EGGSHELL TYPE CATALYST, AND PREPARATION METHOD AND APPLICATION THEREOF IN PROPYLENE HYDROFORMYLATION REACTION

Abstract

An eggshell type catalyst, and a preparation method and application thereof in propylene hydroformylation reaction are provided. The eggshell type catalyst uses phosphine ligand resin pellets with developed pore structure as a carrier and one, two or more than two of metals Rh, Co, Ir, Ru and Pd as active components. The spatial distribution of the active metal components in the resin pellets is effectively regulated through a method of finely regulating the porous channel structure of the carrier resin pellets and adding competitive adsorption and coordination, so that the prepared eggshell type catalyst has the characteristics of high activity in the propylene hydroformylation reaction and good selectivity of n-butyraldehyde in the product aldehyde.

Claims

1. An eggshell type catalyst, characterized in that: active components of the eggshell type catalyst are selected from one, two or more than two of Rh, Co, Ir, Ru and Pd; a carrier of the eggshell type catalyst is a phosphine ligand resin pellet; the phosphine ligand resin pellet is formed by autopolymerization of one or more than one of monodentate ligands of vinyl or copolymerization of monodentate ligands of vinyl and polydentate ligands of vinyl; the particle size of the resin pellet ranges from 0.5-7 mm (preferably 0.5-4 mm); metal active components are coordinated on a surface layer of the polymer pellet to form a catalyst eggshell layer; and the thickness (the depth of the metal activity from a carrier surface coordinated to the carrier) of the catalyst eggshell layer (a surface layer of the carrier containing the metal active components is called the eggshell layer) is 0.1-0.2 mm (preferably 0.1-0.15 mm).

2. The eggshell type catalyst according to claim 1, characterized in that: the range of metal load of the eggshell type catalyst is 0.01-8 wt %, and a preferred range is 0.1-2 wt %; the preparation of the eggshell type catalyst uses a method of excessive solution impregnation; the phosphine ligand resin pellet is added to a solution containing one or more than one of precursors of the active components Rh, Co, Ir, Ru and Pd, stirred fully and coordinated; and active metal of the eggshell type catalyst is coordinated with the phosphine ligand in a resin skeleton to form the catalyst eggshell layer, thereby obtaining the eggshell type catalyst.

3. The eggshell type catalyst according to claim 1, characterized in that: the monodentate ligands of vinyl are one or more than one of the following: ##STR00010## ##STR00011## ##STR00012## the polydentate ligands of vinyl are one or more than one of the following ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017##

4. The eggshell type catalyst according to claim 1, characterized in that: the specific surface area of the phosphine ligand resin pellet is 50-3000 m.sup.2/g, and a preferred range is 200-1500 m.sup.2/g; the pore volume is 0.2-10.0 cm.sup.3/g, and preferably 0.5-3.0 cm.sup.3/g; and the pore size is distributed in the range of 0.01-100.0 nm, and preferably 0.2-10.0 nm.

5. A preparation method of the eggshell type catalyst according to claim 1, characterized in that: a preparation method of the phosphine ligand resin pellet comprises: after fully dissolving one or more than one of monodentate phosphine ligands of vinyl, adding or not adding polydentate phosphine ligands of vinyl, adding a free radical initiator and preparing the phosphine ligand resin pellet by suspension polymerization; the preparation method of the eggshell type catalyst comprises: firstly, adding the phosphine ligand resin pellet to the solution containing a competitive coordination agent and then removing a solvent; then adding the phosphine ligand resin pellet to a precursor impregnation solution containing active metal components; fully stirring to coordinate the active metal components with the phosphine ligand in the surface layer of the resin pellet; and evaporating the solvent to obtain the eggshell type catalyst.

6. The preparation method of the eggshell type catalyst according to claim 5, characterized in that: specific preparation steps of the eggshell type catalyst are: a) under the protection of inert atmosphere gas of 273-493 K (preferably 273-453 K), adding the monodentate phosphine ligands of vinyl to the solvent, adding or not adding polydentate phosphine ligands of vinyl, and stirring evenly for use to obtain a mixed solution; b) under the protection of inert atmosphere gas of 298-433 K (preferably 298-393 K), adding a suspending agent to water to fully dissolve, to obtain an aqueous phase; adding the above mixed solution to the aqueous phase while stirring; adding the free radical initiator; and polymerizing the phosphine ligand into a resin pellet at a stirring speed of 20-2000 r/min (preferably 50-800 r/min); c) taking out solid particles obtained in step b); cleaning by a solvent of 10-1000 (preferably 20-800) times the volume; and then removing the solvent at 298-453 K (preferably 298-393 K) to obtain the phosphine ligand resin pellet; d) under the protection of inert atmosphere gas of 273-453 K (preferably 273-413 K), stirring the phosphine ligand resin pellet obtained in step c) in a solution containing competitive adsorption coordination for 0.1-10 hours (preferably 0.1-5 hours); then removing the solvent at 298-433 K (preferably 298-393 K); then adding the resin pellet to a solution containing the precursors of the active metal components; stirring for 0.1-100 hours, and preferably for a range of 0.5-12 hours; and next, removing the solvent at 273-433 K (preferably 273-393 K) to obtain the eggshell type catalyst, wherein the concentration range of the competitive adsorption coordination and the active metal in the precursor solution is 0.0001-5 mol.Math.L.sup.1 respectively (preferably 0.0001-1 mol.Math.L.sup.1).

