阅读说明：本技术 烯烃氢甲酰化反应的Co基多相催化剂及制备和应用 (Co-based multi-phase catalyst for olefin hydroformylation reaction, preparation and application thereof ) 是由 姜淼 丁云杰 严丽 王国庆 程显波 金明 于 2020-05-26 设计创作，主要内容包括：本发明涉及一种Co基多相催化剂制备方法及其应用,更具体地,涉及一种应用于高碳烯烃氢甲酰化反应的Co基多相催化剂,其由金属组分和有机膦配体聚合物组成,所述金属组分是金属Co,所述有机膦配体聚合物是含有乙烯基的有机膦配体经溶剂热聚合生成具有大比表面积和多级孔道结构的聚合物。本发明催化剂在高碳烯烃氢甲酰化反应中,反应活性和产物醛选择性优异,反应稳定性良好。采用新型Co基多相催化剂,降低了催化剂同反应物和产物的分离成本,适应于大规模工业化生产；同时选用非贵金属Co作为催化剂金属活性组分,有效提高了氢甲酰化反应过程的经济性。(The invention relates to a preparation method and application of a Co-based multi-phase catalyst, in particular to a Co-based multi-phase catalyst applied to hydroformylation of high-carbon olefin, which consists of a metal component and an organic phosphine ligand polymer, wherein the metal component is metal Co, and the organic phosphine ligand polymer is a polymer which is generated by carrying out solvent thermal polymerization on an organic phosphine ligand containing vinyl and has a large specific surface area and a multi-stage pore channel structure. The catalyst of the invention has excellent reaction activity and product aldehyde selectivity and good reaction stability in the hydroformylation reaction of high-carbon olefin. The novel Co-based multi-phase catalyst is adopted, so that the separation cost of the catalyst, reactants and products is reduced, and the method is suitable for large-scale industrial production; meanwhile, non-noble metal Co is selected as the active metal component of the catalyst, so that the economy of the hydroformylation reaction process is effectively improved.)

1. A Co-based multi-phase catalyst for olefin hydroformylation reaction, which is characterized by consisting of a metal component and an organic phosphine ligand polymer; the metal component is metal Co, and the organic phosphine ligand polymer is a polymer generated by the thermal polymerization of an organic phosphine ligand containing a vinyl group through a solvent.

2. The catalyst according to claim 1, wherein the metal component Co represents 0.5% to 50.0% (preferably 1.0% to 20.0%, more preferably 8.0% to 16.0%) of the total weight of the solid heterogeneous catalyst.

3. The catalyst of claim 1, wherein the organophosphine ligand polymer is a polymer produced by the thermal polymerization of a vinyl-containing organophosphine ligand in a solvent, wherein the vinyl-containing organophosphine ligand is selected from one or more of the group consisting of:

4. a catalyst according to claim 1 or 3, wherein the phosphine ligands are selected from two or more of the items described in claim 3 above; preferably, phosphine ligands L1, L5 and L12 are specifically selected, and the corresponding mass ratio of the three is 1:0.2: 0.1.

5. The catalyst as claimed in claim 1 or 3, wherein the specific surface area of the organophosphine ligand polymer is 3000 m-100²Per g, pore volume of 0.1-5.0cm³(ii)/g, the pore size distribution is 0.1-200.0 nm.

6. A process for preparing the solid heterogeneous catalyst of any of claims 1-5, the process comprising:

a) adding a free radical initiator into a phosphine ligand solvent containing vinyl functional groups under the protection atmosphere of 273-473K (preferably 293-423K) and Ar gas, and stirring for 0.5-50h (preferably 1-20 h);

b) standing the solution obtained in the step a) in a hydrothermal autoclave for 0.5-100h (preferably 5-50h) under the protection atmosphere of 273-473K (preferably 323-423K) and Ar gas to perform the solvent thermal polymerization reaction;

c) after the step b) is finished, removing the solvent under vacuum condition to obtain the organic phosphine ligand polymer;

d) the organic phosphine ligand polymer is placed in a solvent containing a metal active component Co, stirred for 0.5-100h (preferably 5-50h) under the protection atmosphere of 273-473K (preferably 293-423K) and Ar gas, and the solvent is removed, so that the Co-based heterogeneous hydroformylation catalyst with the metal active component loaded by the organic phosphine ligand polymer is obtained.

