CN114773171A - Method for propylene hydroformylation reaction by using phosphine oxide polymer supported catalyst - Google Patents

Method for propylene hydroformylation reaction by using phosphine oxide polymer supported catalyst Download PDF

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CN114773171A
CN114773171A CN202210233393.5A CN202210233393A CN114773171A CN 114773171 A CN114773171 A CN 114773171A CN 202210233393 A CN202210233393 A CN 202210233393A CN 114773171 A CN114773171 A CN 114773171A
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phosphine oxide
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hydroformylation
oxide polymer
propylene
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李存耀
丁云杰
严丽
丁玉龙
姜淼
马雷
姬广军
钱磊磊
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Dalian Institute of Chemical Physics of CAS
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    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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Abstract

The invention discloses a method for propylene hydroformylation reaction by using a phosphine oxide polymer supported catalyst, which takes one, two or more than two of metals Rh, Co, Ir, Ru, Pt, Pd and Fe as active components and phosphine oxide polymer as a carrier. The heterogeneous catalyst provided by the invention has good performance in propylene hydroformylation reaction, the proportion of n-butyraldehyde and isobutyraldehyde as products is flexible and adjustable, the n-iso ratio is 0.5-50, the content of propane as a byproduct is lower than 0.1%, the supported catalyst has good stability, and the catalyst is simple and efficient to separate from reactants and products. The supported catalyst is suitable for reactors such as fixed bed, slurry bed, kettle reactor and trickle bed. Compared with the traditional propylene hydroformylation catalyst taking triphenylphosphine as a ligand, the catalyst has higher catalytic activity; the catalyst is stable to air and moisture, and the operation condition is mild.

Description

Method for propylene hydroformylation reaction by using phosphine oxide polymer supported catalyst
Technical Field
The invention belongs to the field of heterogeneous catalysis and fine chemical engineering, and particularly relates to a method for performing propylene hydroformylation reaction by using a phosphine oxide polymer supported catalyst.
Background
The hydroformylation of olefins is an important way to produce aldehyde and alcohol products with high added values, and is the most successful model for homogeneous catalysis industrial application so far. Because the homogeneous catalyst faces the problem of difficult recovery and separation, people invest a great deal of energy in the field of heterogenization of the homogeneous catalyst. However, the problems of low catalyst activity, easy loss of active metal and poor catalyst stability limit the further development of the heterogenization technology.
Of the hydroformylation reactions of all olefins, the hydroformylation of propylene is of primary importance. Butyraldehyde, a product of hydroformylation of propylene, accounts for over 50% of all aldehyde consumption worldwide. The products of propylene hydroformylation are n-butyraldehyde and isobutyraldehyde, which are high value-added chemicals with large industrial consumption. Butyraldehyde hydrogenation can be used for preparing butanol, and oxidation can be used for preparing butyric acid, and the butyraldehyde hydrogenation and the oxidation are chemicals with large using amount. Butyraldehyde is used for preparing unsaturated C8 aldehyde through aldol condensation reaction, 2-vinyl hexanol (butanol-octanol) can be prepared through further hydrogenation reduction, the esterification reaction of butanol-octanol and phthalic acid can prepare the plasticizer DEHP widely applied in PVC (polyvinyl chloride) plastics at present, and the esterification reaction of butanol-octanol and adipic acid can prepare DEHA through reaction, and the DEHA can be used as a plasticizer, a hydraulic agent, a lubricant for an aircraft engine and the like.
The current industrial propylene hydroformylation uses mainly a homogeneous process of DAVY corporation and a water-oil two-phase process of lurgi corporation. In both processes, an excess of phosphine ligand is required to maintain the stability of the catalytically active species. And too high P/Rh ratio (ratio of phosphine ligand to Rh) results in high ratio of n-butyraldehyde to i-butyraldehyde, and too small adjustable range of n-iso ratio. The energy conservation, consumption reduction and benefit optimization of the factory are limited.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a phosphine-containing organic mixed polymer-metal heterogeneous catalyst and an application thereof in the reaction of producing butyraldehyde by propylene hydroformylation.
The technical scheme of the invention is as follows:
introducing propylene and synthesis gas to carry out hydroformylation reaction in the presence of a phosphine oxide polymer supported catalyst;
the phosphine oxide supported catalyst takes one or more than two of metals Rh, Co, Ir, Ru, Pt, Pd and Fe as an active component, and takes phosphine oxide polymer as a carrier;
the phosphine oxide polymer is formed by self-polymerization of a secondary phosphine oxide ligand containing alkylene or copolymerization of the secondary phosphine oxide ligand containing alkylene and a second component containing alkylene;
the secondary phosphine oxide ligand containing alkylene is one or more than two of the following:
Figure BDA0003541201170000021
the second component containing olefin group is selected from one or more than two of the following components:
Figure BDA0003541201170000031
Figure BDA0003541201170000041
Figure BDA0003541201170000051
the secondary phosphine oxide ligand containing an alkylene group and the second component alkylene group containing an alkylene group for polymerization are preferably vinyl functional groups.