7. The preparation method of the eggshell type catalyst according to claim 6, characterized in that: an organic solvent in step a) is selected from one or more than one of toluene, xylene, benzene, n-alkane of C.sub.5-C.sub.15 and cyclohexane; before the resin pellet is polymerized, the concentration range of the monodentate ligands of vinyl in the solvent is 0.01-1000 g/L, preferably 1-100 g/L; a molar ratio of the monodentate ligands to the polydentate ligands is 5:1-200:1 when the monodentate ligands of vinyl and the polydentate ligands of vinyl are added at the same time; a molar ratio of the monodentate phosphine ligands containing alkylene to the free radical initiator is 500:1-10:1, preferably 100:1-10:1; the free radical initiator in step b) is one or more than one of dibenzoyl peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide or azodiisobutyronitrile; the suspending agent is selected from one or more than one of N-dodecyl dimethylamine, sodium stearate, calcium dodecylbenzene sulfonate, polyvinyl alcohol and polyvinylpyrrolidone; and a volume ratio of oil phase and aqueous phase in suspension polymerization is 1000:1-1:1000 (preferably 100:1-1:1000); the solvent for cleaning the resin pellet in step c) is one or more than one of benzene, toluene, xylene, isopropanol, ethanol, dichloromethane, petroleum ether, trichloromethane, water or tetrahydrofuran; the competitive adsorbent and coordination agent in step d) is selected from one or more than one of MgCl.sub.2, MgSO.sub.4, AlCl.sub.3, CaCl.sub.2), CuSO.sub.4 and ZnSO.sub.4; the impregnation of a competitive adsorbent and the active metal uses a method of excessive solution impregnation; a volume ratio of the resin pellet to an impregnation solution is 1:1.01-1:1000 (preferably 1:1.01-1:500); the inert atmosphere gas in steps a), b) and d) are selected from one or more than one of C.sub.02, Ar, He and N.sub.2.

8. The preparation method according to claim 5, characterized in that: the active components are one or more than one of Rh, Co, Ir, Ru and Pd, wherein the precursor of Rh is one or more than one of RhH(CO)(PPh.sub.3).sub.3, Rh(CO).sub.2(acac), RhCl.sub.3 and Rh(CH.sub.3COO).sub.2; the precursor of Co is one or more than one of Co(CH.sub.3COO).sub.2, Co(CO).sub.2(acac), Co(acac).sub.2 and CoCl.sub.2; the precursor of Ir is one or more than one of Ir(CO).sub.3(acac), Ir(CH.sub.3COO).sub.3, Ir(acac).sub.3 and IrCl.sub.4; the precursors of Ru are dichloride (1,5-cyclooctadiene) ruthenium (II), RuCl.sub.3, Ru(acac).sub.3, triruthenium dodecacarbonyl, [RuAr.sub.2(benzene)].sub.2, [RuAr.sub.2(p-cymene)].sub.2, [RuAr.sub.2(mesitylene)].sub.2, [(-ally)Ru(cod)].sub.2 and [(7c-ally)Ru(nbd)].sub.2; the precursor of Pd is one or more than one of Pd(CH.sub.3COO).sub.2, Pd(acac).sub.2, PdCl.sub.2, Pd(PPh.sub.3).sub.4 and PdCl.sub.2(CH.sub.3CN).sub.2, and the range of the metal load in the catalyst is 0.01-8 wt %, preferably 0.1-2 wt %.

9. An application of the eggshell type catalyst according to claim 1 in propylene hydroformylation reaction, comprising a reaction process of loading an eggshell type into a reactor and introducing raw material propylene and mixed gas containing H.sub.2 and CO for propylene hydroformylation reaction.

10. The application according to claim 9, characterized in that: the main components of the mixed gas are H.sub.2 and CO; the volume content of H.sub.2+CO is 10-100% (preferably 30-100%); a volume ratio of H.sub.2/CO is 0.1-10.0 (preferably 0.6-1.5); other gas components are one or more than one of CO.sub.2, N.sub.2, He and Ar; the purity of the raw propylene is 10-100% (preferably 50-100%), and other gas components are one or more than one of CO.sub.2, N.sub.2, He and Ar; reaction temperature is 313-433 K (preferably 343-393 K); reaction pressure is 0.1-6.0 MPa (preferably 0.3-2.0 MPa); airspeed of the mixed gas is 100-10000 h.sup.1 (preferably 300-3000 h.sup.1); propylene airspeed is 0.01-40.0 h.sup.1 (preferably 0.1-10.0); the reactor is a slurry bed, a trickle bed, a tank reactor, a radial reactor or a tubular reactor, preferably the slurry bed reactor; the eggshell type catalyst has high activity; the proportion of n-butyraldehyde in the product aldehyde is high; and this type of eggshell type catalyst exhibits a strong prospect of industrial application.

Description

DESCRIPTION OF DRAWINGS

[0033] FIG. 1 is an N.sub.2 physical adsorption curve of a resin pellet obtained in embodiment 1;

[0034] FIG. 2 is a pore size distribution diagram of a resin pellet obtained in embodiment 1.

DETAILED DESCRIPTION

[0035] The following embodiments better illustrate the present invention, but do not limit the protection scope of the present invention.

Embodiment 1

Preparation Method of Phosphine Ligand Resin Pellet:

[0036] In a CO.sub.2 atmosphere at 20 C., 5 g of tri(3-vinylphenyl) phenylphosphine (ligand L9) is weighed, dissolved in 70 ml of cyclohexane, and stirred evenly for use. In a CO.sub.2 atmosphere at 40 C., 0.5 g of sodium stearate (suspending agent) is dissolved in 20 mL of deionized water; the solution in which phosphine ligands are dissolved is added to the above deionized water in which the suspending agent is dissolved while stirred (mechanical stirring, at stirring speed of 180 r/min); 0.1 g of azodiisobutyronitrile (initiator) is added, and then continuously stirred (mechanical stirring, at stirring speed of 180 r/min) at 90 C. and polymerized for 12 hours.

