CN108579740B - Preparation method and application of efficient catalyst for preparing aldehyde by olefin hydroformylation - Google Patents

Preparation method and application of efficient catalyst for preparing aldehyde by olefin hydroformylation Download PDF

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CN108579740B
CN108579740B CN201810328219.2A CN201810328219A CN108579740B CN 108579740 B CN108579740 B CN 108579740B CN 201810328219 A CN201810328219 A CN 201810328219A CN 108579740 B CN108579740 B CN 108579740B
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nitrate
sulfate
rhodium
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苏芃赫
黄唯平
揣宏媛
陈雅
刘晓彤
朱宝林
张守民
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Nankai University
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
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Abstract

The invention provides a preparation method of a high-efficiency catalyst for preparing aldehyde by olefin hydroformylation, wherein the catalyst is a supported catalyst and consists of a carrier and an active center, the carrier is a cation modified titanium dioxide nanotube, and the active center is nano metal rhodium; the preparation method of the catalyst comprises the following steps: and (2) obtaining a modified titanium dioxide nanotube carrier by adopting an immersion calcining method, then immersing the active center precursor on the carrier, and then reducing to obtain the heterogeneous catalyst. Compared with the traditional homogeneous catalyst, the catalyst provided by the invention has the characteristics of good catalytic performance, easy separation, prolonged service life and recycling use in the liquid phase reaction of preparing aldehyde by olefin hydroformylation, and has wide industrial application value.