7. The method according to claim 6, wherein the solvent used in steps a) and d) is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane, dichloroethane or deionized water;

the free radical initiator used in the step a) is one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile; the weight ratio of the free radical initiator to the organophosphine ligand monomer is from 1:500 to 1:5 (preferably from 1:400 to 1: 10).

8. The method of claim 6, wherein the metallic component Co precursor of step d) is derived from Co (NO)₃)₂、CoCl₂、Co(OAc)₂、Co(acac)₂And Co (acac)₃One or more of them.

9. Use of a Co-based heterogeneous catalyst according to any one of claims 1 to 5 in the hydroformylation of higher olefins.

10. Use of a Co-based multi-phase catalyst according to claim 9 for hydroformylation of higher olefins, wherein higher olefins (olefins with carbon number 4 or more) are reacted with CO/H in the presence of the Co-based multi-phase catalyst₂The mixed gas is used for carrying out the hydroformylation reaction in a trickle bed reactor, a slurry bed reactor or a kettle type reactor, wherein the reaction temperature is 293-^-1(preferably 0.05-8.0 h)^-1) The gas space velocity is 100-^-1(preferably 500-10000 h)^-1)。

Technical Field

The invention relates to a preparation method and application of a Co-based multiphase catalyst for hydroformylation of high-carbon olefins, belonging to the technical field of heterogeneous catalysis.

Background

Hydroformylation, which is a reaction of an olefin with synthesis gas to form aldehydes having one more carbon than the starting olefin, is one of the most important industrial homogeneous catalytic reactions. Hydroformylation is a typical atom-economical reaction, and catalytic processes and catalysts thereof have been studied for nearly 60 years. Currently, approximately over 1200 million tons of aldehydes and alcohols are produced worldwide each year using olefin hydroformylation technology. The reaction can generate aldehyde from raw olefin under less harsh conditions, and the product aldehyde can be further hydrogenated and converted into alcohol. The homogeneous catalysis system has higher catalytic activity and selectivity of target products under mild reaction conditions, but the separation problem of the catalyst and reaction materials is difficult, thus hindering large-scale industrial application of the homogeneous catalysis system. Compared with homogeneous catalysis, heterogeneous catalysis has the greatest advantages that the catalyst and reaction materials are easy to separate, and the main problems of the heterogeneous catalysis are harsh reaction conditions, relatively low reaction activity and the like. At present, the main research focus on hydroformylation is on developing a novel heterogeneous catalyst, which not only has the advantage of easy separation of heterogeneous catalytic catalyst and reaction materials, but also has high reaction activity and mild reaction conditions of homogeneous catalysis.

Rh is a typical noble metal, is scarce in resources and expensive, seriously influences the economy of hydroformylation reaction, and has important practical significance if non-noble metals can be adopted to replace the noble metal Rh for the multiphase hydroformylation reaction. Currently, the only catalysts for hydroformylation are Rh and Co, which are really used in industrial scale production. The outer electronic structures of the metals Rh and Co both have d electronic orbitals, and when the metals Rh and Co act with ligands containing lone-pair electrons, the d electronic orbitals become central atoms or ions of the complexes to generate empty valence electronic orbitals, so that the d electronic orbitals have catalytic action on hydroformylation of olefins. Rh is the most active element in hydroformylation reactions, and Co has relatively low activity, but still has great industrial value. Because the economical efficiency of the process is seriously influenced by the scarcity of resources and high price of the noble metal Rh, the application of the noble metal Co instead of the metal Rh as an active component of the catalyst to the high-carbon olefin heterogeneous hydroformylation reaction is considered.

CN102281948A reports a polymer supported transition metal catalyst complex and method of use, producing a soluble polymer supported Rh catalyst with a narrower molecular weight distribution. However, the catalyst preparation, catalytic reaction and catalyst separation processes are complicated. The preparation of the catalyst requires that a functional monomer, styrene and the like are controlled to synthesize a soluble polymer, then a ligand is introduced, and finally the Rh catalyst is loaded. Compressed gas is required to be added in the catalytic reaction process. The catalyst is separated from the reaction mixture by adopting a nanofiltration mode, and the reaction result is not ideal.