[0037] After cooling to room temperature, 400 mL of resin pellets are filtered out, washed by tetrahydrofuran, and then dried under vacuum at 75 C. for 10 hours to obtain phosphine ligand resin pellets with a diameter range of 0.5 mm-2.5 mm and an average particle size of 1.8 mm. The N.sub.2 physical adsorption curve of the resin pellets is shown in FIG. 1. It is calculated that the pore volume of the polymer pellets is 1.82 cm.sup.3/g and the specific surface area is 908 m.sup.2/g. The pores of the resin pellets are mainly distributed at 0.4-10 nm (FIG. 2, a pore size distribution curve of phosphine ligand resin pellets).

Preparation Method of Eggshell Type Catalyst:

[0038] The resin pellets of 1.5-2.0 mm are screened. 1 g of resin pellets of 1.5-2.0 mm are weighed in a CO.sub.2 atmosphere at 30 C., added to 20 mL of 0.6 mol.Math.L.sup.1 MgSO.sub.4 aqueous solution, and stirred for 1 hour. The filtered resin pellets are dried under vacuum at 80 C. for 10 hours.

[0039] In a CO.sub.2 atmosphere at 35 C., 1 g of resin pellets adsorbed with competitive adsorbents are then added to 50.0 mL of xylene containing 5.1 mg of Rh(CO).sub.2(acac) (CAS No. 14874-82-9), stirred at 45 C. and coordinated for 48 hours.

[0040] The solvent is removed under vacuum at 45 C., to obtain the eggshell type catalyst applied to the hydroformylation reaction of olefin. The cross section is observed by an electron microscope. The active component Rh is uniformly coordinated on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.15 mm. The distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Embodiment 2

[0041] In embodiment 2, when the phosphine ligand resin pellets are prepared, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that 5 g of phosphine ligands L9 is replaced with 2.5 g of phosphine ligands L1 and 2.5 g of phosphine ligand L10. The cross section is observed by an electron microscope. The active component Rh is uniformly coordinated on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.15 mm. The distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Embodiment 3

[0042] In embodiment 3, when the phosphine ligand resin pellets are prepared, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that 5 g of phosphine ligands L9 is replaced with 5 g of phosphine ligands L6. The cross section is observed by an electron microscope. The active component Rh is uniformly coordinated on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.15 mm. The distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Embodiment 4

[0043] In embodiment 4, when the phosphine ligand resin pellets are prepared, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that 5 g of phosphine ligands L9 is replaced with 5 g of phosphine ligands L11. The cross section is observed by an electron microscope. The active component Rh is uniformly coordinated on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.15 mm. The distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Embodiment 5

[0044] In embodiment 5, when the phosphine ligand resin pellets are prepared, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that 5 g of phosphine ligands L9 is replaced with 4.8 g of phosphine ligands L9 and 0.2 g of phosphine ligand BL2. The cross section is observed by an electron microscope. The active component Rh is uniformly coordinated on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.15 mm. The distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Embodiment 6

[0045] In embodiment 6, when the phosphine ligand resin pellets are prepared, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that 5 g of phosphine ligands L9 is replaced with 4.5 g of phosphine ligands L9 and 0.5 g of phosphine ligand BL17. The cross section is observed by an electron microscope. The active component Rh is uniformly coordinated on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.15 mm. The distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Embodiment 7

[0046] In embodiment 7, when the eggshell type catalyst is prepared, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that 0.6 mol.Math.L.sup.1 MgSO.sub.4 aqueous solution is replaced with 1.0 mol.Math.L.sup.1 CaCl.sub.2) aqueous solution, when a competitive adsorbent is impregnated. The cross section is observed by an electron microscope. The active component Rh is uniformly coordinated on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.15 mm. The distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Embodiment 8

[0047] In embodiment 8, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that Rh(CO).sub.2(acac) is replaced with cobalt octacarbonyl of the same molar number. An eggshell type Co-based catalyst can be obtained, and the thickness of an eggshell layer is 0.13 mm.

Embodiment 9

[0048] In embodiment 9, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that Rh(CO).sub.2(acac) is replaced with IrCl.sub.4 of the same molar number. An eggshell type Ir-based catalyst can be obtained, and the thickness of a catalyst layer (shell layer) is 0.17 mm.

Embodiment 10

[0049] In embodiment 10, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that Rh(CO).sub.2(acac) is replaced with [(-ally)Ru(cod)].sub.2 of the same molar number. The thickness of a catalyst layer (shell layer) is 0.14 mm.

Embodiment 11

[0050] In embodiment 11, in the step of impregnating the active metal, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that 50.0 mL of xylene is replaced with 100 mL of 2-methyltetrahydrofuran for preparing the impregnation solution. The thickness of a catalyst layer (shell layer) is 0.17 mm.

Reference Example 1

[0051] In reference example 1, the type and the use amount of the metal Rh precursor in the impregnation process are the same as those of embodiment 1 except that a homogeneous catalyst is prepared by the solvothermal polymerization method mentioned in the previous patent CN104707660B.

