CN113058652B - Zirconium gallate catalyst and application thereof in selective hydrogenation reaction of crotonaldehyde - Google Patents

Zirconium gallate catalyst and application thereof in selective hydrogenation reaction of crotonaldehyde Download PDF

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CN113058652B
CN113058652B CN202110292486.0A CN202110292486A CN113058652B CN 113058652 B CN113058652 B CN 113058652B CN 202110292486 A CN202110292486 A CN 202110292486A CN 113058652 B CN113058652 B CN 113058652B
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crotonaldehyde
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gallate
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王海军
李晓宁
李叶惠
王祥
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    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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Abstract

The invention discloses a zirconium gallate catalyst and application thereof in crotonaldehyde selective hydrogenation reaction, belonging to the technical field of catalytic transfer hydrogenation. The invention takes gallic acid and zirconium salt as raw materials, and the gallic acid and the zirconium salt are mixed according to a specific molar ratio for reaction, so as to prepare the zirconium gallate catalyst for preparing crotyl alcohol by catalyzing crotonaldehyde with excellent selectivity. The method has simple synthesis steps, the used raw materials are cheap and easy to obtain, and the prepared zirconium gallate catalyst can efficiently catalyze the selective conversion of crotonaldehyde into crotyl alcohol; meanwhile, the catalyst prepared by the invention is easy to separate after reaction, can be repeatedly used, meets the requirement of green sustainable development, and has very good industrial application prospect.

Description

Zirconium gallate catalyst and application thereof in selective hydrogenation reaction of crotonaldehyde
Technical Field
The invention relates to a zirconium gallate catalyst and application thereof in crotonaldehyde selective hydrogenation reaction, belonging to the technical field of catalytic transfer hydrogenation.
Background
The selective hydrogenation of unsaturated aldehydes to unsaturated alcohols is an important industrial process in the fields of organic synthesis, pharmaceutical industry, cosmetics and food. According to different hydrogen supply modes, the method is divided into gas-phase hydrogenation and liquid-phase hydrogenation. According to the difference of hydrogen source, it is divided into hydrogen source and non-hydrogen source. The non-hydrogen source of hydrogen is typically formic acid or alcohols, wherein formic acid is corrosive and easily consumes equipment. When alcohols are used as hydrogen source, the principle is that hydrogen is supplied by transfer hydrogenation, carbonyl obtains hydrogen, and alcohols are dehydrogenated to finally become ketone. The early research mostly adopts a gas phase hydrogenation mode, and most of the research in recent years adopts a liquid phase hydrogenation mode to carry out the reaction.
Crotyl alcohol is a representative α, β -unsaturated alcohol compound and important organic synthetic intermediate, and is widely used in various fields such as pharmaceutical intermediates, fine chemicals, and perfumes. Currently, hydrogen is generally used as a hydrogen source for catalyzing the reduction of crotonaldehyde to crotyl alcohol, and catalysts used include Pt-based, Ir-based and other noble metal catalysts. For example, Hongqinghong, etc., a series of supported Ir/FeO are synthesizedx/SiO2A catalyst having a crotyl alcohol conversion of 95% under optimal reaction conditions but in the presence of a reactionToo long time and high reaction energy consumption; shi et al synthesized Pt3Sn/SnO2The catalyst has the advantages that the conversion rate of crotyl alcohol is more than 99% and the selectivity is about 90% under the optimal reaction condition, but the catalyst has the defect of complicated preparation; xu et al synthesized a series of Ir-xMo/TUD-1 catalysts with crotyl alcohol yields of about 86.7% under optimal reaction conditions, which suffered from the disadvantages of cumbersome catalyst preparation and expensive raw material metals used in the preparation process.
Although hydrogenation using hydrogen as a hydrogen source can achieve a good catalytic effect, high pressure is required when hydrogen is used as a hydrogen source. This requires high reaction equipment, is costly and risky, and is economically not valuable for large-scale industrial applications. Therefore, the design and preparation of efficient catalysts and the choice of hydrogen source are critical to improve process efficiency and economics.
Disclosure of Invention
[ problem ] to
Some catalysts have been developed for selective hydrogenation of crotonaldehyde into crotyl alcohol, but these catalysts have problems of complicated synthesis process, use of expensive noble metal raw materials, and the like. In particular, in the selective hydrogenation of crotonaldehyde, the use of H is also present2Low selectivity and yield of the target product.
