Preparation method of catalyst symbiotic system for hydroformylation process
By using monophosphine, bisphosphine and polyphosphine catalyst symbiosis system technology during the hydroformylation process, the problems of unstable and low selectivity of the catalytic system in the prior art are solved, and efficient and environmentally friendly catalyst use is achieved, extending the service life of the catalyst and reducing costs.
Patent Information
- Application Number
- CN202510027192.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-08
- Publication Date
- 2025-04-11
AI Technical Summary
The prior art adopts monophosphine technology in catalytic technology, resulting in unstable catalytic system, large usage, serious waste and loss, which does not meet the requirements of a green circular economy, and the hydroformylation catalyst is not selective, limited conversion rate, and difficult to recycle and apply the catalyst.
Using monophosphine, bisphosphine and polyphosphine catalyst symbiosis system technology, phosphine ligands are added to combine with transition metal catalysts through physical mixing to form active catalytic species, optimize catalytic performance, and improve reaction selectivity and conversion rate.
The stability and efficiency of the catalyst system have been achieved, the selectivity has been increased by 30 times, and the service life has been extended to six to eight years, reducing costs and carbon emissions, and improving reaction efficiency and environmental protection.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of catalyst reaction, in particular to a method for preparing a catalyst symbiotic system for a hydroformylation process. Background Art
[0002] Hydroformylation is an important chemical reaction that involves the reaction of olefins with carbon monoxide and hydrogen in the presence of a catalyst to produce aldehyde compounds with one more carbon atom than the original olefin. This process is also known as carbonyl synthesis or hydroformylation. The aldehydes and their derivatives produced are widely used as plasticizers, fabric additives, surfactants, solvents and fragrances. Catalyst symbionts refer to composite materials composed of two or more different catalytically active components that coexist and interact with each other in space. Compared with single-phase catalysts, symbiotic catalysts have unique properties, such as different diffusion pathways and molecular restrictions, or special crystal pore environments for binding metal active sites. In general, catalyst symbionts are a class of catalytic materials with unique properties and application prospects. With the deepening of research and the advancement of technology, it is believed that catalyst symbionts will show their unique value and application potential in more fields. Hydroformylation is a commonly used method in chemical industry to prepare fatty aldehydes with one more carbon atom than the original olefin. It has become one of the largest homogeneous catalytic reactions in industrial production. Efficient hydroformylation catalysis is of great significance for improving the selectivity and conversion rate of hydroformylation reactions and simplifying the recovery and application process of catalysts.
[0003] This technology is based on the principle that the selectivity and reactivity of the reaction can be greatly improved based on the structural advantages of the novel phosphine ligand. The ligand has two equivalent coordination modes, which greatly enhances its coordination ability. Therefore, in the catalytic reaction system, the balance between different catalytically active species can better move toward species with better selectivity, thereby greatly improving its selectivity in the hydroformylation reaction compared to traditional monodentate and bidentate phosphine ligands. Therefore, the ligand can be efficiently and widely used in the hydroformylation reaction of a series of olefins, while achieving better selectivity and activity than traditional processes.
[0004] However, the existing technology uses monophosphine technology in catalytic technology, which greatly leads to unstable catalytic system, large single-time use amount, and great waste and loss, which does not meet the requirements of the existing green circular economy. The existing technology has problems such as low selectivity of hydroformylation catalyst, limited conversion rate, and difficulty in recycling the catalyst. Therefore, it is urgent to design a method for preparing a catalyst symbiotic system for the hydroformylation process to solve the above problems. Summary of the invention
[0005] The object of the present invention is to provide a method for preparing a catalyst symbiotic system for a hydroformylation process, so as to solve the problems mentioned in the above background technology that the prior art adopts monophosphine technology in catalytic technology, the catalytic system is unstable to a great extent, the single investment amount is large, and the loss is wasted to a great extent, which does not meet the requirements of the existing green circular economy, and the hydroformylation catalyst in the prior art has low selectivity, limited conversion rate, and is difficult to recycle and reuse.