The reaction process is that the prepared catalyst is loaded into a reactor, raw material propylene and mixed gas are introduced, and the main component of the mixed gas is H2And CO, H2The volume content of + CO is 20-100% (preferably 50-100%), H2The volume ratio of/CO is 0.5-5.0 (preferably 0.5-2.0), and the rest gas components are one or more than two of CO2, N2, He and Ar gas; the purity of the raw material propylene is 20-100% (preferably 50-100%), and the rest gas components are one or more of CO2, N2, He and Ar gas; the reaction temperature is 323-453K (preferably 323-403K), the reaction pressure is 0.1-5.0 MPa (preferably 0.5-4.0 MPa), and the gas space velocity of the mixed gas is 100-10000 h-1(preferably 500 to 5000 hours)-1) The space velocity of propylene is 0.01-20.0 h-1(preferably 0.1-8.0) carrying out hydroformylation reaction, wherein the reactor is a fixed bed, a slurry bed, a trickle bed or a tank reactor.
The loading range of the metal active component in the catalyst is 0.01-10 wt%, and preferably 0.01-3 wt%.
The phosphine oxide polymer carrier has a hierarchical pore structure and a specific surface area of 10-3000m2A preferred range is 100-2Per g, pore volume of 0.1-10.0cm3In terms of/g, preferably from 0.3 to 2.0cm3(ii)/g, pore size distribution is 0.01-100.0nm, preferably 0.1-5.0 nm;
the metal loading amount of the active component in the catalyst is in the range of 0.01-10 wt%, and the preferable range is 0.1-3 wt%. The phosphine oxide polymer is prepared by the following steps:
after a secondary phosphine oxide ligand containing alkylene is dissolved or the secondary phosphine oxide containing alkylene and a second component containing alkylene are dissolved and mixed, initiating the alkylene in the organic phosphine ligand to carry out polymerization reaction by a free radical initiator to generate a phosphine oxide polymer carrier with a hierarchical porous structure;
the preparation process of the phosphine oxide polymer supported catalyst comprises the following steps: and fully stirring and coordinating the precursor of the active metal component and the phosphine oxide polymer carrier in a solvent, forming a firm chemical bond between the active metal component and the exposed P in the phosphine oxide polymer carrier, and evaporating the solvent to obtain the phosphine oxide polymer supported catalyst.
The specific preparation steps of the phosphine oxide supported catalyst are as follows:
a) under the inert gas atmosphere 273-473K (preferably 298-433K), adding a secondary phosphine oxide ligand containing an alkylene group into a solvent, or adding a secondary phosphine oxide ligand containing an alkylene group and a second component containing an alkylene group into the solvent, adding a free radical initiator, and stirring the mixture for 0.1-100 hours to obtain a prepolymer solution, wherein the preferable stirring time range is 0.1-20 hours;
b) transferring the prepolymer mixed solution prepared in the step a) into a polymerization reactor, and carrying out polymerization reaction for 1-100 hours by adopting one or more methods of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like to obtain a phosphine oxide polymer;
c) removing the solvent from the phosphine oxide polymer obtained in the step b) under 273-403K to obtain the phosphine oxide polymer with the hierarchical pore structure, namely the carrier of the phosphine oxide polymer supported catalyst;
d) adding the phosphine oxide polymer carrier obtained in the step c) into a solvent containing an active metal component precursor under an inert gas atmosphere of 273-; the concentration of the active metal in the precursor solution is in the range of 0.001-1mol L-1 (preferably 0.01-1mol L-1).
The solvent in the steps a) and d) is one or more than two of methanol, ethanol, dichloromethane, trichloromethane, benzene, toluene, xylene, water or tetrahydrofuran;
the free radical initiator in the step a) is one or more than two of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, cyclohexanone peroxide or dibenzoyl peroxide.
The molar ratio of secondary alkylene-containing phosphine oxide ligand to second alkylene-containing component described in step a) is from 0.01:1 to 100:1, preferably from 1:1 to 1:10, and the molar ratio of secondary alkylene-containing phosphine oxide ligand to free-radical initiator is from 500:1 to 10:1, preferably from 100:1 to 10: 1. The concentration of the secondary phosphine oxide containing an alkylene group in the solvent before polymerization to an organic polymer is in the range of 0.01 to 1000g/L, preferably 0.1 to 10 g/L; the inert gases in the steps a), b) and d) are respectively selected from one or more than two of Ar, He, N2 and CO 2.