Balue et al (J.mol.Catal.A., Chem,1999,137:193-203) use cation exchange resin as a carrier to form a heterogeneous catalyst by immobilizing rhodium sulfur compounds, and the cycle experiment of styrene hydroformylation shows that the heterogeneous catalyst has poor stability and the phenomenon of Rh loss is serious. Zeelie et al (appl.Catal.A: Gen, 2005,285:96-109) modified styrene and p-styrene diphenylphosphine on polyethylene fibers, Rh (acac) (CO)₂The catalyst is anchored on a modified polyethylene fiber, and the ethylene hydroformylation result shows that the catalyst has higher conversion rate but poor stability under the conditions of 100 ℃ and 5bar, the reaction activity is sharply reduced after 50 hours of reaction, and the catalyst deactivation phenomenon is serious.

Ricken et al (J.mol.Catal.A: Chem,2006,257:78-88) subject the ligand NIXANTPHOS to various functional modifications, the modified ligand and Rh (acac) (CO)₂The catalyst is loaded on a polyglycerol polymer, and the experiment of hydroformylation of 1-octene shows that the conversion rate of the catalyst can reach about 90% under the conditions of 80 ℃ and 20 bar. However, polymer carriers purchased commercially or prepared by conventional free radical polymerization of styrene are subject to gel formation, polymerizationThe problems of swelling, limited loading of phosphorus ligands in the polymer backbone, and loss of catalytically active components have severely limited the commercial use of such catalysts.

Sudheesh et al (Journal of Molecular Catalysis A: Chemical, 2008, 296: 61-70) HRh (CO) (PPh)₃)₃The catalyst is encapsulated in the HMS mesoporous molecular sieve in situ and is applied to hydroformylation of long-chain olefin. The authors focus on the reaction of 1-hexene in a slurry bed, and discuss the effects of temperature, carbon monoxide partial pressure, hydrogen partial pressure, catalyst amount and the like on the reaction activity, and the catalyst recycling experiment shows that the catalyst has good reusability. Subsequently, N.Sudheesh et al (Applied Catalysis A: General,2012,415-₃)₃The catalytic system in situ encapsulated in the HMS mesoporous molecular sieve is applied to hydroformylation of propylene, and the HMS mesoporous molecular sieve is used as a nanoscale reactor, shows higher stability in a recycling experiment, but has larger difference in reaction activity compared with a homogeneous catalytic system.

Ki-Chang Song et al (Catalysis Today,2011,164:561-₄(CO)₁₂Reacting with amino group modified on inner surface to obtain Rh₄(CO)₁₂Immobilized on SBA-15. Another method is to directly modify the surface of SBA-15 with N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane through Rh₄(CO)₁₂Reacting with amino modified on the inner and outer surfaces of the molecular sieve to Rh₄(CO)₁₂Immobilized on SBA-15. Researches show that the immobilized catalyst formed by the second treatment method has better activity and stability in hydroformylation reaction, and authors explain that the reason for better catalyst activity is that the internal and external surfaces are simultaneously modified to enable Rh to be added₄(CO)₁₂More uniformly distributed inside and outside the molecular sieveThe surface, thereby the homogeneous catalyst has larger free space. The authors have shown that the higher n/i values of heterogeneous catalysts are due to steric hindrance of the ligands, favoring the formation of linear aldehydes.

US4252678 discloses the preparation of a colloidal dispersion containing a transition metal such as Rh, wherein the transition metal component is present in the form of a 1.0 to 20.0 nm colloidal dispersion in combination with a catalyst system comprising a hydroxy terminated (styrene/butadiene) functionalized copolymer and applied to the hydroformylation of 1-octene. The catalyst prepared by the method cannot be applied to fixed bed and trickle bed reactors, and the catalyst and the product are difficult to separate.

