CN111298810A - Method for improving yield and selectivity of cinnamyl alcohol - Google Patents

Abstract

The invention relates to a method for improving the yield and selectivity of α -unsaturated aldehyde, particularly for the catalytic hydrogenation of cinnamaldehyde to cinnamyl alcohol, and the obtained PtCoS alloy nanoparticles in a cubic shape are used as a hydrogenation catalyst, so that the PtCoS alloy nanoparticles not only show good cinnamaldehyde selective hydrogenation performance, but also are beneficial to separation, recovery and utilization compared with the traditional liquid phase catalyst, and can effectively avoid a vulcanization passivation step before reaction.

Description

Method for improving yield and selectivity of cinnamyl alcohol

Technical Field

The invention belongs to the technical field of selective hydrogenation reaction, and particularly relates to a method for improving the yield and selectivity of α -unsaturated aldehyde, particularly cinnamic alcohol generated by catalytic hydrogenation of cinnamic aldehyde.

Background

α -unsaturated aldehyde is an important chemical raw material and intermediate, cinnamaldehyde (abbreviated as CAL) is the most representative compound in α -unsaturated aldehyde, and has two double bonds of C ═ O and C ═ C, so research on cinnamaldehyde hydrogenation has very important significance, and the selective hydrogenation product of C ═ C double bond phenylpropylaldehyde (HCAL) is an important perfume raw material and widely applied to various fragrance essences, especially the preparation of lilac, jasmine, rose and other essences.

The noble metal catalyst has the advantages of high activity, large treatment capacity, good catalyst stability, long service life, simple and convenient operation and the like, so the noble metal catalyst is more suitable for selective hydrogenation reaction than other catalysts. However, the catalyst is expensive, and the catalyst activity is too high in the initial stage of the reaction, so that the problems of carbon deposition and temperature runaway of the catalyst are caused. Therefore, the noble metal catalyst needs to be passivated with organic sulfides during the start-up of the hydrogenation process. But usually H is used after loading the catalyst₂S or organic sulfur is subjected to high-temperature purging, on one hand, gas leakage is easily caused and harms the life safety of human bodies and the environmental pollution, on the other hand, the requirement on start-up operation is higher, the production potential safety hazard is easily caused, and the consumption of energy consumption and human resources is increased, so that the preparation of the nano catalyst with the precious metal Pt and the non-precious metal S alloy has important significance on catalytic hydrogenation reaction.

How to further improve the catalytic activity, stability and catalytic selectivity of the Pt active center of the catalyst has been a major scientific and key technical problem concerned by scientists in the related field. In order to improve the catalytic activity of Pt, previous studies have mainly utilized the synergistic or electronic structure effect of two or more components by forming an alloy; and regulating the appearance of the nanocrystalline to change the atomic arrangement on the surface of the catalyst, and improving the catalytic selectivity of Pt on different reaction systems by utilizing the surface structure effect of catalytic reaction. At present, a solvothermal method is a commonly used synthesis method in the synthesis process of precious metal alloys, and has the advantages of low cost, environmental friendliness, clean surface and the like, but because the reduction potentials of different metal salts are greatly different, a problem for constructing a metal alloy and nonmetal composite alloy catalyst with a certain morphology is faced by scientists.

Disclosure of Invention

Aiming at the technical problems, the invention solves the technical problems that the traditional catalyst in the hydrogenation reaction of cinnamyl aldehyde is low in yield, difficult to recover and low in cinnamyl alcohol yield, and the existing Pt nano-structured catalyst is poor in catalytic selectivity, needs to be vulcanized in initial application, is high in preparation cost and the like, and provides the method for improving the yield and the selectivity of the generated cinnamyl alcohol.

In order to realize the purpose, the invention is realized by the following technical scheme:

the selective hydrogenation reaction of cinnamaldehyde is carried out in a 2ml high-pressure reaction kettle, 2mg of PtCoS alloy nano catalyst with cubic morphology is loaded into a reactor, and 1ml of toluene (solvent) and 0.2mmol of cinnamaldehyde reactant are rapidly added. Checking the tightness of the device, replacing air with hydrogen for 3 times, discharging oxygen in the reactor, pressurizing to 0.8MPa with hydrogen, and reacting the reactor in a temperature-controlled magnetic stirrer, wherein the experimental steps of the preparation method of the PtCoS alloy nano catalyst with the cubic morphology are as follows:

1. 100 mu L H₂PtCl₆(0.1M)、100μL CoCl₂(0.1M) and 240. mu.L NaOH (0.2M), 3mL Na₂SO₃(0.02M) was added to 4.56mL of deionized water to prepare a growth solution, which was left to stand and aged overnight;

2. to the growth solution, 800. mu.L of deionized water, 1mL of PVP (5 wt%), 200. mu.L of HCOOH, and 300mg of glycine were added under magnetic stirring, and stirred for 10 min.