[0006] To achieve the above object, the present invention provides the following technical solutions:
[0007] A method for preparing a catalyst symbiotic system for a hydroformylation process: the technology is a monophosphine, diphosphine and polyphosphine catalyst symbiotic system for a hydroformylation process;
[0008] The monophosphine is usually added to the reaction system by physical mixing, and the monophosphine ligand is combined with the transition metal catalyst to form an active catalytic species. The addition of the diphosphine is also usually done by physical mixing, and attention should be paid to the ratio of the ligand to the metal and the order of addition. The addition of the polyphosphine requires special attention to the ratio of the ligand to the metal catalyst and the reaction conditions to optimize the catalytic performance. The monophosphine, diphosphine and polyphosphine catalysts are added in sequence to adapt to the reaction rate of the hydroformylation process.
[0009] The symbiotic chemical formula of the monophosphine, diphosphine and polyphosphine catalysts is as follows:
[0010]
[0011] Preferably, the selectivity and reactivity of the phosphine ligand used are higher than those of conventional monophosphine and diphosphine ligands, wherein the selectivity is thirty times higher than that of conventional monophosphine ligands.
[0012] Preferably, the new phosphine ligand is used in a small amount. Compared with the traditional PPh3, which is added in three times the equivalent relative to the metal, the new phosphine ligand only needs to be added in three times or less the equivalent relative to the metal.
[0013] Preferably, the monophosphine can precisely adjust the electronic and spatial properties of the ligand by changing the substituent at the phosphorus center, the diphosphine can respectively realize the dearyl monoalkylation or dialkylation of DPPP by changing the stoichiometry of the alkylating agent, and the polyphosphine can generate multi-dentate mixed functional group ligands by introducing heteroatoms such as nitrogen, oxygen or sulfur. The polyphosphine can achieve a more efficient and environmentally friendly chemical reaction process by finely regulating the electronic and spatial properties of these ligands.
[0014] Preferably, the method can realize the direct conversion of mixed olefins into aldehydes in one step, and further realize the production of novel butanol.
[0015] Preferably, under the action of the co-catalyst of monophosphine, diphosphine and polyphosphine catalyst, olefin reacts with carbon monoxide and hydrogen to generate aldehyde having one more carbon atom than the original one, and the efficiency of the reaction is increased exponentially.
[0016] Preferably, the catalyst system consists of:
[0017] Monophosphine catalyst: A compound with a single phosphine group;
[0018] Bisphosphine catalyst: a compound with two phosphine groups;
[0019] Polyphosphine catalyst: A compound having multiple phosphine groups.
[0020] Preferably, the synthesis of the catalyst is:
[0021] Monophosphine catalyst: prepared by common organic synthesis methods;
[0022] Bisphosphine catalysts: prepared by specific synthetic routes;
[0023] Polyphosphine catalysts: synthesized by gradually introducing phosphine groups, or by multi-step reactions to prepare compounds with multiple phosphine groups.
[0024] Preferably, the porous structure of the monophosphine catalyst in the hydroformylation process ensures that the Rh active species exists in the monophosphine porous polymer in the form of single-atom dispersion;
[0025] The diphosphine catalyst in the hydroformylation process participates in multiple catalytic cycle steps and can be used in combination with the designed and synthesized monophosphine porous polymer encapsulated single-atom Rh catalyst to make up for the lack of regional selectivity of the monophosphine catalyst;
[0026] The polyphosphine catalyst of the hydroformylation process is based on its ability to provide multiple coordination sites, thereby enhancing the binding force with the metal center and compensating for the poor metal binding force of the monophosphine catalyst and the diphosphine catalyst;
[0027] The monophosphine, diphosphine and polyphosphine catalyst symbiotic system meets different requirements for catalytic reaction activity and selectivity.