[0052] A specific implementation method is as follows: 50 g of phosphine ligands L9 and 1 g of azodiisobutyronitrile are dissolved in 500 ml of tetrahydrofuran in a 1000 ml enamel high-pressure reactor, stirred for 2 hours, and immobilized under protection of 373K nitrogen for 24 hours to perform polymerization reaction. Then, the solution is cooled to room temperature, and the solvent is removed at room temperature to obtain a powdered polymer of the phosphine ligand. 5.1 mg of Rh(CO).sub.2(acac) is dissolved in 30.0 mL of tetrahydrofuran under the protection atmosphere of 298K and inert gas. 1.0 g of powdered polymer carrier of phosphine ligand (crushed to 200-300 meshes) is added. The mixture is stirred under the protection atmosphere of 298K and inert gas for 24 hours. Then, the solvent is vacuumed away at room temperature, to obtain a homogeneous powdered catalyst for the hydroformylation reaction.

Reference Example 2

[0053] In reference example 2, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that there is no step of impregnating the competitive adsorbent. The cross section is observed by an electron microscope. The active component Rh is uniformly coordinated on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.04 mm. The distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Reference Example 3

[0054] In reference example 3, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that there is no step of impregnating the competitive adsorbent and 50.0 mL of xylene is replaced with 5.0 mL of xylene for preparing the impregnation solution. The cross section is observed by an electron microscope. The active component Rh is uniformly coordinated on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.02 mm. The distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Reference Example 4

[0055] In reference example 4, the preparation steps of the eggshell type catalyst are changed to: [0056] 1 g of resin pellets of 1.5-2.0 mm are weighed in a CO.sub.2 atmosphere at 30 C., added to 20 mL of 0.6 mol.Math.L.sup.1 MgSO.sub.4 aqueous solution, and stirred for 1 hour. The filtered resin pellets are dried under vacuum at 80 C. for 10 hours. [0057] 1 g of resin pellets adsorbed with competitive adsorbents are added to 500.0 mL of xylene containing 5.1 mg of Rh(CO).sub.2(acac) (CAS No. 14874-82-9) at 10 C., stirred at 10 C. and coordinated for 48 hours.

[0058] The solvent is removed under vacuum at 45 C., to obtain the eggshell type catalyst applied to the hydroformylation reaction of olefin. The cross section is observed by an electron microscope. The active component Rh is uniformly distributed on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.22 mm, and the distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Reference Example 5

[0059] In reference example 5, when the resin pellets are prepared, the synthesis process of the resin pellets is the same as that of embodiment 1, except that 5 g of ligands L9 is replaced with 5 g of monodentate phosphine ligands of vinyl

##STR00009##

The preparation steps of the eggshell type catalyst are changed to: [0060] 1 g of resin pellets of 1.5-2.0 mm are weighed in a CO.sub.2 atmosphere at 70 C., added to 20 mL of 0.6 mol.Math.L.sup.1 MgSO.sub.4 aqueous solution, and stirred for 1 hour. The filtered resin pellets are dried under vacuum at 80 C. for 10 hours. [0061] 1 g of resin pellets adsorbed with competitive adsorbents are added to 500.0 mL of xylene containing 5.1 mg of Rh(CO).sub.2(acac) (CAS No. 14874-82-9) at 10 C., stirred at 10 C. and coordinated for 48 hours.

[0062] The solvent is removed under vacuum at 45 C., to obtain the eggshell type catalyst applied to the hydroformylation reaction of olefin. The cross section is observed by an electron microscope. The active component Rh is uniformly distributed on the surface layer of the polymer pellets. The thickness of the catalyst layer (shell layer) containing metal Rh is 0.27 mm, and the distribution of Rh in the eggshell layer is uniform. The measured metal load of the catalyst is 0.20%.

Reference Example 6

[0063] In reference example 6, when the eggshell type catalyst is prepared, the active metal is not impregnated, and only the competitive adsorbent is impregnated. The synthesis pre and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1. Specific steps are as follows:

Preparation of Eggshell Type Catalyst:

[0064] The resin pellets of 1.5-2.0 mm are screened. 1 g of resin pellets of 1.5-2.0 mm are weighed in a CO.sub.2 atmosphere at 30 C., added to 20 mL of mixed aqueous solution of 0.6 mol.Math.L.sup.1 MgSO.sub.4, 0.6 mol.Math.L.sup.1 MgCl.sub.2, 0.6 mol.Math.L.sup.1 MgSO.sub.4, 0.6 mol.Math.L.sup.1 AlCl.sub.3, 0.6 mol.Math.L.sup.1 CaCl.sub.2), 0.6 mol.Math.L.sup.1 CuSO.sub.4 and 0.6 mol.Math.L.sup.1 ZnSO.sub.4, and stirred for 1 hour. The filtered resin pellets are dried under vacuum at 80 C. for 10 hours.

Embodiment 12

[0065] 1 g of the catalysts prepared in embodiments 1-11 and reference examples 1-6 are loaded into a slurry bed reactor with a capacity of 100 ml, and 60 ml of valeraldehyde is added as slurry liquid. The reaction mixed gas (H.sub.2:CO:C.sub.3H.sub.6=1:1:1) is introduced. The hydroformylation reaction is carried out at 378K, 0.8 MPa, an airspeed of the reaction mixed gas of 1000 h.sup.1 and a stirring rate of 600 RPM. In the reaction, a collection tank at constant temperature of 10 C. is used for collection. The reaction products and the slurry liquid carried by tail gas are all dissolved in the collection tank. The collected liquid is analyzed by HP-7890N gas chromatography with HP-5 capillary column and FID, and ethanol is used as the internal standard. The tail gas is analyzed online by HP-7890N gas chromatography with Porapak-QS column and TCD. Reaction results are listed in Table 1.