3. The mixture was transferred to a 20mL reaction vessel and placed in an oven at 200 ℃ for 8 hours.

4. Centrifuging the reacted solution of step 3, and then adding deionized water: the mixed solution of ethanol 1:1 (mass ratio) was washed 3 times to obtain cubic PtCoS nanocrystals.

It is noted that, for the morphology regulation effect of glycine, previous research shows that glycine has an important effect on the morphology regulation of precious metal alloys and tends to form concave structures, but no research is currently applied to the morphology regulation of metal and nonmetal composite alloys, and in this research, we surprisingly found that, in the process of reducing a precursor by PVP, the synergistic effect of glycine and sulfite can promote metal and nonmetal composite alloys to form cubic alloys, and a nano linear PtCoS alloy is obtained without adding glycine, and for the cinnamaldehyde hydrogenation reaction, a cubic catalyst has extremely high selectivity for cinnamaldehyde hydrogenation to form cinnamyl alcohol, and has an important meaning for exploring a cinnamaldehyde catalytic hydrogenation mechanism.

The invention has the beneficial effects that: according to the preparation method, chloroplatinic acid, cobalt chloride and sodium sulfite are used as raw materials, PVP is used as a reducing agent, glycine is used as a shape regulating agent, the PtCoS alloy nano particles with the cubic shape are prepared through a hydrothermal method, energy consumption is reduced, and the preparation method is green and clean. The obtained PtCoS alloy nano particles with the cubic morphology not only show good selective hydrogenation performance of cinnamaldehyde, but also are beneficial to separation and recycling compared with the traditional liquid phase catalyst, can avoid passivation treatment of noble metal alloy before use, and has wide application prospect.

Drawings

FIG. 1 is TEM bright field and dark field patterns of PtCoS alloy nanoparticles prepared in example 1;

FIG. 2 is an EDS element area scan spectrum of PtCoS alloy nanoparticles prepared in example 1;

figure 3 is a cinnamaldehyde hydrogenation pathway of the present application;

FIG. 4 is a TEM spectrum of the PtCoS alloy nanoparticles prepared in comparative example 1.

Detailed Description

The following examples are intended to illustrate the practice and advantageous effects of the present invention, but are not to be construed as limiting the scope of the present invention.

Example 1

The selective hydrogenation of cinnamaldehyde was carried out in a 2ml autoclave, 2mg of catalyst was charged into the reactor, and 1ml of toluene (solvent) and 0.2mmol of cinnamaldehyde reactant were rapidly added. Checking the tightness of the device, replacing air with hydrogen for 3 times, discharging oxygen in the reactor, pressurizing to 0.8MPa with hydrogen, and reacting in a temperature-controlled magnetic stirrer. As shown in fig. 1, the hydrogenation products are cinnamyl alcohol (COL), phenylpropyl aldehyde (HCAL) and phenylpropyl alcohol (HCOL), and the conversion rate of CAL and the selectivity of hydrogenation products of the prepared PtCoS alloy nano-catalyst with cubic morphology are shown in table 1, wherein the reaction time is calculated by adding up from the beginning of the reaction: the experimental steps of the preparation method of the PtCoS alloy nano catalyst with the cubic morphology are as follows:

1) will be 100 μ L H₂PtCl₆(0.1M)、100μL CoCl₂(0.1M) and 240. mu.L NaOH (0.2M), 3mL Na₂SO₃(0.02M) was added to 4.56mL of deionized water to prepare a growth solution, which was left to stand and aged overnight;

2) to the growth solution of step 1, 800. mu.L of deionized water, 1mL of PVP (5 wt%), 200. mu.L of HCOOH and 300mg of glycine were added under magnetic stirring, and stirred for 10 min.

3) The solution obtained in step 2) was transferred to a 20mL reaction kettle and placed in an oven at 200 ℃ for 8 h.

4) Centrifuging the solution after the reaction in the step 3), and then adding deionized water: the mixed solution of ethanol 1:1 (mass ratio) was washed 3 times to obtain cubic PtCoS nanocrystals as shown in fig. 2 and 3.