[0028] Compared with the prior art, the present invention has the following beneficial effects:
[0029] The method for preparing a catalyst symbiotic system for a hydroformylation process solves the problem of existing catalyst investment losses at low cost through the technology of the monophosphine, diphosphine and polyphosphine catalyst symbiotic system for the hydroformylation process, reduces the use cost, environmental carbon emission cost, safety risk and other issues. The invented technology of the monophosphine, diphosphine and polyphosphine catalyst symbiotic system fully meets the existing conditions. The technical innovation of the hydroformylation reaction based on high-efficiency and high-selectivity phosphine ligands is that the developed catalyst is a phosphine ligand, breaking the traditional single system of monophosphine, diphosphine and the recently developed tetraphosphine ligand. The selectivity and reactivity of the phosphine ligand used in the technology are higher than those of the traditional monophosphine and diphosphine ligands, wherein the selectivity is thirty times higher than that of the traditional monophosphine ligand, reflecting the practicality of the equipment design.
[0030] The method for preparing a catalyst symbiotic system for a hydroformylation process realizes the stability of the catalyst system through the technology of the symbiotic system of monophosphine, diphosphine and polyphosphine catalysts for the hydroformylation process. The service life of the traditional technology is about three years, while the catalyst of the symbiotic system can be used for six to eight years, which greatly saves the cycle investment cost. The invented technology of the symbiotic system of monophosphine, diphosphine and polyphosphine catalysts fully meets the existing conditions. The technical innovation of the hydroformylation reaction based on high-efficiency and high-selectivity phosphine ligands is as follows: the amount of new phosphine ligand used in this technology is small. Compared with the traditional PPh3 (3 times the equivalent added relative to the metal), the new phosphine ligand only needs to be added at 3 times or less the equivalent relative to the metal, which can realize the direct conversion of mixed olefins into aldehydes in one step, and further realize the production of butyl octanol, which reflects the comprehensiveness of the equipment design. DETAILED DESCRIPTION
[0031] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0032] The present invention relates to a symbiotic system technology of monophosphine, diphosphine and polyphosphine catalysts for hydroformylation process; the monophosphine is usually added to the reaction system by physical mixing, and the monophosphine ligand is combined with the transition metal catalyst to form an active catalytic species; the addition of the diphosphine is usually also by physical mixing, and attention should be paid to the ratio of the ligand to the metal and the order of addition; the addition of the polyphosphine requires special attention to the ratio of the ligand to the metal catalyst and the reaction conditions to optimize the catalytic performance; the monophosphine, diphosphine and polyphosphine catalysts are added in sequence to adapt to the reaction rate of the hydroformylation process; the selectivity of the phosphine ligand used is The new phosphine ligand has higher reactivity than traditional monophosphine and diphosphine ligands, wherein the selectivity is thirty times higher than that of traditional monophosphine ligands, and the new phosphine ligand is used in small amounts. Compared with traditional PPh3, three times the equivalent of metal is added, while the new phosphine ligand only needs to be added in three times or less equivalents relative to the metal. The monophosphine can accurately adjust the electronic and spatial properties of the ligand by changing the substituent of the phosphorus center, and the diphosphine can respectively realize the dearyl monoalkylation or dialkylation of DPPP by changing the stoichiometry of the alkylating agent. The polydentate mixed functional group ligand is generated by introducing heteroatoms such as nitrogen, oxygen or sulfur. The polyphosphine can achieve a more efficient and environmentally friendly chemical reaction process by finely regulating the electronic and spatial properties of these ligands.
[0033] The monophosphine ligand, diphosphine, and polyphosphine have different corresponding conversion rates, selectivities, and amounts of transition metal used under different formula ratios. The mixed olefins can be directly converted into aldehydes in one step, and the production of new butyl octanol can be further realized. Under the action of the co-catalyst of the monophosphine, diphosphine, and polyphosphine catalysts, the olefins react with carbon monoxide and hydrogen to generate aldehydes with one more carbon atom than the original ones, and the reaction efficiency is doubled.
[0034] Catalyst system composition:
[0035] Monophosphine catalyst: A compound with a single phosphine group;
[0036] Bisphosphine catalyst: a compound with two phosphine groups;
[0037] Polyphosphine catalyst: A compound having multiple phosphine groups.
[0038] Catalyst synthesis:
[0039] Monophosphine catalyst: prepared by common organic synthesis methods;
[0040] Bisphosphine catalysts: prepared by specific synthetic routes;
[0041] Polyphosphine catalysts: synthesized by gradually introducing phosphine groups, or by multi-step reactions to prepare compounds with multiple phosphine groups.