In summary, the general idea of the above-mentioned studies on homogeneous heterogenization is to make organic functional groups interact with a homogeneous catalyst, so as to make the homogeneous catalyst immobilized on a heterogeneous carrier, and the biggest problems of these methods are the loss of the homogeneous catalyst and the reduction of the activity of the homogeneous catalyst immobilized on the carrier, which are the biggest bottlenecks restricting the homogeneous immobilization of hydroformylation. On the other hand, the existing researches are mainly conducted on Rh-based hydroformylation systems, and Rh is a typical precious metal, so that the resources are scarce and the price is high, and the economical efficiency of the hydroformylation reaction process is seriously influenced. Therefore, the development of Co-based heterogeneous hydroformylation reaction system has important practical application significance.

Disclosure of Invention

In order to solve the problems, the invention aims to provide a Co-based multi-phase catalyst for hydroformylation of high-carbon olefins, which can reduce the separation cost of the catalyst, reactants and products and is suitable for large-scale industrial production; meanwhile, non-noble metal Co is selected as the active metal component of the catalyst, so that the economy of the hydroformylation reaction process is effectively improved.

Therefore, the invention provides a Co-based multiphase catalyst for hydroformylation of high-carbon olefins, which is characterized by consisting of a metal component and an organic phosphine ligand polymer. The metal component is metal Co, and the organic phosphine ligand polymer is a polymer which is generated by carrying out solvent thermal polymerization on an organic phosphine ligand containing a vinyl group and has a large specific surface area and a hierarchical pore structure.

In a preferred embodiment, the metal component Co comprises from 0.5% to 50.0% (preferably from 1% to 20.0%) by weight of the total solid heterogeneous catalyst.

In a preferred embodiment, the metal component Co precursor is derived from Co (NO)₃)₂、CoCl₂、Co(OAc)₂、Co(acac)₂And Co (acac)₃One or more of them.

In a preferred embodiment, the organophosphine ligand polymer is a polymer produced by the thermal polymerization of a vinyl-containing organophosphine ligand in a solvent, wherein the vinyl-containing organophosphine ligand is selected from one or more of the group consisting of:

in a preferred embodiment, the phosphine ligand is selected from two or more of the above, specifically selected from phosphine ligands L1, L5 and L12, in a corresponding mass ratio of 1:0.2: 0.1.

In a preferred embodiment, the specific surface area of the organic ligand polymer is 100-3000m²Per g, pore volume of 0.1-5.0cm³(ii)/g, the pore size distribution is 0.1-200.0 nm.

In a preferred embodiment, the method for preparing the Co-based heterogeneous catalyst comprises: a) adding a free radical initiator into a phosphine ligand solvent containing vinyl functional groups under the protection atmosphere of 273-473K (preferably 293-423K) and Ar gas, and stirring for 0.5-50h (preferably 1-20 h); b) standing the solution obtained in the step a) in a hydrothermal autoclave for 0.5-100h (preferably 5-50h) under the protection atmosphere of 273-473K (preferably 323-423K) and Ar gas to perform the solvent thermal polymerization reaction; c) after the step b) is finished, removing the solvent under vacuum condition to obtain the organic phosphine ligand polymer; d) the organic phosphine ligand polymer is placed in a solvent containing a metal active component Co, stirred for 0.5-100h (preferably 5-50h) under the protection atmosphere of 273-473K (preferably 293-423K) and Ar gas, and then the solvent is pumped out under vacuum condition, thus obtaining the Co-based heterogeneous hydroformylation catalyst with the metal active component loaded by the organic phosphine ligand polymer.

In a preferred embodiment, the solvent used in steps a) and d) of the above catalyst preparation method is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane, dichloroethane or deionized water; the free radical initiator used in the step a) is one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile; the weight ratio of the free radical initiator to the organophosphine ligand monomer is from 1:500 to 1:5 (preferably from 1:400 to 1: 10).

