio of 23.7g:60g. Syngas (CO / H2 molar ratio of 1:2) was introduced to carry out a contact reaction at a temperature of 172℃ and a pressure of 8MPa for 19 hours. The reaction products were analyzed by chromatography: α-triisobutene conversion rate was 77.0wt%, pentamethyl-heptane was 37.7wt%, and C13 alcohol was 54.7wt%.
[0071] A comparison between Example 3 and Example 4 shows that using a tubular reactor significantly extends the reaction time to 30 hours, resulting in a better reaction effect.
[0072] Example 5
[0073] This example illustrates the stability test of a continuous tubular reaction.
[0074] A cobalt-phosphine catalyst solution and syngas (CO / H2 molar ratio of 1:2) were added to a pretreatment reactor. The pretreatment reactor temperature was 100℃, the pressure was 8MPa, and the pretreatment time was 0.5 hours. The pretreated cobalt-phosphine catalyst solution and olefin material were introduced into a tubular reactor at a mass ratio of 20.5g:52g. Syngas (CO / H2 molar ratio of 1:2) was introduced to carry out a contact reaction at a reaction temperature of 172℃ and a pressure of 8MPa for 250 hours (without the addition of cobalt and phosphine ligands). The reaction products were analyzed by chromatography: α-triisobutene conversion rate was 90wt%, pentamethyl-heptane was 28.2wt%, and C13 alcohol was 68.5wt%.
[0075] The results above show that the method provided by this invention has a low catalyst-to-oil ratio (the mass ratio of cobalt-phosphine catalyst solution to olefin is only 0.13-0.67), which overcomes the defect of high catalyst-to-oil ratio in traditional hydroformylation reactions and significantly improves the utilization rate of the reactor; moreover, the method of this invention has high hydroformylation activity for triisobutylene with large steric hindrance.
[0076] The preferred embodiments of the invention have been described in detail above; however, the invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in this invention and are all within the protection scope of this invention.
Claims
1. A method for hydroformylation of multi-branched olefins, characterized in that, The method includes: In the presence of a cobalt-phosphine catalyst solution, olefin materials containing triisobutylene and syngas are introduced into the reactor for contact reaction. The mass concentration of cobalt in the cobalt-phosphine catalyst solution is 0.01wt%-2.0wt%, preferably 0.02wt%-1.0wt%. The triisobutylene is α-triisobutylene and β-triisobutylene in a mass ratio of 1:1-2; The mass ratio of the cobalt-phosphine catalyst solution to the olefin material is 0.1-0.8:
1.
2. The method according to claim 1, wherein, The method further includes: pretreating the cobalt-phosphine catalyst solution prior to the contact reaction; The pretreatment method includes: introducing syngas into a preprocessor so that the syngas reacts with the cobalt-phosphine catalyst solution to obtain a pretreated cobalt-phosphine catalyst solution.
3. The method according to claim 2, wherein, The pretreatment conditions include: a temperature of 50℃-200℃, preferably 75℃-150℃, more preferably 90℃-120℃; a pressure of 1MPa-12MPa, preferably 3MPa-10MPa, more preferably 3MPa-6MPa; and a time of 0.1h-10h, preferably 1h-3h.
4. The method according to any one of claims 1-3, wherein, The conditions for the contact reaction include: a temperature of 60℃-250℃, preferably 100℃-220℃, more preferably 150℃-200℃; and a pressure of 1MPa-10MPa, preferably 2MPa-8MPa, more preferably 3MPa-5MPa. Preferably, when the reactor is a batch reactor, the contact reaction time is 1-40 hours, more preferably 3-20 hours, and even more preferably 5-10 hours; Preferably, when the reactor is a tubular reactor, the contact reaction time is 1-50 hours, more preferably 20-40 hours, and even more preferably 25-40 hours.
5. The method according to any one of claims 2-4, wherein, The syngas participating in the contact reaction and the syngas participating in the pretreatment reaction may be the same or different; Preferably, the syngas participating in the contact reaction and the syngas participating in the pretreatment reaction are both mixed gases containing CO and H2; In the mixed gas, the molar ratio of CO to H2 is 4:1 to 1:4; preferably 3:1 to 1:3; more preferably 2:1 to 1:
2.
6. The method according to any one of claims 1-5, wherein, The olefin material is obtained by polymerizing C4 olefins; Preferably, the C4 olefin is at least one of the following: C4 produced by a refinery catalytic cracking unit, C4 produced by cracking to produce ethylene, and C4 produced as a byproduct of methanol-to-olefins production.
7. The method according to any one of claims 1-6, wherein, The reactor is a tubular reactor.
8. The method according to claim 1, wherein, The cobalt-phosphine catalyst solution is a recycled cobalt-phosphine catalyst solution.
9. The method according to any one of claims 1-8, wherein, The method also includes preparing the cobalt-phosphine catalyst solution using the following steps: (1) In the presence of a solvent, cobalt-containing raw materials and phosphine ligands are mixed to obtain mixture I; (2) In the presence of syngas, the mixture I is mixed and reacted to obtain a cobalt-phosphine catalyst solution.
10. The method according to claim 9, wherein, In step (1), the phosphine ligand is selected from at least one of phosphite, triarylphosphine, trialkylphosphine, and alkylarylphosphine.
11. The method according to claim 9 or 10, wherein, In step (1), the cobalt-containing raw material is selected from at least one of cobalt carbonate, cobalt formate, cobalt acetate, cobalt stearate, cobalt oxide, cobalt metal, cobalt octacarbonyl, and cobalt isooctanoate; Preferably, the solvent is selected from toluene, xylene, benzene, methanol, ethanol, and C4-C4 solvents. 10 At least one of the alcohols.
12. The method according to any one of claims 9-11, wherein, In step (2), the conditions for the mixing reaction include: a temperature of 80-180℃, preferably 100℃-150℃; a pressure of 1MPa-6MPa, preferably 2MPa-4MPa; and a time of 0.5h-24h, preferably 1h-15h, more preferably 3h-10h.