[0042] The porous structure of the monophosphine catalyst in the hydroformylation process ensures that the Rh active species exists in the monophosphine porous polymer in the form of single-atom dispersion;
[0043] The diphosphine catalyst in the hydroformylation process participates in multiple catalytic cycle steps and can be used in combination with the designed and synthesized monophosphine porous polymer encapsulated single-atom Rh catalyst to make up for the lack of regional selectivity of the monophosphine catalyst;
[0044] The polyphosphine catalyst in the hydroformylation process can provide multiple coordination sites, thereby enhancing the binding force with the metal center and compensating for the poor metal binding force of the monophosphine catalyst and the diphosphine catalyst.
[0045] The monophosphine, diphosphine and polyphosphine catalyst symbiosis system meets different requirements for catalytic reaction activity and selectivity.
[0046] The symbiotic chemical formula of the monophosphine, diphosphine and polyphosphine catalysts is as follows:
[0047]
[0048] The following are multiple groups of embodiments provided by the present invention:
[0049] An embodiment provided by the present invention:
[0050] A method for preparing a catalyst symbiotic system for a hydroformylation process includes scheme 1: component A accounts for 11%, component B accounts for 1%, and component C accounts for 1%, the required amount of transition metal is 350ppm, the reaction temperature is 85-100 degrees Celsius, the pressure is 1.3-2.2mpa, the conversion rate is 95.2%, and the normal-iso ratio is 15:1.
[0051] An embodiment provided by the present invention:
[0052] A method for preparing a catalyst symbiotic system for a hydroformylation process, scheme 2: component A accounts for 10%, component B accounts for 1.5%, component C accounts for 1.5%, the required amount of transition metal is 320ppm, the reaction temperature is 85-100 degrees Celsius, the pressure is 1.3-2.2mpa, the conversion rate is 95.8%, the normal-iso ratio is 14.5:1; the constant ventilation time is 72 hours, and the activity test is 55.
[0053] An embodiment provided by the present invention:
[0054] A method for preparing a catalyst symbiotic system for a hydroformylation process, scheme 3: component A accounts for 9%, component B accounts for 2%, component C accounts for 2%, the required amount of transition metal is 300ppm, the reaction temperature is 85-100 degrees Celsius, the pressure is 1.3-2.2mpa, the conversion rate is 96.4%, the normal-iso ratio is 14.2:1; the constant ventilation time is 72 hours, and the activity test is 56.
[0055] An embodiment provided by the present invention:
[0056] A method for preparing a catalyst symbiotic system for a hydroformylation process, scheme 4: component A accounts for 9%, component B accounts for 2%, component C accounts for 2%, the required amount of transition metal is 300ppm, the reaction temperature is 85-95 degrees Celsius, the pressure is 1.3-2.2mpa, the conversion rate is 96.4%, the normal-iso ratio is 13:1; the constant ventilation time is 72 hours, and the activity test is 58.
[0057] An embodiment provided by the present invention:
[0058] A method for preparing a catalyst symbiotic system for a hydroformylation process, 5: component A accounts for 8%, component B accounts for 3%, component C accounts for 3%, the required amount of transition metal is 260ppm, the reaction temperature is 85-90 degrees Celsius, the pressure is 1.3-2.2mpa, the conversion rate is 97.1%, the normal-iso ratio is 12.5:1; the constant ventilation time is 72 hours, and the activity test is 59.
[0059] An embodiment provided by the present invention:
[0060] A method for preparing a catalyst symbiotic system for a hydroformylation process, scheme 6: component A accounts for 7%, component B accounts for 3.5%, and component C accounts for 3.5%. The required amount of transition metal is 240ppm, the reaction temperature is 80-90 degrees Celsius, the pressure is 1.3-2.2mpa, the conversion rate is 97.8%, and the normal-iso ratio is 10:1; the constant ventilation time is 72 hours, and the activity test is 61.