Description

Preparation method and application of efficient catalyst for preparing aldehyde by olefin hydroformylation
Technical Field
The technical scheme of the invention relates to the field of preparation methods of supported catalysts, and particularly relates to a preparation method of a high-efficiency catalyst for preparing aldehyde by olefin hydroformylation.
Background
Hydroformylation is one of the classical reactions currently used in the chemical industry to produce aldehydes by the addition of olefins to synthesis gas under specific conditions of temperature, pressure and catalyst assistance. Hydroformylation of aldehyde products is the preparation of various fine chemicals, such as: plasticizers and the like and important pharmaceutical intermediates. In addition, a chiral product can be synthesized by hydroformylation of an asymmetric olefin (vinyl acetate) or the like, which is valuable in synthesis of pharmaceuticals, agricultural chemicals, natural products, and the like. Since the functional group of the olefin containing functional group can negatively affect the metal catalytic active center, the high regioselectivity control of the hydroformylation reaction of the functionalized olefin is still a hotspot and difficulty in the research field.
Another technical difficulty of homogeneous catalyst catalyzed hydroformylation of olefins is the separation of the catalyst from the product and the prevention of loss of the active component. The homogeneous catalysis system has high catalytic activity, good selectivity and mild reaction condition, and the olefin hydroformylation reaction is mainly the homogeneous catalysis system in industry. However, most of the catalytic active centers used in the reaction are noble metals, are easily dissolved in a reaction solvent, and are difficult to recover, so that a large amount of waste is caused, and the production cost is greatly increased.
The heterogeneous catalyst immobilization is an effective means for solving the problem that the catalyst and a product are difficult to separate, namely, a catalytic active center is riveted on a carrier under certain conditions, but the existing immobilized hydroformylation catalyst is poor in general reaction activity, and the industrialization way is hindered. Chinese patent CN10144475A discloses a method for preparing a catalyst with supported active rhodium complex by using mesoporous molecular sieve or silica as carrier, haloalkyl trimethylsilane and lithium diphenylphosphine as coupling agent, the catalyst obtained by the method has firm active center, is not easy to run off, can be well separated from the reaction system, but has poor catalyst activity and low olefin conversion rate. U.S. Pat. No. 3527809 discloses a preparation method of a rhodium-tertiary phosphine catalyst, which has the advantages of good reaction activity, mild reaction conditions and catalyst recovery, but because the product aldehyde and the catalyst are in a uniform solution, the catalyst can be recovered only by adopting a distillation or reduced pressure distillation method, the recovery method can cause energy waste, particularly for the separation of high-boiling-point aldehyde, and in addition, the method is ineffective for the temperature-sensitive product aldehyde, and can cause the decomposition and the conversion of the aldehyde.
In order to eliminate or reduce the influence of functional groups and solve the technical problem that the catalyst is difficult to recover, a novel functional catalyst with high conversion rate and aldehyde generation selectivity is developed by taking a titanium dioxide nanotube with high specific surface area and a one-dimensional structure after being modified by metal cations as a carrier. The modified titanium dioxide nanotube can effectively disperse and support metal active centers, improve the reaction activity and stability of the catalyst, and overcome the defect that the catalyst and a product are difficult to separate in a homogeneous system. The catalyst has the characteristics of good catalytic activity and good stability, and is suitable for industrial application.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a preparation method of a high-efficiency catalyst for preparing aldehyde by olefin hydroformylation. The method takes cation modified titanium dioxide nanotubes as a carrier and adopts an impregnation-reduction method to prepare the olefin hydroformylation catalyst with high reaction activity and stability. So as to overcome the defect that the catalyst and the product are difficult to separate in the traditional homogeneous system; so as to overcome the defects of poor catalyst activity and the like.
The technical scheme adopted by the invention for solving the problem is as follows:
a preparation method of a high-efficiency catalyst for preparing aldehyde by olefin hydroformylation comprises the following steps:
(1) preparing a chloride, nitrate, sulfate or dihydrogen phosphate aqueous solution containing modified cations for later use;
(2) putting a certain amount of titanium dioxide nanotubes into a flask, adding a proper amount of the aqueous solution, stirring, centrifuging, drying and calcining for later use;
(3) preparing a rhodium trichloride aqueous solution, putting the rhodium trichloride aqueous solution into a round-bottom flask, adding the modified titanium dioxide nanotube carrier obtained in the step (2) under a stirring condition, and stirring at normal temperature for 2-24 hours;
(4) then centrifugally transferring the mixture in the step (3) to a light reaction tube, and reducing by illumination;
(5) and (4) centrifuging and drying the product obtained in the step (4) to obtain the modified titanium dioxide nanotube supported rhodium catalyst.
The chloride in the step (1) of the technical scheme can be sodium chloride, potassium chloride, calcium chloride, strontium chloride and magnesium chloride. The nitrate can be sodium nitrate, potassium nitrate, calcium nitrate, strontium nitrate, and magnesium nitrate. The sulfate can be sodium sulfate, potassium sulfate, calcium sulfate, strontium sulfate, and magnesium sulfate. The dihydric phosphate can be sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, strontium dihydrogen phosphate, and magnesium dihydrogen phosphate.
The invention has the following advantages:
1. the modified titanium dioxide nanotube loaded rhodium catalyst obtained by the method is provided. The modified nanotube has higher specific surface area, and is beneficial to the exposure of catalytic active sites and the diffusion of substrates. As shown in FIG. 1, no diffraction peak of rhodium is found in the X-ray diffraction test result of the modified titanium dioxide nanotube, which indicates that the nano metal rhodium is highly dispersed in the modified titanium dioxide nanotube. As shown in fig. 2, rhodium nanoparticles (about 1-3nm in size) were uniformly distributed on the surface and inside of the modified nanotubes.
2. The method adopted by the invention is simple and effective, has few process steps, is green and environment-friendly, and has low cost.
3. The raw materials of chloride, nitrate, sulfate, dihydric phosphate, sodium hydroxide, rhodium trichloride and the like are all common chemical reagents.
4. The catalyst prepared by the invention is suitable for mass production and can be used for industrial mass production.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is an XRD spectrum of the modified titania nanotube catalyst of example 1, wherein (A) is modified titania nanotubes and (B) is the product after loading metal rhodium;