The active component is one or more than two of Rh, Co, Ir, Ru, Pt, Pd or Fe, wherein the precursor of Rh is RhH (CO) (PPh)3)3、Rh(CO)2(acac)、RhCl3、Rh(CH3COO)2One or more than two of (a); the precursor of Co is Co (CH)3COO)2、Co(CO)2(acac)、Co (acac)2、CoCl2One or more than two of the above; the precursor of Ir is Ir (CO)3(acac) or Ir (CH)3COO)3、Ir(acac)3、IrCl4One or more than two of the above; the precursor of Ru is dichloro (cyclooctyl-1, 5-diene) ruthenium (II) and RuCl3、Ru(acac)3Dodecacarbonyltriruthenium, [ RuAr ]2(benzene)]2、 [RuAr2(p-cymene)]2、[RuAr2(mesitylene)]2、[(π-ally)Ru(cod)]2、 [(π-ally)Ru(nbd)]2One or more than two of the above; the precursor of Pt is Pt (acac)2、PtCl4、PtCl2(NH3)2One or more than two of the above; the precursor of Pd is Pd (CH)3COO)2、Pd(acac)2、 PdCl2、Pd(PPh3)4、PdCl2(CH3CN)2One or more than two of (a); the precursor of Fe is Fe (acac)3、FeCl3、FeCl2One or more than two of FeS, ferrocene and nonacarbonyl diiron, and the metal loading range in the catalyst is 0.01-10 wt%, preferably 0.1-3 wt%.
The reaction principle of the invention is as follows:
the invention creatively introduces alkylene onto a secondary phosphine oxide organic monomer, and utilizes the polymerization reaction of alkylene on monomer molecules to prepare a functional polymer carrier with developed pores. The coordination of P and metal in the phosphine oxide polymer phase can form a high-performance catalyst suitable for propylene hydroformylation, and due to the unique electronic effect and steric effect of secondary phosphine oxide, the catalyst prepared after the vinyl phosphine oxide is crosslinked with styrene and the like (L1-L6 in the claims), the catalyst prepared after the vinyl phosphine oxide is crosslinked with vinyl monodentate phosphine ligand and the like (L25-L43 in the claims), the catalyst prepared after the vinyl phosphine oxide is crosslinked with vinyl monodentate phosphine ligand and the like (L7-L24 in the claims), the positive-to-differential ratio in propylene hydroformylation is more than 1.5, and the catalyst prepared after the vinyl phosphine oxide is crosslinked with vinyl polydentate phosphine ligand and the like (L7-L24 in the claims), and the positive-to-differential ratio is between 10 and 50. The proportion of the n-butyraldehyde and the isobutyraldehyde is flexible and adjustable. The active metal component can be dispersed in the phosphine oxide supported catalyst in a monoatomic or ionic manner, so that the metal utilization efficiency is greatly improved. The carrier phosphine oxide polymer skeleton has higher P concentration, is easy to form double or multiple metal-P coordination bonds with the active metal component, and the coordination bonds have stronger bonding capability, so that the active component is not easy to lose, and the catalyst has long-range stability and is suitable for industrial application.
The invention has the beneficial effects that:
the heterogeneous catalyst provided by the invention has good performance in propylene hydroformylation reaction, the ratio of n-butyraldehyde and isobutyraldehyde is flexible and adjustable, the normal-iso ratio is 0.5-50, the content of propane as a byproduct is lower than 0.1%, the supported catalyst has good stability, and the catalyst is simple and efficient to separate from reactants and products. The supported catalyst is suitable for reactors such as fixed bed, slurry bed, kettle reactor and trickle bed. Compared with the traditional propylene hydroformylation catalyst taking triphenylphosphine as a ligand, the catalyst has higher catalytic activity; the catalyst is stable to air and moisture, and the operation conditions are not required to be harsh. The method for propylene hydroformylation based on the phosphine oxide supported catalyst is green and environment-friendly, and has low pollutant emission. The phosphine oxide supported catalyst is suitable for reaction processes of fixed beds, slurry beds, kettle reactors, trickle beds and the like, and the method for producing butyraldehyde by the hydroformylation reaction of propylene can obviously improve the conversion rate of olefin and regulate the normal-to-iso ratio of aldehyde products. Meanwhile, the catalyst and the method provided by the patent can solve the problems of poor stability and selectivity, serious loss of metal components and the like existing for a long time in the heterogenization process of the olefin hydroformylation reaction. The cost of the propylene hydroformylation industrial production is reduced, the catalyst has good stability, and the separation of reactants and products from the catalyst is simple and efficient, thereby providing a new industrialized technology for producing butyraldehyde by propylene hydroformylation.
Drawings
FIG. 1 is a diagram of distyrylphosphine oxide (secondary phosphine oxide ligand A)1H NMR spectrum.
FIG. 2 is a diagram of distyrylphosphine oxide (secondary phosphine oxide ligand A)13C NMR spectrum.
FIG. 3 is a drawing of distyrylphosphine oxide (secondary phosphine oxide ligand A)31P NMR spectrum.
Detailed Description
The following examples illustrate the invention better without limiting its scope.