[ solution ]
In order to solve the problems, gallic acid is selected as a ligand for the first time, hydroxyl on a benzene ring is coordinated with zirconium through a coprecipitation method, the structure can provide an acid site and a basic site which are necessary for reaction, and compared with other reported catalysts, the catalyst zirconium gallate (Zr-GA) prepared by the method has the advantages of abundant and easily available raw materials, simple preparation process, no excessive energy loss and the like.
The invention provides a method for preparing a zirconium gallate catalyst for selectively catalyzing crotonaldehyde to prepare crotyl alcohol, which takes gallic acid and zirconium salt as raw materials according to a molar ratio of 1: (1-4) mixing and reacting, after the reaction is finished, carrying out solid-liquid separation, collecting the solid, and drying.
In one embodiment of the invention, the method comprises: respectively dispersing gallic acid and zirconium salt in a solvent to obtain corresponding gallic acid solution and zirconium salt solution; then, the zirconium salt solution is dripped into the gallic acid solution to be mixed and stirred for reaction, and after the reaction is finished, the mixture is washed and dried to obtain the zirconium gallate catalyst (abbreviated as Zr-GA).
In one embodiment of the invention, the zirconium salt solution used in the method is ZrCl4In DMF.
In one embodiment of the present invention, the molar ratio of gallic acid to zirconium in the zirconium salt solution in the method may be preferably 1:2, mixing.
In one embodiment of the invention, the reaction is carried out by continuously stirring for 2-4 h at room temperature (20-30 ℃), and then standing and aging for 5-8 h at 70-90 ℃.
In one embodiment of the invention, after the reaction is finished, performing suction filtration at normal pressure, collecting solid filter residue, washing the filter residue 3-5 times with DMF (dimethyl formamide) and 3-5 times with isopropanol, and drying the washed filter residue in a vacuum drying oven overnight to obtain the catalyst Zr-GA.
The invention provides a zirconium gallate catalyst for selectively catalyzing crotonaldehyde to prepare crotyl alcohol by utilizing the method.
The invention provides a method for preparing crotyl alcohol by catalyzing selective hydrogenation reduction of crotonaldehyde, which takes zirconium gallate as a catalyst.
In one embodiment of the invention, the method for preparing crotyl alcohol by catalytic selective hydrogenation reduction of crotonaldehyde is to perform a reduction reaction by using crotonaldehyde as a substrate and zirconium gallate as a catalyst; wherein the mass ratio of the catalyst to the crotonaldehyde is (0.625-2.5): 1.
in one embodiment of the invention, the reaction temperature of the reduction reaction is 110-150 ℃; preferably 120-150 ℃; further preferably 130 ℃ and 150 ℃.
In one embodiment of the invention, the reaction time of the reduction reaction is 0.5-2 h; preferably 1-2 h; further preferably 1.5 h.
In one embodiment of the present invention, the reduction reaction is carried out in a solvent, which is isopropanol.
In one embodiment of the present invention, the initial reaction concentration of crotonaldehyde to solvent in the reduction reaction is from 8mg/mL to 10 mg/mL.
In an embodiment of the present invention, in the method for preparing crotyl alcohol by catalytic selective hydrogenation reduction of crotonaldehyde, the mass ratio of the catalyst to crotonaldehyde may be preferably 5: 4.
the invention provides the zirconium gallate catalyst, a method for preparing the catalyst and application of the method for catalyzing selective hydrogenation reduction of crotonaldehyde into crotyl alcohol in pharmaceutical intermediates, fine chemicals and essence perfumes.
Has the advantages that:
(1) according to the invention, gallic acid and zirconium salt are adopted for the first time to prepare the catalyst Zr-GA, and the catalyst is used for catalyzing selective hydrogenation reduction of crotonaldehyde into crotyl alcohol, the raw materials of the prepared catalyst are easy to obtain and low in price, the preparation conditions are mild, the preparation efficiency is high, and the yield is between 60% and 80%;
(2) the catalyst disclosed by the invention is simple in preparation process, is a heterogeneous catalyst, is easy to separate after reaction, and accords with the green sustainable development strategy;
(3) the reaction conditions for catalyzing the conversion of the carbonyl compound into the alcohol are mild, the reaction temperature is 383K-413K, the reaction time is 0.5-2 h, and the yield of the crotyl alcohol obtained by catalyzing the selective hydrogenation reduction of the crotonaldehyde is high and reaches more than 92%. For example, the crotyl alcohol yield can reach 92.37% after the reaction is carried out for 1.5h at the temperature of 403K.
Drawings
FIG. 1 is an XRD spectrum of Zr-GA (1:2) obtained in example 1.
FIG. 2 is a scanning electron micrograph of Zr-GA (1:2) obtained in example 1.