[0061] An embodiment provided by the present invention:
[0062] A method for preparing a catalyst symbiotic system for a hydroformylation process, scheme 7: component A accounts for 6%, component B accounts for 4%, component C accounts for 4%, the required amount of transition metal is 210ppm, the reaction temperature is 80-85 degrees Celsius, the pressure is 1.3-2.2mpa, the conversion rate is 98%, the normal-iso ratio is 8.5:1; the constant ventilation time is 72 hours, and the activity test is 62.
[0063] An embodiment provided by the present invention:
[0064] A method for preparing a catalyst symbiotic system for a hydroformylation process, scheme 8: component A accounts for 5%, component B accounts for 5%, component C accounts for 4%, the required amount of transition metal is 180ppm, the reaction temperature is 75-85 degrees Celsius, the pressure is 1.3-2.2mpa, the conversion rate is 98.4%, the normal-iso ratio is 7:1; the constant ventilation time is 72 hours, and the activity test is 63.
[0065] An embodiment provided by the present invention:
[0066] A method for preparing a catalyst symbiotic system for a hydroformylation process, scheme 9: component A accounts for 4%, component B accounts for 6%, and component C accounts for 4%. The required amount of transition metal is 150ppm, the reaction temperature is 75-80 degrees Celsius, the pressure is 1.3-2.2mpa, the conversion rate is 98.9%, and the normal-iso ratio is 6.5:1; the constant ventilation time is 72 hours, and the activity test is 65.
[0067] An embodiment provided by the present invention:
[0068] A method for preparing a catalyst symbiotic system for a hydroformylation process, scheme 10: component A accounts for 3%, component B accounts for 6%, and component C accounts for 4.5%. The required amount of transition metal is 100 ppm, the reaction temperature is 73-78 degrees Celsius, the pressure is 1.3-2.2 MPa, the conversion rate is 99.2%, and the normal-iso ratio is 5:1; the constant ventilation time is 72 hours, and the activity test is 68.
[0069] A monophosphine, diphosphine and polyphosphine catalyst symbiotic system technology for a hydroformylation process, the implementation of the original plan or the implementation plan that does not adopt the patent plan, the patent of the present invention is a monophosphine, diphosphine and polyphosphine catalyst symbiotic system technology for a hydroformylation process, when C is greater than 4.5%, the viscosity of the fluid is large, which affects the normal work of the dynamic equipment. With the increase of diphosphine and polyphosphine in the reaction system, the use of transition metals can be significantly reduced, the reflected temperature liquid is better, the conversion rate is higher, and the side reactions are less; it has good economic benefits in terms of operating economy.
[0070] Working principle: In actual use, the monophosphine, diphosphine and polyphosphine catalyst symbiosis system technology used in the hydroformylation process can solve the existing catalyst investment loss problem at low cost, reduce the use cost, environmental carbon emission cost, safety risk and other issues. The invented monophosphine, diphosphine and polyphosphine catalyst symbiosis system technology fully meets the existing conditions and is based on the hydroformylation reaction technology of high-efficiency and high-selectivity phosphine ligands. Innovation point: The developed catalyst is a phosphine ligand, breaking the traditional single system of monophosphine, diphosphine and the recently developed tetraphosphine ligand. The selectivity and reactivity of the phosphine ligand used in this technology are higher than those of the traditional monophosphine and diphosphine ligands, and the selectivity is thirty times higher than that of the traditional monophosphine ligand ( The ratio of PPh3 ligand to iso-ratio is 7-10:1, and the ratio of new phosphine ligand system is 5-15:1), which realizes the stability of the catalyst system. The service life of traditional technology is about three years, while the catalyst of the symbiotic system can be used for six to eight years, which greatly saves the cycle investment cost. The invented monophosphine, diphosphine and polyphosphine catalyst symbiotic system technology fully meets the existing conditions. The technical innovation point of the hydroformylation reaction based on high-efficiency and high-selectivity phosphine ligand is: the amount of new phosphine ligand used in this technology is small. Compared with the traditional PPh3 (3 times the equivalent added relative to the metal), the new phosphine ligand only needs to be added at 3 times or less the equivalent relative to the metal, which can realize the direct conversion of mixed olefins to aldehydes in one step, and further realize the production of butyl octanol.