In a preferred embodiment, the above-mentioned Co-based multi-phase catalyst is used for hydroformylation of high carbon olefins by reacting high carbon olefins (olefins having 4 or more carbon atoms) with CO/H in the presence of the Co-based multi-phase catalyst₂The mixed gas is used for carrying out the hydroformylation reaction in a trickle bed reactor, a slurry bed reactor or a kettle type reactor, wherein the reaction temperature is 293-^-1(preferably 0.05-8.0 h)^-1) The gas space velocity is 100-^-1(preferably 500-10000 h)^-1)。

The benefits of the present invention include, but are not limited to, the following: compared with the existing hydroformylation reaction technology applied in industry, the novel Co-based multiphase catalyst is adopted, so that the separation cost of the catalyst, reactants and products is reduced, and the method is suitable for large-scale industrial production; meanwhile, non-noble metal Co is selected as the active metal component of the catalyst, so that the economy of the hydroformylation reaction process is effectively improved. The catalyst of the invention has excellent reaction activity and product aldehyde selectivity and good reaction stability in the hydroformylation reaction of high-carbon olefin.

Detailed Description

In order to better illustrate the preparation method of the Co-based multi-phase catalyst and the application thereof in the hydroformylation of high carbon olefins, the following examples of the preparation of catalyst samples and the application thereof in the reaction process are given, but the invention is not limited to the examples. Unless otherwise specifically stated, the contents and percentages in the present application are calculated as "mass".

Example 1

7.69g of tris (4-vinylbenzene) phenylphosphine, 1.54g of bis (3-vinylbenzene) phenylphosphine and 0.77g of a pyrrole bidentate phosphine ligand containing a vinyl group were dissolved in 100ml of a tetrahydrofuran solvent under an atmosphere of 298K and Ar gas, and 0.25g of azobisisobutyronitrile, a radical initiator, was added to the above solution and stirred for 0.5 h. And transferring the stirred solution into a hydrothermal autoclave, and carrying out solvothermal polymerization for 24h under the protection of 373K and Ar gas. Cooling to room temperature after the polymerization, and removing the solvent in vacuum at 338K to obtain the organic phosphine ligand polymer (the specific surface area of which is 950 m)²G, pore volume of 1.26cm³(ii)/g, pore size distribution is 0.2-80.0 nm). Under the protection of 298K and Ar gas, 1.68g of cobalt acetate is weighed and dissolved in 100ml of ethanol solvent, 5.0g of the organic phosphine ligand polymer prepared above is added, and stirring is carried out for 24 hours. Subsequently, the solvent was evacuated under 338K conditions, i.e., a Co-based multi-phase catalyst with metal components supported by the phosphine ligand polymer was obtained.

The prepared Co-based multi-phase catalyst is put into a high-pressure reaction kettle, then 1-hexene raw material and toluene solvent are added, and hydroformylation reaction is carried out under the conditions of 423K, 3.0MPa and 24h of reaction time. The reaction product is collected by a centrifugal separation method, the separated product is analyzed on an Agilent 7890A gas chromatograph by using a hydrogen flame detector (FID) with an HP-5 capillary column, and the product is calculated by an internal standard method by using n-propanol as an internal standard substance. The reaction results are shown in Table 1.

Example 2

In example 2, the procedure was followed as in example 1 except that 5.0g of tris (4-vinylbenzene) ylphosphine and 5.0g of tris (3-vinylbenzene) ylphosphine were weighed out in place of 7.69g of tris (4-vinylbenzene) ylphosphine, 1.54g of bis (3-vinylbenzene) phenylphosphine and 0.77g of pyrrole ring bidentate phosphine ligand having a vinyl group were dissolved in 100ml of tetrahydrofuran solvent. The reaction results are shown in Table 1.

Example 3

In example 3, the procedure was the same as in example 1 except that 10.0g of tris (4-vinylbenzene) ylphosphine was weighed out instead of 7.69g of tris (4-vinylbenzene) ylphosphine, 1.54g of bis (3-vinylbenzene) phenylphosphine and 0.77g of pyrrole ring bidentate phosphine ligand having a vinyl group were dissolved in 100ml tetrahydrofuran solvent. The reaction results are shown in Table 1.

Example 4

In example 4, the procedure was the same as in example 1 except that 0.05g of azobisisobutyronitrile, a radical initiator, was added instead of 0.25g of azobisisobutyronitrile. The reaction results are shown in Table 1.

Example 5

In example 5, the procedure was the same as in example 1 except that 333K solvothermal polymerization was used instead of 373K solvothermal polymerization. The reaction results are shown in Table 1.