FIG. 3 is a transmission electron micrograph of Zr-GA (1:2) obtained in example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Determination of crotyl alcohol yield and crotonaldehyde conversion by gas chromatography:
the gas chromatograph parameters were set as follows: the temperature of a column box is 150 ℃, the temperature of a detector is 200 ℃, and the temperature of an auxiliary I is 200 ℃; each injection sample is 0.3 μ L.
Figure BDA0002982851760000031
Figure BDA0002982851760000032
EXAMPLE 1 Synthesis of catalyst zirconium gallate (Zr-GA)
The Zr-GA catalyst is synthesized by the following steps:
0.466g of zirconium chloride and 0.172g of gallic acid in DMF were mixed to give a mixture with a concentration of 0.1mol L-1And the concentration of the zirconium chloride solution is 0.05mol L-1The gallic acid solution and the zirconium chloride solution are respectively mixed according to the molar ratio of gallic acid to zirconium chloride of 1:1, 1:2, 1:3 and 1:4, the mixture is continuously stirred for 2h at room temperature, kept stand and aged for 8h at 80 ℃, the mixture is filtered under normal pressure after stirring, the filter residue is washed by isopropanol for 5 times and DMF for 5 times, and the washed filter residue is dried in a vacuum drying oven for overnight, so that the yield of the catalyst Zr-GA (1:1) is 63.57%, the yield of the Zr-GA (1:2) is 78.28%, the yield of the Zr-GA (1:3) is 64.23% and the yield of the Zr-GA (1:4) is 72.92%.
Figure BDA0002982851760000041
m (vacuum drying to obtain catalyst): the quality of the catalyst obtained after vacuum drying;
m (gallic acid + zirconium oxychloride): the sum of the mass of the gallic acid and the zirconium chloride used as raw materials for preparing the catalyst.
Example 2
(1) 0.08g crotonaldehyde and 100mg of the catalyst Zr-GA (1:2) prepared in example 1 were weighed into a reaction vessel containing 10mL of isopropanol;
(2) placing the reactors in 130 deg.C oil bath, stirring for 1 hr and 1.5 hr, cooling, collecting 0.3 μ L solution after reaction, and measuring crotyl alcohol yield and crotonaldehyde conversion rate with gas chromatograph, wherein the crotonaldehyde conversion rate is 88.92% and the crotyl alcohol yield is 83.72% after stirring for 1 hr in 130 deg.C oil bath; the reaction was stirred in an oil bath at 130 ℃ for 1.5h to give crotonaldehyde with 95.63% conversion and crotyl alcohol yield of 92.37%.
XRD test and transmission electron micrograph of the catalyst Zr-GA (1:2) used in this example were taken.
FIG. 1 is an XRD spectrum of Zr-GA (1:2) in example 2. FIG. 2 is a scanning electron micrograph of Zr-GA (1:2) in example 2. FIG. 3 is a transmission electron micrograph of Zr-GA (1:2) in example 2. It can be seen from fig. 1 that Zr — GA is an amorphous structure, and from fig. 2 and 3, it can be seen that the catalyst is porous and has no uniform shape, many voids exist between particles, and the particles are nano-sized.
Example 3
(1) 0.08g crotonaldehyde and 100mg of the catalyst Zr-GA (1:2) prepared in example 1 were weighed into a reaction vessel containing 10mL of isopropanol;
(2) placing the reactors in an oil bath at 140 deg.C respectively, stirring for 1 hr and 1.5 hr, cooling, and measuring crotyl alcohol yield and crotonaldehyde conversion rate with gas chromatograph from 0.3 μ L of the reacted solution, wherein the crotonaldehyde conversion rate is 91.24% and the crotyl alcohol yield is 89.21% after stirring for 1 hr in the oil bath at 140 deg.C; stirring and reacting for 1.5h in an oil bath kettle at the temperature of 140 ℃ to obtain the crotonaldehyde with the conversion rate of 92.77% and the crotyl alcohol yield of 90.03%.
Example 4
(1) 0.08g crotonaldehyde and 100mg of the catalyst Zr-GA (1:2) prepared in example 1 were weighed into a reaction vessel containing 10mL of isopropanol;
(2) placing the reactors in an oil bath kettle at 120 deg.C respectively, stirring for reaction for 0.5h and 1h, cooling after reaction, and measuring crotyl alcohol yield and crotonaldehyde conversion rate with gas chromatograph from 0.3 μ L of reacted solution, wherein the crotonaldehyde conversion rate is 37.92% and the crotyl alcohol yield is 30.19% after stirring for reaction for 0.5h in the oil bath kettle at 120 deg.C; the reaction was stirred in an oil bath at 120 ℃ for 1h to give crotonaldehyde in 56.73% conversion and crotyl alcohol in 52.72% yield.