Example 1
The preparation method comprises the following specific preparation steps: under the protection of Ar gas at 273K, 9 g of p-chlorostyrene is dissolved in 50ml of 2-methyltetrahydrofuran and is stirred uniformly for standby. 1.7 g of magnesium chips are put into a three-neck flask, the temperature of the flask is raised to about 60 ℃, about 5 ml of mixed solution of p-chlorostyrene and 2-methyltetrahydrofuran is dripped, after the color of the reaction solution becomes dark green, the rest mixed solution is continuously dripped after the reaction solution is boiled violently (initiated by a grignard reagent), and the dripping temperature is kept at 338K. After the dropwise addition, the reaction is continued for 1 hour at 65 ℃ to obtain the p-chlorostyrene Grignard reagent solution. And cooling to 273K, adding a mixed solution of 50ml of 2-methyltetrahydrofuran and 4.5g of diethyl phosphite, and continuing to perform heat preservation reaction for 1h after the dropwise addition is finished. 10 ml of 30 wt% NH4Cl solution is added for annihilation reaction, and the mixture is divided into two layers after standing.Taking out the upper oil layer, distilling under reduced pressure to remove solvent (60 deg.C) to obtain yellowish oily liquid, adding 10 ml n-heptane to heat the oily liquid to 60 deg.C for dissolving, cooling to 273K, recrystallizing, and drying to obtain distyrylphosphine oxide (vinyl secondary phosphine oxide ligand A)6.05 g (yield is about 73%, product is confirmed by nuclear magnetic and high resolution mass spectrometry), and figures 1-3 are nuclear magnetic of distyrylphosphine oxide A1H、13C and31and (4) a spectrum P.
Preparation of phosphine oxide porous organic polymers: 5.0g of distyrylphosphine oxide monomer A and 50.0g of a second component (ligand L2, CAS No. 100-42-5) of styrene were dissolved in 550 ml of tetrahydrofuran under Ar protection at 25 ℃, and then 0.01 g of a radical initiator AIBN (azobisisobutyronitrile) was added thereto and stirred for 2 hours to obtain a prepolymer solution. And transferring the prepolymer solution into an autoclave, and carrying out thermal polymerization for 24 hours at 100 ℃ under the Ar protective atmosphere by using a bulk polymerization method. After the polymerization kettle is cooled to room temperature, the solvent is removed in vacuum at room temperature, and the polymer CPOL-1SPO10VB (yield 100%) copolymerized by the distyrylphosphine oxide and the styrene is obtained. N of CPOL-1SPO10VB2The physical adsorption curve and the pore size distribution diagram show a multi-stage pore structure, the specific surface area is 924 m2/g calculated by the BET method, and the pore size is mainly distributed between 0.1 and 5nm calculated by the NLDFT method.
Phosphine oxide polymer supported highly dispersed rhodium-based catalysts: 298K, under the protection of Ar gas, 26.7mg of tris (triphenylphosphine) carbonyl rhodium hydride (I) (CAS number 17185-29-4) is weighed and dissolved in tetrahydrofuran solvent (10.0 ml), 1.0 g of the phosphine oxide polymer CPOL-1SPO10VB is added, the mixture is continuously stirred for 10 hours under the argon atmosphere at 25 ℃, and the solvent is removed under the vacuum condition of 318K, thus obtaining the phosphine oxide polymer self-supported high-dispersion catalyst Rh/CPOL-1SPO10VB, and the measured metal rhodium loading is 0.29%. And (5) observing the metal rhodium in a monodisperse state by using an STEM electron microscope. The thermogravimetric curve of the Rh/CPOL-1SPO10VB catalyst shows that under the nitrogen atmosphere, the catalyst has a weight loss peak of decomposition only at the temperature of more than 430 ℃, and is very stable at the temperature of less than 430 ℃.
Example 2
In example 2, the synthesis process and conditions were the same as in example 1 except that 50.0g of the second component styrene was not added.
Example 3
In example 3, the synthesis procedures and conditions were the same as those in example 1 except that 50.0g of divinylbiphenyl (ligand L4) as a second component was used in place of styrene (L2 in the claims).
Example 4
In example 4, the method and catalyst synthesis process and conditions were the same as in example 1 except that 1100.0ml of tetrahydrofuran was used instead of 550.0ml of tetrahydrofuran as a solvent in the ligand polymerization step.
Example 5
In example 5, the same procedure and conditions as in example 1 were repeated except that the tris (triphenylphosphine) rhodium (I) carbonylhydride was replaced with the same number of moles of cobalt (II) acetate, to thereby obtain a highly dispersed Co-based catalyst.
Example 6
In example 6, the highly dispersed Ir-based catalyst was obtained by following the same synthesis procedure and conditions as in example 1, except that the tris (triphenylphosphine) carbonylrhodium (I) hydride was replaced with the same molar amount of Ir (CH3COO) 3.
Example 7
In example 7, the synthesis procedures and conditions were the same as in example 1, except that tris (triphenylphosphine) carbonylrhodium (I) hydride was replaced with the same molar number of [ RuAr2 (bezene) ] 2.
Example 8
In example 8, the synthesis procedure and conditions were the same as in example 1, except that tris (triphenylphosphine) rhodium (I) carbonylhydride was replaced with the same molar amount of FeS.