fig. 2 is a TEM spectrum of the modified titania nanotube catalyst in example 1, wherein (a) is the modified titania nanotube, and (B) is the product after loading metal rhodium.
Detailed Description
Example 1
(1) Preparing a sodium chloride aqueous solution with a certain concentration for later use;
(2) putting 1g of titanium dioxide nanotube into a flask, adding 20ml of the aqueous solution, stirring, centrifuging, drying, and calcining at 353K for later use;
(3) preparing a rhodium trichloride aqueous solution with the mass fraction of 0.5%, putting the rhodium trichloride aqueous solution into a round-bottom flask, adding the modified titanium dioxide nanotube carrier obtained in the step (2) under the stirring condition, and stirring at normal temperature for 2 hours;
(4) then, centrifugally transferring the mixture in the step (3) to a light reaction tube, and reducing for 2 hours by illumination;
(5) centrifuging and drying the product obtained in the step (4) to obtain the modified titanium dioxide nanotube loaded rhodium catalyst
(6) Weighing a certain amount of the obtained catalyst, reaction substrates of vinyl acetate and solvent of toluene, adding the catalyst, the reaction substrates of vinyl acetate and solvent of toluene into a high-pressure reaction kettle for a catalytic experiment, and calculating the catalytic activity of the catalyst according to gas phase data.
According to TEM test, the product is rhodium nano-particles with uniform size dispersed on the surface and in the interior of the sodium modified titanium dioxide nano-tube.
Example 2
The sodium chloride in step (1) in example 1 was changed to potassium chloride. The other steps are the same as in example 1. Example 2 was obtained.
Example 3
The sodium chloride in step (1) in example 1 was changed to calcium chloride. The other steps are the same as in example 1. Example 3 was obtained.
Example 4
The sodium chloride in step (1) in example 1 was changed to strontium chloride. The other steps are the same as in example 1. Example 4 was obtained.
Example 5
The sodium chloride in step (1) in example 1 was changed to magnesium chloride. The other steps are the same as in example 1. Example 5 was obtained.
Examples 6 to 10
The sodium chloride in step (1) in example 1 was changed to sodium nitrate, potassium nitrate, calcium nitrate, strontium nitrate, and magnesium nitrate, respectively. The other steps are the same as in example 1. The product was obtained as in examples 1-5.
Examples 11 to 15
The sodium chloride in step (1) in example 1 was changed to sodium sulfate, potassium sulfate, calcium sulfate, strontium sulfate, and magnesium sulfate, respectively. The other steps are the same as in example 1. The product was obtained as in examples 1-5.
Examples 16 to 20
The sodium chloride in step (1) in example 1 was changed to sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, strontium dihydrogen phosphate, and magnesium dihydrogen phosphate, respectively. The other steps are the same as in example 1. The product was obtained as in examples 1-5.
Examples 21 to 25
353K in step (2) in examples 1 to 5 was changed to 573K. The other steps are the same as in examples 1 to 5. The product obtained was the same as in examples 1 to 5.
Examples 26 to 30
The immersion stirring in step (3) of examples 1 to 5 was changed to immersion stirring for reaction for 24 hours, and the other steps were the same as in examples 1 to 5. The product obtained was the same as in examples 1 to 5.
Examples 31 to 35
The 0.5% in step (3) in example 1 was changed to 1%. The other steps are the same as in examples 1 to 5. The product was obtained as in examples 1-5.
Examples 36 to 40
The rhodium chloride in step (3) in examples 1 to 5 was changed to rhodium acetate, and the other steps were the same as in examples 1 to 5. The product obtained was the same as in examples 1 to 5.
Examples 41 to 45
The light irradiation time 2h in step (4) in examples 1 to 5 was changed to 6h, and the other steps were the same as in examples 1 to 5. The product obtained was the same as in examples 1 to 5.
Example 46
The reaction substrate in step (6) in example 1 was changed to cyclohexene, the solvent was changed to tetrahydrofuran, and the other steps were the same as in example 1. Example 46 was obtained.
Example 47
The reaction substrate in step (6) in example 2 was changed to cyclohexene, the solvent was changed to tetrahydrofuran, and the other steps were the same as in example 2. Example 47 was obtained.
Example 48
The reaction substrate in step (6) in example 3 was changed to cyclohexene, the solvent was changed to tetrahydrofuran, and the other steps were the same as in example 2. Example 48 was obtained.
Example 49
The reaction substrate in step (6) in example 4 was changed to cyclohexene, the solvent was changed to tetrahydrofuran, and the other steps were the same as in example 2. Example 49 was obtained.
Example 50
The reaction substrate in step (6) in example 5 was changed to cyclohexene, the solvent was changed to tetrahydrofuran, and the other steps were the same as in example 2. Example 50 was obtained.
Evaluation the above catalyst catalyzed hydroformylation of olefins in a GS-0.25 type autoclave. The specific experimental steps are as follows: 5ml of the reaction substrate, 0.4g of the catalyst and 65ml of the reaction solvent were placed in an autoclave, which was then closed. Firstly, a certain amount of CO gas is introduced to replace the air in the kettle, and the air is charged and discharged twice. After the replacement is finished, filling CO and H with total pressure of 6 volume ratio 1: 12. And after the pressure is stable, starting the heating device and the stirring device. When the temperature is close to 100 ℃, the heating voltage is reduced, and the reaction is carried out under the set constant temperature condition. And stopping the reaction after the preset reaction time is reached, and cooling the reaction kettle to room temperature. Firstly, discharging gas in a reaction kettle, opening the high-pressure kettle in a fume hood, taking out reaction mixed liquid (after centrifugally treating and separating a catalyst and the reaction liquid), and qualitatively and quantitatively analyzing a reaction sample by using GC-MS and Shimadzu GC-2014.
TABLE 1 hydroformylation reaction Performance of novel modified titanium dioxide nanotubes Supported rhodium catalyst
Catalyst numbering Conversion rate% Total selectivity of aldehyde produced% Branch to straight
Example 1 100 80.36 100∶0
Example 2 100 79.65 100∶0
Example 3 100 64.59 100∶0
Example 4 100 78.65 100∶0
Example 5 100 76.84 100∶0
Example 46 100 100 -
Example 47 100 98.35 -
Example 48 100 94.56 -
Example 49 100 92.65 -
Example 50 100 90.13 -
From the results in the table, the novel supported catalyst for the hydroformylation of olefins provided by the invention has the advantages of simple preparation method, simple reaction process and device, stable reaction performance, high yield, good catalyst recycling result, capability of effectively solving the problems of metal component loss or ligand loss, difficult catalyst recycling and the like in the prior art, and wide industrial application prospect, and can be used for reaction in a conventional high-pressure autoclave reactor.
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.