TABLE-US-00001 TABLE 1 Performance of Propylene Hydroformylation of Slurry Bed of Catalyst in Embodiment 1-Embodiment 11 and Reference Examples Pore Size Aldehyde Distribution Propylene Selectivity/ n- Entry Catalysts S.sub.BET/(m.sup.2/g) (nm) TOF(h.sup.1) % butyraldehyde:isobutyraldehyde 1 Embodiment 1 902 0.2-10.0 733.6 99.0 8.7 2 Embodiment 2 873 0.1-8.0 744.5 98.7 10.9 3 Embodiment 3 794 0.3-9.0 953.2 99.0 8.0 4 Embodiment 4 705 0.1-8.0 719.0 99.0 9.8 5 Embodiment 5 897 0.1-10.0 1236.7 98.8 29.7 6 Embodiment 6 840 0.1-9.0 724.4 98.9 33.2 7 Embodiment 7 903 0.2-10.0 716.3 98.7 8.9 8 Embodiment 8 904 0.2-10.0 111.6 97.4 8.4 9 Embodiment 9 902 0.2-10.0 63.3 98.0 8.1 10 Embodiment 903 0.2-10.0 74.2 97.4 8.0 10 11 Embodiment 902 0.2-10.0 736.3 98.8 9.0 11 12 Reference 1131 0.1-5.0 605.7 97.3 8.3 example 1 13 Reference 905 0.2-10.0 739.3 98.7 2.6 example 2 14 Reference 903 0.2-10.0 636.4 98.6 2.5 example 3 15 Reference 899 0.2-10.0 653.1 98.9 8.7 example 4 16 Reference 549 0.2-4.0 606.2 99.1 8.9 example 5 17 Reference 902 0.2-10.0 0 example 6

[0066] It can be seen from Table 1 that embodiments 1-11 are the eggshell type catalyst. The ratio of n-butyraldehyde to isobutyraldehyde in the product aldehyde can be basically above 8.0, and the value of propylene TOF can be above 700 h.sup.1. When the copolymerization solution of monophosphine ligands and polydentate phosphine ligands is adopted to prepare resin pellets to prepare the eggshell type catalyst, the ratio of n-butyraldehyde to isobutyraldehyde in the product butyaldehyde can be about 30 (embodiments 5 and 6). In embodiments 8, 9 and 10, the active metals are Co, Ir and Ru, respectively, and have lower reaction performance than the catalysts with the active metal of Rh (embodiment 1) (however, Co, Ir, Ru, etc. have lower price and are more suitable for non-Rh metals in some industrial occasions). When the active center is Rh, it can be seen that the activity of the propylene hydroformylation reaction of the eggshell type catalyst is higher than that of the homogeneous catalyst of the corresponding reference example (reference example 1) and the selectivity of n-butyraldehyde is similar. When there is no step of impregnating the competitive adsorbent (reference example 2), the ratio of n-butyraldehyde to isobutyraldehyde in the eggshell type catalyst is 2.6. The impregnation of the competitive adsorbent can improve the spatial distribution of the active components of the catalyst in the resin pellets, so that the selectivity of n-butyraldehyde is higher in the propylene hydroformylation reaction. The eggshell layer (0.02 mm) of the catalyst prepared by reference example 3 is thinner than the eggshell layers of the catalysts prepared by embodiments 1-11. Thus, the selectivity of the product n-butyraldehyde is significantly lower than that of embodiment 1 and the activity is also lower than that of embodiment 1. The thicknesses of the eggshell layers prepared by reference example 4 and reference example 5 are 0.22 mm and 0.27 mm, respectively, which are thicker than that of embodiment 1. The selectivity of n-butyraldehyde is not significantly improved compared with embodiment 1, and the reactivity of propylene is lower than that of embodiment 1. This may be because the thickness of the eggshell layer is too thick and deeper active species Rh is unable to come into full contact with a reaction substrate. To sum up, appropriate thickness of the eggshell layer can ensure high n-butyraldehyde selectivity (the ratio of n-butyraldehyde to isobutyraldehyde is greater than 8), while ensuring high activity of propylene hydroformylation reaction (except for non-Rh metals, the TOF value of propylene is basically above 700 h.sup.1). In reference example 6, only the competitive adsorbent is impregnated, and it is found from a test that there is no activity of propylene hydroformylation reaction. This proves that the competitive adsorbent only regulates the distribution of the active metal in the eggshell type catalyst during the preparation of the catalyst, but cannot catalyze the hydroformylation reaction of propylene. The spatial distribution of the active metal components in the resin pellets is effectively regulated through a method of finely regulating the porous channel structure of carrier resin pellets and adding the competitive coordination agent, so that the prepared eggshell type catalyst has the characteristics of high activity in the propylene hydroformylation reaction and good selectivity of n-butyraldehyde in the product aldehyde. The eggshell type catalyst has high mechanical strength of carrier resin pellets (measured as about 40 N/pellet), can exist stably in organic solvents without swelling or powdering, and is suitable for industrial application of propylene hydroformylation.

Embodiment 13

[0067] In embodiment 13, when the eggshell type catalyst is prepared, in the step of impregnating the competitive adsorbent, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that 0.6 mol.Math.L.sup.1 MgSO.sub.4 aqueous solution is replaced with 0.6 mol.Math.L.sup.1 MgCl.sub.2, AlCl.sub.3, CaCl.sub.2), CuSO.sub.4, ZnSO.sub.4, NaCl, KCl, NaNO.sub.3 and NaHCO.sub.3. The performance results of propylene hydroformylation are shown in Table 2 by the evaluation method of embodiment 12.