Example 9
A comparative Rh/CPOL-10VB1PPh3 catalyst was prepared using the same synthetic procedures and conditions as in example 1, except that in example 9, the same moles of tris (4-vinylphenyl) phosphine were used in place of distyrylphosphine oxide monomer A.
Example 10
In example 10, the synthesis procedure and conditions were the same as in example 1 except that the same number of moles of ligand B was used instead of distyrylphosphine oxide monomer A.
Example 11
In example 11, the synthesis procedure and conditions were the same as in example 1 except that the same number of moles of ligand E was used in place of distyrylphosphine oxide monomer A.
Example 12
In example 12, the synthesis procedure and conditions were the same as in example 1 except that the same number of moles of ligand H was used in place of distyrylphosphine oxide monomer A.
Example 13
In example 13, the synthesis procedure and conditions were the same as in example 1 except that the same number of moles of ligand I was used in place of distyrylphosphine oxide monomer A.
Example 14
In example 14, the synthesis procedure and conditions were the same as in example 1 except that the same molar number of ligand O was used in place of the distyrylphosphine oxide monomer A.
Example 15
In example 15, the synthesis procedure and conditions were the same as in example 1 except that the same number of moles of ligand P was used in place of distyrylphosphine oxide monomer A.
Example 16
In example 16, the synthesis procedure and conditions were the same as in example 1 except that the same molar number of ligands R was used in place of the distyrylphosphine oxide monomer A.
Example 17
2g of the catalysts prepared in examples 1 to 16 were charged into a fixed bed reactor, and both ends were charged with quartz sand. Introducing reaction gas mixture (H)2:CO:C3H61:1:1, V/V/V), at 383K, 1.0MPa, and the space velocity of reaction mixture gas is 1000h-1The hydroformylation is carried out under the conditions. The reaction was collected by absorption in a collection tank containing 60ml of chilled deionized water and the reaction product was completely dissolved in the water in the collection tank. The aqueous solution obtained was subjected to HP-7890N gas chromatography using an HP-5 capillary column and a FID detectorAnalysis, ethanol was used as internal standard. The reaction tail gas after water absorption was analyzed on-line by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 1.
TABLE 1. example 1-example 16 catalyst specific surface area, pore size distribution and propylene hydroformylation Performance
Figure BDA0003541201170000101
Figure BDA0003541201170000111
The Rh catalyst coordinated with triphenylphosphine (comparative example) is prepared in example 9, and the Rh catalyst coordinated with phosphine oxide is prepared in example 1, and it can be seen from the reaction data of propylene hydroformylation that the Rh catalyst coordinated with phosphine oxide has higher hydroformylation activity, and the ratio of normal aldehyde to iso-aldehyde is low, which is irreplaceable for the case where isobutyraldehyde is required to be produced more. In examples 5, 6, 7 and 8, the active metal components were Co, Ir, Ru and Fe, respectively, and the reactivity was lower than that of the catalyst in which the active metal was Rh. When the active center is Rh, the data in the table show that the phosphine oxide coordinated Rh catalyst has higher propylene hydroformylation reaction activity than the triphenylphosphine coordinated Rh catalyst, and the aldehyde selectivity is better. The final catalyst aldehyde prepared by copolymerization of different phosphine oxide monomers and styrene has slightly different normal-to-iso ratios, when the periphery of P contains large steric hindrance groups, the normal-to-iso ratio of the aldehyde is slightly larger than 1, the catalyst aldehyde prepared by phosphine oxide monomer H in example 12 has a normal-to-iso ratio of up to 1.63, and the lowest normal-to-iso ratio of butyraldehyde can be about 0.7 (example 3).
Example 18
0.5g of the catalyst prepared in example 16 was charged into a 50 ml-capacity slurry bed reactor, 30ml of valeraldehyde was added as a slurry, and a reaction mixture gas (H) was introduced2:CO:C3H61:1:1), 398K, 1.0MPa, reaction mixture air speed 2000h-1And stirring at 750 revolutions per minuteAnd (3) performing hydroformylation reaction. The reaction was absorbed and collected in a collection tank containing 60ml of cooled deionized water, and the reaction product and the slurry liquid entrained with the tail gas were all dissolved in the water in the collection tank.
The conversion of propylene was 88.4%, the selectivity of butyraldehyde was 99.9%, and the normal-to-iso ratio of butyraldehyde was 1.45.
Example 19
The synthesis procedure was the same as in example 1 except that styrene (L2 in the claim) was replaced with the claimed second component, vinyl monodentate phosphine ligand (L25-L43 in the claim).
2g of the prepared catalyst is respectively loaded into a fixed bed reactor, and quartz sand is loaded at two ends of the fixed bed reactor. Introducing reaction gas mixture (H)2:CO:C3H61:1:1, V/V/V), at 403K, 1.0MPa, and the space velocity of reaction mixture gas is 1000h-1The hydroformylation reaction is carried out under the conditions. The reaction was collected by absorption in a collection tank containing 60ml of cooled deionized water, and the reaction product was completely dissolved in the water in the collection tank. The aqueous solution obtained was analysed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using ethanol as internal standard. The reaction tail gas after water absorption was analyzed on-line by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 2.