Claims (1)

1. A preparation method of an aldehyde catalyst by olefin hydroformylation comprises the following steps:
(1) preparing a chloride, nitrate, sulfate or dihydrogen phosphate aqueous solution containing modified cations for later use;
(2) putting a certain amount of titanium dioxide nanotubes into a flask, adding a proper amount of the aqueous solution, stirring, centrifuging, drying and calcining for later use;
(3) preparing a rhodium trichloride aqueous solution, putting the rhodium trichloride aqueous solution into a round-bottom flask, adding the modified titanium dioxide nanotube carrier obtained in the step (2) under a stirring condition, and stirring at normal temperature for 2-24 hours;
(4) then centrifugally transferring the mixture in the step (3) to a light reaction tube, and reducing by illumination;
(5) centrifuging and drying the product obtained in the step (4) to obtain the modified titanium dioxide nanotube-loaded rhodium catalyst, wherein nano metal rhodium is uniformly distributed on the surface and inside the modified nanotube, and the size of rhodium nanoparticles is 1-3 nm;
the chloride in the step (1) is sodium chloride, potassium chloride, strontium chloride and magnesium chloride; the nitrate is sodium nitrate, potassium nitrate, strontium nitrate, and magnesium nitrate; the sulfate is sodium sulfate, potassium sulfate, strontium sulfate, magnesium sulfate; the dihydric phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate, strontium dihydrogen phosphate, and magnesium dihydrogen phosphate.
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钛氧纳米管固载Rh催化剂催化腈基烯烃氢甲酰化反应性能;李君 等;《分子催化》;20161231;第30卷(第6期);摘要、1.1.2 固载活性金属Rh、表1 *

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