TABLE-US-00002 TABLE 2 Performance of Propylene Hydroformylation of Slurry Bed of Monophosphine Ligand Catalysts Prepared by Different Competitive Adsorbents Eggshell Pore Size Layer Aldehyde Competitive Distribution Thickness Propylene Selectivity/ n- Entry Adsorbent S.sub.BET/(m.sup.2/g) (nm) (mm) TOF(h.sup.1) % butyraldehyde:isobutyraldehyde 1 MgSO.sub.4 902 0.2-10.0 0.15 733.6 99.0 8.7 2 MgCl.sub.2 900 0.2-10.0 0.10 766.9 99.1 3.2 3 AlCl.sub.3 901 0.2-10.0 0.20 695.5 99.1 13.5 4 CaCl.sub.2 905 0.2-10.0 0.12 754.8 98.9 5.8 5 CuSO.sub.2 899 0.2-10.0 0.19 705.7 99.5 9.4 6 ZnSO.sub.2 904 0.2-10.0 0.18 724.9 99.2 9.8 7 NaCl 900 0.2-10.0 0.02 615.8 98.5 2.1 8 KCl 898 0.2-10.0 0.02 564.1 98.3 2.2 9 NaNO.sub.3 901 0.2-10.0 0.02 256.8 98.0 2.4 10 NaHCO.sub.3 899 0.2-10.0 0.02 189.5 97.3 2.3

[0068] It can be seen from Table 2 that the thickness of the eggshell type catalyst can be significantly changed by using different competitive adsorbents of MgCl.sub.2, AlCl.sub.3, CaCl.sub.2), CuSO.sub.4 and ZnSO.sub.4. On the premise of ensuring a high TOF value of propylene (>690 h.sup.1), the ratio of n-butyraldehyde to isobutyraldehyde is significantly changed. The ratio of n-butyraldehyde to isobutyraldehyde is as high as 13.5 and as low as 3.2, which could not be achieved by using only monophosphine ligand for preparation of the catalyst in the early stage.

[0069] Salts of monovalent metal of NaCl, KCl, NaNO.sub.3 and NaHCO.sub.3 are used as the competitive adsorbents, which cannot adjust the thickness of the eggshell layer. The ratio of n-butyraldehyde to isobutyraldehyde is similar to that of reference example 3 without adding the competitive adsorbents. Most crucially, when the anion is NO.sub.3.sup. or HCO.sub.3.sup., the activity of the catalyst may be affected and the TOF value of propylene is only about 200 h.sup.1.

Embodiment 14

[0070] In embodiment 14, when the eggshell type catalyst is prepared, in the step of impregnating the competitive adsorbent, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 5, except that 0.6 mol.Math.L.sup.1 MgSO.sub.4 aqueous solution is replaced with 0.6 mol.Math.L.sup.1 MgCl.sub.2, AlCl.sub.3, CaCl.sub.2), CuSO.sub.4, ZnSO.sub.4, NaCl, KCl, NaNO.sub.3 and NaHCO.sub.3. The performance results of propylene hydroformylation are shown in Table 3 by the evaluation method of embodiment 12:

TABLE-US-00003 TABLE 3 Performance of Propylene Hydroformylation of Slurry Bed of Monophosphine/Diphosphine Copolymerization Catalysts Prepared by Different Competitive Adsorbents Eggshell Pore Size Layer Aldehyde Competitive Distribution Thickness Propylene Selectivity/ n- Entry Adsorbent S.sub.BET/(m.sup.2/g) (nm) (mm) TOF(h.sup.1) % butyraldehyde:isobutyraldehyde 1 MgSO.sub.4 897 0.2-10.0 0.15 1236.7 98.8 29.7 2 MgCl.sub.2 895 0.2-10.0 0.10 1524.7 99.2 17.3 3 AlCl.sub.3 891 0.2-10.0 0.20 1126.8 99.1 42.5 4 CaCl.sub.2 898 0.2-10.0 0.13 1446.0 99.3 18.7 5 CuSO.sub.2 903 0.2-10.0 0.20 1098.9 98.9 39.2 6 ZnSO.sub.2 900 0.2-10.0 0.20 1132.2 98.8 41.8 7 NaCl 902 0.2-10.0 0.02 1008.1 98.7 13.2 8 KCl 901 0.2-10.0 0.02 966.41 98.4 12.5 9 NaNO.sub.3 907 0.2-10.0 0.02 323.4 98.3 11.1 10 NaHCO.sub.3 889 0.2-10.0 0.02 297.1 96.8 12.8

[0071] It can be seen from Table 3 that the thickness of the monophosphine/diphosphine copolymerization eggshell type catalyst can be significantly changed by using competitive adsorbents of MgCl.sub.2, AlCl.sub.3, CaCl.sub.2), CuSO.sub.4 and ZnSO.sub.4. The TOF value of propylene can be regulated in the range of 1127-1525 h.sup.1, and the ratio of n-butyraldehyde to isobutyraldehyde can also be regulated in a large range. The ratio of n-butyraldehyde to isobutyraldehyde is as high as 42.5 and as low as 3.2.

[0072] Salts of monovalent metal of NaCl, KCl, NaNO.sub.3 and NaHCO.sub.3 are used as the competitive adsorbents, which cannot adjust the thickness of the eggshell layer. The ratio of n-butyraldehyde to isobutyraldehyde is much smaller than the results of salts of bivalent and trivalent metals of MgCl.sub.2, AlCl.sub.3, CaCl.sub.2), CuSO.sub.4 and ZnSO.sub.4. Most crucially, when the anion is NO.sub.3 or HCO.sub.3, the activity of the catalyst may be affected and the TOF value of propylene is only about 300 h.sup.1.