TABLE 2 specific surface area of secondary phosphine oxide and monophosphine ligand copolymerization catalyst and propylene hydroformylation Performance
Figure BDA0003541201170000112
Figure BDA0003541201170000121
As can be seen from the table, the catalyst prepared by crosslinking the vinylphosphine oxide with the vinyl monodentate phosphine ligand, etc., has a normal-to-iso ratio of more than 1.5 and less than 15 in the propylene hydroformylation, and the ratio of n-butyraldehyde to isobutyraldehyde of the product is flexible and adjustable. When the vinyl monophosphine ligand is selected from L25-L24, the normal-to-iso ratio of butyraldehyde is less than 10, and the vinyl position of the monophosphine ligand in L42 and L43 is closer to a P functional site, so that a pore channel confinement effect can be caused after polymerization, and the positive-to-iso ratio of the finally prepared catalyst butyraldehyde is respectively 10.4 and 13.5, and is slightly greater than 10 due to steric hindrance of a framework.
Example 20
The synthesis procedure was the same as in example 1 except that styrene (L2 in the claims) was replaced with the second component of vinyl-polyterthyrophosphine ligand (L7-L24 in the claims).
2g of the prepared catalyst is respectively loaded into a fixed bed reactor, and quartz sand is loaded at two ends of the fixed bed reactor. Introducing reaction gas mixture (H)2:CO:C3H61:1:1, V/V/V), 373K, 1.0MPa, and the space velocity of the reaction mixture gas is 1000h-1The hydroformylation is carried out under the conditions. The reaction was collected by absorption in a collection tank containing 60ml of cooled deionized water, and the reaction product was completely dissolved in the water in the collection tank. The aqueous solution obtained was analysed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using ethanol as internal standard. The reaction tail gas after water absorption was analyzed on-line by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 3.
TABLE 3 specific surface area and propylene hydroformylation Performance of the catalyst for copolymerization of Secondary phosphine oxide with multidentate phosphine ligand
Figure BDA0003541201170000122
Figure BDA0003541201170000131
As can be seen from the table, the catalyst prepared by crosslinking the vinylphosphine oxide, the vinyl-based polydentate phosphine ligand and the like has a normal-to-iso ratio of 10-50, and the ratio of n-butyraldehyde to iso-butyraldehyde is flexible and adjustable. The conversion rate of the propylene is basically over 70 percent, the positive-to-differential ratio of the butyraldehyde product is basically 15-45, the positive-to-differential ratio of the product of the catalyst is greatly influenced by the structure of the multidentate phosphorus ligand, wherein the positive-to-differential ratio of the butyraldehyde product is high due to the fact that L13, L14, L15, L16 and L23 are high in steric hindrance effect, the positive-to-differential ratio of the prepared catalyst butyraldehyde is over 30, and the positive-to-differential ratio of the butyraldehyde product prepared by copolymerizing L13 and the vinyl phosphine oxide ligand is the highest and can reach 43.2.
Example 21
5g of the catalyst prepared in the embodiment 1 and the embodiment 9 is put into a quartz tube, and the catalyst is treated for 5 hours at 80 ℃, the air pressure is 1.1bar, and the space velocity is 1000h-1, so as to obtain the treated catalyst. 2g of the prepared catalyst is respectively loaded into a fixed bed reactor, and quartz sand is loaded at two ends of the fixed bed reactor. Introducing reaction gas mixture (H)2:CO:C3H61:1:1, V/V/V), at 403K, 1.0MPa, and the space velocity of reaction mixture gas is 1000h-1The hydroformylation reaction is carried out under the conditions. The reaction was collected by absorption in a collection tank containing 60ml of cooled deionized water, and the reaction product was completely dissolved in the water in the collection tank. The aqueous solution obtained was analysed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using ethanol as internal standard. The reaction tail gas after water absorption was analyzed on-line by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 4.
TABLE 4 catalyst specific surface area and propylene hydroformylation Performance after air treatment in examples 1 and 9
Figure BDA0003541201170000132
The Rh catalyst coordinated by triphenylphosphine (comparative example) was prepared in example 9, the Rh catalyst coordinated by phosphine oxide was prepared in example 1, and the propylene hydroformylation performance of example 9 was significantly decreased after air treatment (compare with data in table 1), probably due to the unstable oxidation of triphenylphosphine in air, while the hydroformylation performance of example 1 catalyst was not significantly changed after treatment, which shows that the phosphine oxide catalyst is stable to air and moisture, the catalyst stability is better, the operation condition is not required to be too severe, and the industrial production is more facilitated.
Comparative example 1
In comparative example 1, except that the same number of moles of vinyl monodentate phosphine ligand was used
Figure BDA0003541201170000141
The synthesis procedure was the same as in example 1 except that styrene (L2 in the claims) was replaced.