[0071] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.
Claims
1. A method for preparing a catalyst symbiotic system for a hydroformylation process, characterized in that: The present invention relates to a monophosphine, diphosphine and polyphosphine catalyst symbiotic system technology for hydroformylation process; The monophosphine is usually added to the reaction system by physical mixing, and the monophosphine ligand is combined with the transition metal catalyst to form an active catalytic species. The diphosphine is added by physical mixing and attention is paid to the ratio of the ligand to the metal and the order of addition. The addition of the polyphosphine needs to pay attention to the ratio of the ligand to the metal catalyst and the reaction conditions to optimize the catalytic performance. The monophosphine, diphosphine and polyphosphine catalysts are added in sequence to adapt to the reaction rate of the hydroformylation process; The symbiotic chemical formula of the monophosphine, diphosphine and polyphosphine catalysts is as follows:
2. The method for preparing a catalyst symbiotic system for a hydroformylation process according to claim 1, characterized in that: The selectivity and reactivity of the phosphine ligand are higher than those of the conventional monophosphine and diphosphine ligands, wherein the selectivity is thirty times higher than that of the conventional monophosphine ligand.
3. The method for preparing a catalyst symbiotic system for a hydroformylation process according to claim 1, characterized in that: The new phosphine ligand is used in small amounts. Compared with the traditional PPh3, which requires three times the amount of metal, the new phosphine ligand only needs to be added in three times or less equivalents relative to the metal.
4. The method for preparing a catalyst symbiotic system for a hydroformylation process according to claim 1, characterized in that: The monophosphine can precisely adjust the electronic and spatial properties of the ligand by changing the substituent at the phosphorus center, the diphosphine can respectively achieve the dearyl monoalkylation or dialkylation of DPPP by changing the stoichiometry of the alkylating agent, and the polyphosphine can generate multi-dentate mixed functional group ligands by introducing heteroatoms such as nitrogen, oxygen or sulfur. The polyphosphine can finely control the electronic and spatial properties of these ligands.
5. The method for preparing a catalyst symbiotic system for a hydroformylation process according to claim 1, characterized in that: The mixed olefins are converted directly to aldehydes in one step.
6. The method for preparing a catalyst symbiotic system for a hydroformylation process according to claim 5, characterized in that: Under the action of the co-catalyst of monophosphine, diphosphine and polyphosphine catalyst, olefin reacts with carbon monoxide and hydrogen to generate aldehyde having one more carbon atom than the original one.
7. The method for preparing a catalyst symbiotic system for a hydroformylation process according to claim 1, characterized in that: Catalyst system composition: Monophosphine catalyst: A compound with a single phosphine group; Bisphosphine catalyst: a compound with two phosphine groups; Polyphosphine catalyst: A compound having multiple phosphine groups.
8. The method for preparing a catalyst symbiotic system for a hydroformylation process according to claim 1, characterized in that: Catalyst synthesis: Monophosphine catalyst: prepared by common organic synthesis methods; Bisphosphine catalysts: prepared by specific synthetic routes; Polyphosphine catalysts: synthesized by gradually introducing phosphine groups, or by multi-step reactions to prepare compounds with multiple phosphine groups.
9. The method for preparing a catalyst symbiotic system for a hydroformylation process according to claim 1, characterized in that: The porous structure of the monophosphine catalyst in the hydroformylation process ensures that the Rh active species exists in the monophosphine porous polymer in the form of single-atom dispersion; The diphosphine catalyst in the hydroformylation process participates in multiple catalytic cycle steps and can be used in combination with the designed and synthesized monophosphine porous polymer encapsulated single-atom Rh catalyst to make up for the lack of regional selectivity of the monophosphine catalyst; The polyphosphine catalyst in the hydroformylation process can provide multiple coordination sites to compensate for the poor metal binding of monophosphine catalysts and diphosphine catalysts; The monophosphine, diphosphine and polyphosphine catalyst symbiotic system has catalytic reaction activity.