Embodiment 15

[0073] In embodiment 15, when the eggshell type catalyst is prepared, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that the monodentate ligand L9 is replaced with other monodentate ligands/polydentate ligands mentioned in claims for autopolymerization. The performance results of propylene hydroformylation are shown in Table 4 by the evaluation method of embodiment 12:

TABLE-US-00004 TABLE 4 Performance of Propylene Hydroformylation of Slurry Bed of Autopolymerization Eggshell Type Catalysts Prepared by Different Ligands Eggshell Pore Size Layer Aldehyde Distribution Thickness Propylene Selectivity/ n- Entry Ligand S.sub.BET/(m.sup.2/g) (nm) (mm) TOF(h.sup.1) % butyraldehyde:isobutyraldehyde 1 L1 1109 0.2-10.0 0.15 974.2 99.3 7.0 2 L2 768 0.2-10.0 0.15 655.8 97.8 8.2 3 L3 799 0.2-10.0 0.15 856.7 98.6 6.5 4 L4 783 0.2-10.0 0.15 887.9 98.5 6.1 5 L5 568 0.2-10.0 0.15 900.8 98.6 5.4 6 L6 765 0.2-10.0 0.13 1347.9 98.8 4.2 7 L7 557 0.1-0.8 0.12 1237.3 97.9 3.9 8 L8 346 0.1-0.8 0.12 900.2 97.9 4.3 9 L9 832 0.2-10.0 0.15 733.6 99.0 8.7 10 L10 175 0.1-0.5 0.17 382.0 98.5 11.5 11 L11 645 0.1-0.6 0.16 525.8 98.9 12.4 12 L12 548 0.1-0.8 0.14 899.6 98.8 10.0 13 BL1 89.8 0.1-0.5 0.17 459.0 99.4 42.5 14 BL2 85.3 0.1-0.5 0.20 430.1 99.2 37.6 15 BL3 80.1 0.1-0.5 0.18 397.4 99.3 30.1 16 BL8 90.4 0.1-0.5 0.18 444.4 99.5 18.9 17 BL10 78.9 0.1-0.5 0.19 378.9 99.5 23.2 18 BL12 538 0.1-0.8 0.19 589.3 99.3 23.5 19 BL13 80.2 0.1-0.5 0.20 408.7 99.1 25.6 20 BL14 504 0.1-0.6 0.19 833.2 99.0 21.4 21 BL15 553 0.1-0.8 0.18 600.2 99.4 30.2 22 BL16 562 0.1-0.8 0.20 589.1 99.6 28.7 23 BL17 134 0.1-0.5 0.17 405.6 99.7 30.7 24 BL18 564 0.1-0.6 0.18 677.9 99.6 45.8

[0074] It can be seen from Table 4 that the ratio of n-butyraldehyde to isobutyraldehyde in the eggshell type catalysts prepared by autopolymerization of different monophosphine ligands ranges from 4 to 15. When the same monomer is used, the eggshell type catalyst prepared has higher ratio of n-butyraldehyde to isobutyraldehyde than the catalyst with the same ligand prepared by the previous patent CN202110589670.1. The eggshell type catalysts prepared by autopolymerization of diphosphine ligands BL12, BL14, BL15, BL16 and BL18 containing 4 vinyls have TOF values in the range of 589-833 h.sup.1 and ratios of n-butyraldehyde to isobutyraldehyde in the range of 21-45. Other eggshell type catalysts prepared by bisphosphine ligands (BL1-BL11, BL13 and BL17) with two vinyls have higher ratios of n-butyraldehyde to isobutyraldehyde (23-42), but lower specific surface area and less desirable activity (TOF range is 378-459 h.sup.1). These ligands are suitable for the preparation of high performance eggshell type catalysts in the solution of copolymerization with monophosphine ligands (embodiments 5 and 6, with TOF range of 724-1236 h.sup.1, and the range of the ratios of n-butyraldehyde to isobutyraldehyde of 29-33).

Reference Example 7

[0075] In reference example 7, when the eggshell type catalyst is prepared, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that Rh(CO).sub.2(acac) is replaced with Pt(acac).sub.2 of the same molar number. An eggshell type Pt-based catalyst can be obtained, and the thickness of an eggshell layer is 0.15 mm.

Reference Example 8

[0076] In reference example 8, the synthesis process and conditions of the resin pellets and the eggshell type catalyst are the same as those of embodiment 1, except that Rh(CO).sub.2(acac) is replaced with Fe(acac).sub.3 of the same molar number. An eggshell type Fe-based catalyst can be obtained, and the thickness of an eggshell layer is 0.15 mm.

Embodiment 16

[0077] 1 g of the prepared eggshell type catalysts (the Rh eggshell type catalyst in embodiment 1, the Co eggshell type catalyst in embodiment 8, the Ir eggshell type catalyst in embodiment 9, the Ru eggshell type catalyst in embodiment 10, the Pt eggshell type catalyst in reference example 7, and the Fe eggshell type catalyst in reference example 8) of different metals are loaded into a slurry bed reactor with a capacity of 100 ml, and 60 ml of valeraldehyde is added as slurry liquid. The reaction mixed gas (H.sub.2:CO:C.sub.3H.sub.6=1:1:1) is introduced. The hydroformylation reaction is carried out at 378K, 0.8 MPa, an airspeed of the reaction mixed gas of 1000 h.sup.1 and a stirring rate of 600 RPM. In the reaction, a collection tank at constant temperature of 10 C. is used for collection. The reaction products and the slurry liquid carried by tail gas are all dissolved in the collection tank. The collected liquid is analyzed by HP-7890N gas chromatography with HP-5 capillary column and FID, and ethanol is used as the internal standard. The tail gas is analyzed online by HP-7890N gas chromatography with Porapak-QS column and TCD. Reaction results are listed in Table 5.