Example 5
(1) 0.08g crotonaldehyde and 100mg of the catalyst Zr-GA (1:2) prepared in example 1 were weighed into a reaction vessel containing 10mL of isopropanol;
(2) placing the reactor in an oil bath kettle at 150 deg.C, stirring for 1.5 hr and 2 hr, cooling, collecting 0.3 μ L of the solution after reaction, measuring crotyl alcohol yield and crotonaldehyde conversion rate with gas chromatograph, and stirring for 1.5 hr in the oil bath kettle at 150 deg.C to obtain crotonaldehyde conversion rate of 99.9% and crotyl alcohol yield of 87.32%; the crotonaldehyde conversion rate is 99.9 percent and the crotyl alcohol yield is 83.06 percent after stirring and reacting for 2 hours in an oil bath kettle at the temperature of 120 ℃.
Example 6
(1) 0.08g crotonaldehyde and 100mg of the catalyst Zr-GA (1:2) prepared in example 1 were weighed into a reaction vessel containing 10mL of isopropanol;
(2) placing the reactor in 150 deg.C oil bath, stirring for 0.5 hr and 1 hr, cooling, collecting 0.3 μ L solution after reaction, measuring crotyl alcohol yield and crotonaldehyde conversion rate with gas chromatograph, and stirring for 0.5 hr in 150 deg.C oil bath to obtain crotonaldehyde conversion rate of 57.72% and crotyl alcohol yield of 51.34%; the reaction was stirred in an oil bath at 150 ℃ for 1h to give crotonaldehyde with 83.14% conversion and crotyl alcohol yield of 78.49%.
Example 7
(1) 0.08g of crotonaldehyde, 100mg of the catalysts Zr-GA (1:1), Zr-GA (1:2), Zr-GA (1:3) and Zr-GA (1:4) prepared in example 1 were weighed into a reaction vessel containing 10mL of isopropanol;
(2) placing the reactors in 130 deg.C oil bath respectively, stirring for 1.5h, cooling after reaction, and measuring crotyl alcohol yield and crotonaldehyde conversion rate with GAs chromatograph from 0.3 μ L of reacted solution, wherein the crotonaldehyde conversion rate is 73.92% and the crotyl alcohol yield is 54.33% with Zr-GA (1:1) as catalyst; the conversion rate of crotonaldehyde obtained by using Zr-GA (1:2) as a catalyst was 95.63%, and the yield of crotyl alcohol was 92.37%; the conversion rate of crotonaldehyde obtained by using Zr-GA (1:3) as a catalyst was 91.74%, and the yield of crotyl alcohol was 79.32%; the conversion of crotonaldehyde was 89.30% and the yield of crotyl alcohol was 77.42% using Zr-GA (1:4) as the catalyst.
Example 8 recycle of catalyst for Secondary use in preparation of crotyl alcohol
(1) The solution obtained in example 2 was centrifuged to obtain Zr-GA (1:2) which had been used, washed several times with isopropanol, dried in a vacuum oven at 60 ℃ for 14 hours, and then 100mg of the solution was added to a reaction vessel containing 0.08g of crotonaldehyde and 10mL of isopropanol.
(2) The reactors were placed in 130 ℃ oil bath and stirred for 1.5 hours, after the reaction was completed and cooled, 0.3. mu.L of the reacted solution was taken and the crotyl alcohol yield and crotonaldehyde conversion rate were measured by gas chromatography. The conversion of crotonaldehyde was 93.34% and the crotyl alcohol yield was 90.21%.
Example 9 preparation of crotyl alcohol with three cycles of catalyst catalysis of crotonaldehyde
(1) The solution obtained after the reaction in example 8 was centrifuged to obtain Zr-GA (1:2) which had been used, washed several times with isopropanol, dried in a vacuum oven at 60 ℃ for 14 hours, and then 200mg of the solution was added to a reaction vessel containing 0.08g of crotonaldehyde and 10mL of isopropanol.
(2) The reactors were placed in 130 ℃ oil bath and stirred for 1.5 hours, after the reaction was completed and cooled, 0.3. mu.L of the reacted solution was taken and the crotyl alcohol yield and crotonaldehyde conversion rate were measured by gas chromatography. The conversion of crotonaldehyde was 90.76% and the yield of crotyl alcohol was 87.31%.