Comparative example 2
In comparative example 2, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003541201170000142
The rest of the synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer A was replaced.
Comparative example 3
In comparative example 3, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003541201170000143
The synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer A was replaced.
Comparative example 4
In comparative example 4, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003541201170000144
The synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer A was replaced.
Comparative example 5
In comparative example 5, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003541201170000151
The synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer A was replaced.
Comparative example 6
In comparative example 6, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003541201170000152
The synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer A was replaced.
Comparative example 7
In comparative example 7, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003541201170000153
The rest of the synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer A was replaced.
2g of the prepared catalyst is respectively loaded into a fixed bed reactor, and quartz sand is loaded at two ends of the fixed bed reactor. Introducing reaction gas mixture (H)2:CO:C3H61:1:1, V/V/V), at 403K, 1.0MPa, and the space velocity of reaction mixture gas is 1000h-1The hydroformylation is carried out under the conditions. The reaction was collected by absorption in a collection tank containing 60ml of chilled deionized water and the reaction product was completely dissolved in the water in the collection tank. The aqueous solution obtained was analysed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using ethanol as internal standard. After absorption with water, the reaction off-gas was analyzed on-line by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 5.
TABLE 5 comparative examples 1-2 catalyst specific surface area and propylene hydroformylation data
Figure BDA0003541201170000154
Figure BDA0003541201170000161
As can be seen from the table, when the second component was selected as a triphenylphosphine ligand with two vinyl groups in the ortho-position upon polymerization, the specific surface area of the catalyst prepared after copolymerization with the secondary phosphine oxide A monomer was 687m2/g, but the propylene conversion was only 16.9, which is significantly lower than the data in example 1 (comparative example 1). When the ortho position of the secondary phosphine oxide has a large steric hindrance group, the propylene hydroformylation performance of the prepared catalyst is obviously influenced (comparative examples 2, 3 and 5), the F atom is arranged on the C ortho position connected with the secondary phosphine oxide ligand P, the activity of the propylene hydroformylation reaction is also obviously reduced (comparative examples 4 and 6), the propylene conversion rate of the catalyst prepared by copolymerizing the monomer and the styrene in the comparative example 7 is 11.1 percent and is obviously lower than that of the catalyst prepared in the example 1 (Table 1, the propylene conversion rate is 85.5 percent).

Claims (10)

1. A method for propylene hydroformylation reaction by using a phosphine oxide polymer supported catalyst, which is characterized in that:
in the presence of a phosphine oxide polymer supported catalyst, introducing propylene and synthesis gas to carry out hydroformylation reaction;
the phosphine oxide supported catalyst takes one or more than two of metals Rh, Co, Ir, Ru, Pt, Pd and Fe as active components, and takes phosphine oxide polymer as a carrier;
the phosphine oxide polymer is formed by self-polymerization of secondary phosphine oxide ligand containing alkylene or copolymerization of the secondary phosphine oxide ligand containing alkylene and second component containing alkylene;
the secondary phosphine oxide ligand containing alkylene is one or more than two of the following:
Figure FDA0003541201160000011
the second component containing an alkenyl group is selected from one or more of the following:
Figure FDA0003541201160000021
Figure FDA0003541201160000031
Figure FDA0003541201160000041
2. the process for the hydroformylation of propylene according to claim 1, wherein:
the secondary phosphine oxide ligand comprising an alkylene group and the second component alkylene group comprising an alkylene group used in the polymerization are preferably vinyl functional groups.
3. The method for the hydroformylation of propylene according to claim 1, wherein the catalyst obtained by the preparation is charged into a reactor, and the raw material propylene and a mixed gas containing a major component of H are introduced2And CO, H2The volume content of + CO is 20-100% (preferably 50-100%), H2The volume ratio of/CO is 0.5-5.0 (preferably 0.5-2.0), and the rest gas component is CO2、N2One or more than two of He and Ar gas; the purity of the raw material propylene is 20-100% (preferably 50-100%), and the rest gas components are CO2、N2One or more than two of He and Ar gas; the reaction temperature is 323-453K (preferably 323-403K), the reaction pressure is 0.1-5.0 MPa (preferably 0.5-4.0 MPa), and the gas space velocity of the mixed gas is 100-10000 h-1(preferably 500 to 5000 hours)-1) The space velocity of propylene is 0.01-20.0 h-1(preferably 0.1-8.0) and performing hydroformylation reaction, wherein the reactor is a fixed bed, a slurry bed, a trickle bed or a kettle reactor.
4. The process for the hydroformylation of propylene according to claim 1, wherein: the loading range of the metal active component in the catalyst is 0.01-10 wt%, and preferably 0.01-3 wt%.