TABLE-US-00005 TABLE 5 Performance of Propylene Hydroformylation of Slurry Bed of Eggshell Type Catalysts of Different Active Metals Pore Size Aldehyde Distribution Propylene Selectivity/ n- Entry Catalysts S.sub.BET/(m.sup.2/g) (nm) TOF(h.sup.1) % butyraldehyde:isobutyraldehyde 1 Rh in 902 0.2-10.0 733.6 99.0 8.7 embodiment 1 2 Co in 904 0.2-10.0 111.6 97.4 8.4 embodiment 8 3 Ir in 0.2-10.0 63.3 98.0 8.1 embodiment 9 902 4 Ru in 903 0.2-10.0 74.2 97.4 8.0 embodiment 10 5 Pt in reference 905 0.2-10.0 60.4 98.2 2.7 example 7 6 Fe in reference 902 0.2-10.0 34.2 97.3 4.2 example 8

[0078] It can be seen from Table 5 that when the active metals are Rh, Co, Ir and Ru, the ratio of n-butyraldehyde to isobutyraldehyde can basically be above 8, while the ratios of n-butyraldehyde to isobutyraldehyde for Pt and Fe are only 2.7 and 4.2, which is not a preferred solution of the patent.

Embodiment 17

[0079] In embodiment 17, the implementation process is the same as that of embodiment 16 except that the reaction condition is adjusted to 418K and 1 Mpa. The reaction under the condition is measured, and the results are listed in Table 6.

TABLE-US-00006 TABLE 6 Performance of Propylene Hydroformylation of Slurry Bed of Eggshell Type Catalysts of Different Active Metals at 418K and 1 MPa Pore Size Aldehyde Distribution Propylene Selectivity/ n- Entry Catalysts S.sub.BET/(m.sup.2/g) (nm) TOF(h.sup.1) % butyraldehyde:isobutyraldehyde 1 Rh in 902 0.2-10.0 1634.2 98.8 8.6 embodiment 1 2 Co in 904 0.2-10.0 659.1 97.1 8.2 embodiment 8 Ir in 3 embodiment 9 902 0.2-10.0 611.3 97.8 7.9 4 Ru in 903 0.2-10.0 701.4 97.1 7.7 embodiment 10 5 Pt in reference 905 0.2-10.0 346.2 97.0 2.2 example 7 6 Fe in reference 902 0.2-10.0 289.5 96.1 3.8 example 8

[0080] It can be seen from Table 6 that after the reaction temperature is increased to 418K and the pressure is increased to 1 MPa, the TOF value of the Rh eggshell type catalyst can reach 1634, and the ratio of n-butyraldehyde to isobutyraldehyde is still maintained at a high level. The TOF values (TOF values range from 611 to 701 h.sup.1) of Co, Ir and Ru eggshell type catalysts are also increased significantly. The TOF values of Pt and Fe eggshell type catalysts are only increased to about 300 h.sup.1, which is not a preferred solution of the patent.

Embodiment 18

[0081] 1 g of the catalysts prepared by preferred embodiments 1, 2, 5 and 6 of the patent are loaded into a fixed bed reactor respectively, and both ends of the bed layers of the catalysts are loaded with quartz sand. The reaction mixed gas (H.sub.2:CO:C.sub.3H.sub.6=1:1:1, V/V/V) is introduced. The hydroformylation reaction is carried out at 378K, 0.8 MPa, and an airspeed of the reaction mixed gas of 1000 h.sup.1. In the reaction, a collection tank containing 100 ml of cooled deionized water is used for absorption and collection. The reaction product butyraldehyde is fully dissolved in the water in the collection tank. The obtained aqueous solution is analyzed by HP-7890N gas chromatography with HP-5 capillary column and FID, and ethanol is used as the internal standard. After absorption by the water, the reaction tail gas is analyzed online by HP-7890N gas chromatography with Porapak-QS column and TCD. Reaction results are listed in Table 7.

TABLE-US-00007 TABLE 7 Performance of Propylene Hydroformylation of Fixed Bed of Catalysts in Embodiments 1, 2, 5 and 6 Pore Size Aldehyde Distribution Propylene Selectivity/ n- Entry Catalysts S.sub.BET/(m.sup.2/g) (nm) TOF(h.sup.1) % butyraldehyde:isobutyraldehyde 1 Embodiment 902 0.2-10.0 670.5 99.1 10.0 1 2 Embodiment 873 0.1-8.0 688.4 98.9 12.8 2 3 Embodiment 897 0.1-10.0 1200.1 99.0 33.1 5 4 Embodiment 840 0.1-9.0 690.2 99.2 36.2 6

[0082] It can be seen from Table 7 that when the reactor situation is a fixed bed reactor, the eggshell type catalyst exhibits better performance, and compared with the slurry bed reactor, the ratio of n-butyraldehyde to isobutyraldehyde is significantly increased (which is more than 10 for the eggshell type catalyst prepared by autopolymerization of monophosphine ligands, and more than 33 for the eggshell type catalyst prepared by monophosphine and diphosphine copolymerization). The selectivity of the product aldehyde is slightly increased, while the TOF of propylene is slightly decreased. The reactor form can be flexibly selected according to the requirements for the product.