Example 10 preparation of crotyl alcohol with four cycles of catalytic crotonaldehyde with catalyst
(1) The solution obtained after the reaction in example 9 was centrifuged to obtain Zr-GA (1:2) which had been used, washed several times with isopropanol, dried in a vacuum oven at 60 ℃ for 14 hours, and then 100mg of the solution was added to a reaction vessel containing 0.08g of crotonaldehyde and 10mL of isopropanol.
(2) The reactors were placed in 130 ℃ oil bath and stirred for 1.5 hours, after the reaction was completed and cooled, 0.3. mu.L of the reacted solution was taken and the crotyl alcohol yield and crotonaldehyde conversion rate were measured by gas chromatography. The conversion of crotonaldehyde was 88.42% and the yield of crotyl alcohol was 84.72%.
Example 11 preparation of crotyl alcohol Using catalyst catalysis of crotonaldehyde five cycles
(1) The solution obtained in example 10 was centrifuged to obtain Zr-GA (1:2) which had been used, washed several times with isopropanol, dried in a vacuum oven at 60 ℃ for 14 hours, and then 100mg of the solution was added to a reaction vessel containing 0.08g of crotonaldehyde and 10mL of isopropanol.
(2) The reactors were placed in 130 ℃ oil bath and stirred for 1.5 hours, after the reaction was completed and cooled, 0.3. mu.L of the reacted solution was taken and the crotyl alcohol yield and crotonaldehyde conversion rate were measured by gas chromatography. The conversion of crotonaldehyde was 82.72% and the yield of crotyl alcohol was 79.39%.
Example 12
(1) 0.08g crotonaldehyde and 100mg of the catalyst Zr-GA (1:2) prepared in example 1 were weighed into a reaction vessel containing 5mL of isopropanol;
(2) placing the reactor in an oil bath at 130 deg.C, stirring for 1.5h, cooling, taking a small amount of solution after reaction, and measuring crotyl alcohol yield and crotonaldehyde conversion rate by GC to obtain crotonaldehyde conversion rate of 56.32% and crotyl alcohol yield of 49.26%.
Example 13
(1) 0.08g of crotonaldehyde and 200mg of the catalyst Zr-GA (1:2) prepared in example 1 were weighed into a reaction vessel containing 10mL of isopropanol;
(2) placing the reactor in 130 deg.C oil bath, stirring for 1.5h, cooling, collecting 0.3 μ L of the solution after reaction, and measuring crotyl alcohol yield and crotonaldehyde conversion rate with gas chromatograph to obtain crotonaldehyde conversion rate of 71.27% and crotyl alcohol yield of 65.43%.
Comparative example 1
(1) Weighing 0.08g of crotonaldehyde and 100mg of gallic acid, and adding the crotonaldehyde and the gallic acid into a reaction kettle containing 10mL of isopropanol;
(2) placing the reactor in 130 deg.C oil bath, stirring for 1.5h, cooling, collecting 0.3 μ L of the solution after reaction, and measuring crotyl alcohol yield and crotonaldehyde conversion rate with gas chromatograph to obtain crotonaldehyde conversion rate of 5.3% and crotyl alcohol yield of 0.77%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (4)

1. A method for preparing crotyl alcohol by catalyzing crotonaldehyde to carry out selective hydrogenation reduction is characterized in that crotonaldehyde is used as a substrate, and reduction reaction is carried out under the action of a zirconium gallate catalyst; wherein the mass ratio of the zirconium gallate catalyst to the crotonaldehyde is 0.625: 1;
the reduction reaction is carried out in a solvent, wherein the solvent is isopropanol; the initial reaction concentration of the crotonaldehyde relative to the solvent is 8mg/mL-10 mg/mL; the reaction temperature of the reduction reaction is 130-140 ℃;
the preparation method of the gallic acid zirconium catalyst takes gallic acid and zirconium salt as raw materials, and the molar ratio is 1:2 mixing and reacting, after the reaction is finished, carrying out solid-liquid separation, collecting the solid, and drying.
2. The method according to claim 1, wherein in the preparation method of the zirconium gallate catalyst, the reaction is performed by continuously stirring at room temperature for 2-4 hours, and then standing and aging at 70-90 ℃ for 5-8 hours.
3. The method of claim 1, wherein the preparation of the zirconium gallate catalyst comprises: respectively dispersing gallic acid and zirconium salt in a solvent to obtain corresponding gallic acid solution and zirconium salt solution; and then dropwise adding the zirconium salt solution into the gallic acid solution, mixing and stirring for reaction, and after the reaction is finished, washing and drying the mixture to obtain the zirconium gallate catalyst, which is abbreviated as Zr-GA.
4. The method according to any one of claims 1 to 3, wherein the reaction time of the reduction reaction is 0.5 to 2 hours.
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