5. The process for the hydroformylation of propylene as claimed in claim 1, wherein the hydroformylation is carried out in the presence of a catalyst: the phosphine oxide polymer carrier has a hierarchical pore structure and a specific surface area of 10-3000m2A preferred range is 100-2Per g, pore volume of 0.1-10.0cm3In terms of/g, preferably from 0.3 to 2.0cm3(ii)/g, pore size distribution is 0.01-100.0nm, preferably 0.1-5.0 nm;
the metal loading of the active component in the catalyst is in the range of 0.01-10 wt%, and the preferable range is 0.1-3 wt%.
6. The process for the hydroformylation of propylene according to claim 1, wherein:
the phosphine oxide polymer is prepared by the following steps:
after a secondary phosphine oxide ligand containing alkylene is dissolved or the secondary phosphine oxide containing alkylene and a second component containing alkylene are dissolved and mixed, initiating the alkylene in the organic phosphine ligand to carry out polymerization reaction by a free radical initiator to generate a phosphine oxide polymer carrier with a hierarchical porous structure;
the preparation process of the phosphine oxide polymer supported catalyst comprises the following steps: and fully stirring and coordinating a precursor of the active metal component and the phosphine oxide polymer carrier in a solvent, forming a firm chemical bond between the active metal component and the exposed P in the phosphine oxide polymer carrier, and evaporating the solvent to obtain the phosphine oxide polymer supported catalyst.
7. The process for the hydroformylation of propylene according to claim 1, wherein:
the specific preparation steps of the phosphine oxide supported catalyst are as follows:
a) under an inert gas atmosphere 273-473K (preferably 298-433K), adding a secondary phosphine oxide ligand containing alkylene or adding the secondary phosphine oxide ligand containing alkylene and a second component containing alkylene into a solvent, adding a free radical initiator, and stirring the mixture for 0.1-100 hours to obtain a prepolymer solution, wherein the preferable stirring time range is 0.1-20 hours;
b) transferring the prepolymer mixed solution prepared in the step a) into a polymerization reactor, and carrying out polymerization reaction for 1-100 hours by adopting one or more methods of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like to obtain a phosphine oxide polymer;
c) removing the solvent from the phosphine oxide polymer obtained in the step b) under 273-403K to obtain the phosphine oxide polymer with the hierarchical pore structure, namely the carrier of the phosphine oxide polymer supported catalyst;
d) adding the phosphine oxide polymer carrier obtained in the step c) into a solvent containing an active metal component precursor under an inert gas atmosphere of 273-; the concentration of the active metal in the precursor solution is in the range of 0.001-1mol L-1(preferably 0.01-1mol L)-1)。
8. The process for the hydroformylation of propylene according to claim 7, wherein: the solvent in the steps a) and d) is one or more than two of methanol, ethanol, dichloromethane, trichloromethane, benzene, toluene, xylene, water or tetrahydrofuran;
the free radical initiator in the step a) is one or more than two of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, cyclohexanone peroxide or dibenzoyl peroxide.
9. The process for the hydroformylation of propylene according to claim 7, wherein: the molar ratio of secondary alkylene-containing phosphine oxide ligand to second alkylene-containing component described in step a) is from 0.01:1 to 100:1, preferably from 1:1 to 1:10, and the molar ratio of secondary alkylene-containing phosphine oxide ligand to free-radical initiator is from 500:1 to 10:1, preferably from 100:1 to 10: 1. The concentration of the secondary phosphine oxide containing an alkylene group in the solvent before polymerization to an organic polymer is in the range of 0.01 to 1000g/L, preferably 0.1 to 10 g/L; the inert gases in the steps a), b) and d) are respectively selected from Ar, He and N2And CO2One or more than two of them.
10.The process for the hydroformylation of propylene according to claim 7, wherein: the active component is one or more than two of Rh, Co, Ir, Ru, Pt, Pd or Fe, wherein the precursor of Rh is RhH (CO) (PPh)3)3、Rh(CO)2(acac)、RhCl3、Rh(CH3COO)2One or more than two of (a); the precursor of Co is Co (CH)3COO)2、Co(CO)2(acac)、Co(acac)2、CoCl2One or more than two of (a); ir precursors are Ir (CO)3(acac) and Ir (CH)3COO)3、Ir(acac)3、IrCl4One or more than two of (a); the precursor of Ru is dichloro (cyclooctyl-1, 5-diene) ruthenium (II) and RuCl3、Ru(acac)3Dodecacarbonyltriruthenium, [ RuAr)2(benzene)]2、[RuAr2(p-cymene)]2、[RuAr2(mesitylene)]2、[(π-ally)Ru(cod)]2、[(π-ally)Ru(nbd)]2One or more than two of the above; the precursor of Pt is Pt (acac)2、PtCl4、PtCl2(NH3)2One or more than two of (a); the precursor of Pd is Pd (CH)3COO)2、Pd(acac)2、PdCl2、Pd(PPh3)4、PdCl2(CH3CN)2One or more than two of the above; the precursor of Fe is Fe (acac)3、FeCl3、FeCl2One or more than two of FeS, ferrocene and nonacarbonyl diiron, and the metal loading range in the catalyst is 0.01-10 wt%, preferably 0.1-3 wt%.
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