Example 6

In example 6, the procedure was the same as in example 1 except that 0.336g of cobalt acetate was weighed out instead of 1.68g of cobalt acetate in 100ml of ethanol solvent. The reaction results are shown in Table 1.

Example 7

In example 7, the procedure was the same as in example 1 except that 3.35g of cobalt acetylacetonate was weighed out instead of 1.68g of cobalt acetate dissolved in 100ml of ethanol solvent. The reaction results are shown in Table 1.

Example 8

In example 8, the procedure was the same as in example 1 except that 2.78g of cobalt nitrate hydrate was weighed out instead of 1.68g of cobalt acetate in 100ml of ethanol solvent. The reaction results are shown in Table 1.

Example 9

In example 9, the procedure was the same as in example 1 except that the hydroformylation evaluation reaction temperature 373K was used instead of the hydroformylation evaluation reaction temperature 423K. The reaction results are shown in Table 1.

Example 10

In example 10, the procedure was the same as in example 1 except that the hydroformylation evaluation reaction pressure was 1MPa instead of the hydroformylation evaluation reaction pressure of 3 MPa. The reaction results are shown in Table 1.

Example 11

In example 11, the procedure was the same as in example 1 except that the hydroformylation evaluation reaction time 16h was used instead of the hydroformylation evaluation reaction time 24 h. The reaction results are shown in Table 1.

Example 12

In example 12, the procedure was the same as in example 1 except that 1-octene, which is a reaction raw material for evaluation, was hydroformylated instead of 1-hexene, which is a reaction raw material for evaluation. The reaction results are shown in Table 1.

Example 13

In example 13, the procedure was the same as in example 1 except that 1-dodecene as a reaction raw material for hydroformylation evaluation was used instead of 1-hexene as a reaction raw material for hydroformylation evaluation. The reaction results are shown in Table 1.

Comparative example 1

In comparative example 1, except that TiO was used₂The carrier replaces the organic phosphine ligand polymer and is used for the preparation of the catalyst and the evaluation of the subsequent heterogeneous hydroformylation reaction, and other processes are the same as the example 1. The reaction results are shown in Table 1.

Comparative example 2

In comparative example 2, except that Al was used₂O₃The carrier replaces the organic phosphine ligand polymer and is used for the preparation of the catalyst and the evaluation of the subsequent heterogeneous hydroformylation reaction, and other processes are the same as the example 1. The reaction results are shown in Table 1.

Comparative example 3

In comparative example 3, except that SiO was used₂The carrier replaces the organic phosphine ligand polymer and is used for the preparation of the catalyst and the evaluation of the subsequent heterogeneous hydroformylation reaction, and other processes are the same as the example 1. The reaction results are shown in Table 1.

TABLE 1 results of Co-based multiphase catalyst hydroformylation of higher olefins

As can be seen from the reaction data of the above examples 1-3, when the phosphine ligands L1, L5 and L12 are selected, and the corresponding mass ratio of the three is 1:0.2:0.1, the Co-based multi-phase catalyst high-carbon olefin hydroformylation reaction shows the optimal olefin conversion rate and the optimal target product aldehyde selectivity. Comparison of the reaction data of example 1 and example 6 shows that the appropriate cobalt metal is beneficial for increasing the olefin conversion of the hydroformylation of higher olefins. Comparison of the reaction data of example 1, example 9 and example 10 shows that suitable reaction temperature and pressure are beneficial to improve the olefin conversion rate and the target product aldehyde selectivity of the hydroformylation reaction of higher olefins. According to the results of the reaction data of examples 1 to 13 and comparative examples 1 to 3, the Co-based multi-phase catalyst provided by the invention is used for the hydroformylation reaction of high-carbon olefins, and the novel Co-based multi-phase catalyst designed and developed for the hydroformylation reaction of high-carbon olefins has excellent reaction activity and selectivity and good reaction stability; because the novel Co-based multi-phase catalyst is adopted, the separation cost of the catalyst, reactants and products is reduced, and the catalyst is suitable for large-scale industrial production; meanwhile, non-noble metal Co is selected as the active metal component of the catalyst, so that the economy of the hydroformylation reaction process is effectively improved.

The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.