According to the data in table 1, when PtCoS catalyst with cubic morphology is reacted at 25 ℃ for 1h, the CAL conversion is only 3.0%, and only C ═ C bond hydrogenation product HCAL is contained in the product. At the reaction time of 2.5h, C ═ O bonds are generated in the product, COL and C ═ O, C ═ C bonds are generated in the product, and HCOL is simultaneously hydrogenated, but the C ═ C bonds are mainly hydrogenated to generate HCAL. The CAL conversion rate is obviously increased after 5.5h of reaction, the conversion rate reaches 72.1% after 7h of reaction, the HCAL content in the product is gradually reduced, the selectivity of the C ═ O bond hydrogenation to COL is increased to 34%, and the HCOL content of the product obtained by simultaneous hydrogenation of two double bonds is also gradually increased to 11.3%. At 10h of reaction, the CAL conversion increased to 99.4%. From the viewpoint of product selectivity, as the conversion rate increases, the content of HCAL in the hydrogenation product gradually decreases from 100% at the beginning to 60.1%, the selectivity of hydrogenation on cinnamaldehyde C ═ O bond to COL increases to 34% first and then gradually decreases to 18.7%, and C ═ O, C ═ C bond while the hydrogenation product HCOL continuously increases to 21.2%. It can be seen that HCAL and COL are further hydrogenated to produce HCOL as the reaction proceeds.

TABLE 1 CAL hydrogenation of PtCoS catalysts with cubic morphology

Comparative example 2

On the basis of example 1, without adding glycine, the obtained nanowire morphology is PtCoS ternary alloy as shown in fig. 4, and the prepared catalyst is shown in table 2 of CAL conversion and hydrogenation product selectivity under the same experimental conditions as example 1, wherein the reaction time is calculated cumulatively from the beginning of the reaction:

as shown in table 2, the nano wire catalyst PtCoS reacted at 25 ℃ for 1 hour, the CAL conversion was only 4.3%, and only C ═ C bond hydrogenation product HCAL was present in the product. At the reaction time of 2.5h, C ═ O bonds are generated in the product, COL and C ═ O, C ═ C bonds are generated in the product, and HCOL is simultaneously hydrogenated, but the C ═ C bonds are mainly hydrogenated to generate HCAL. The conversion rate reaches 77.5% after 7h of reaction, the selectivity of HCAL and COL in the product is not changed greatly, and the HCOL content of the product obtained by simultaneously hydrogenating two double bonds is gradually increased to 4.5%. At 10h of reaction time, the CAL conversion increased to 99.9%. From the point of view of product selectivity, the hcl content in the hydrogenation product gradually decreased with increasing conversion from 100% at the beginning to 81.3%, the selectivity of hydrogenation on the C ═ O bond of cinnamaldehyde to COL was 0, and the C ═ O, C ═ C bond while the hcl content in the hydrogenation product increased continuously to 18.7%. It can be seen that HCAL and COL are further hydrogenated to produce HCOL as the reaction proceeds.

TABLE 2 CAL hydrogenation of PtCoS catalysts in nanowire form

Comparative example 3

On the basis of example 1, no precursor Na was added₂SO₃Then obtained isThe nanocrystalline is PtCo binary alloy and is partially in an irregular thorn-shaped shape. The obtained PtCo binary alloy catalyst was subjected to the same experimental conditions as in example 1, and the obtained catalyst was subjected to CAL conversion and hydrogenation product selectivity data shown in table 3, wherein the reaction time is calculated cumulatively from the start of the reaction:

TABLE 3 CAL hydrogenation of PtCo catalyst

According to the data in table 3, when the bimetallic catalyst PtCo is reacted at 25 ℃ for 1 hour, the CAL conversion rate reaches 90.3%, and the product contains hydrogenation products of C ═ C bond, HCAL, C ═ O bond, COL and C ═ O, C ═ C bond, and the hydrogenation products of HCOL are simultaneously hydrogenated, and the hydrogenation of C ═ C bond to produce HCOL is the main. Reaction 2.5 conversion reached 99.9%, with hydrogenation on cinnamaldehyde C ═ O bond to COL selectivity 0, and C ═ O, C ═ C bond with increasing hydrogenation product HCOL to 98.8%, and almost complete conversion to HCOL at 3 h.

In the comparison and investigation of the catalytic selective hydrogenation performance of cinnamaldehyde, the catalyst PtCoS has low conversion rate to CAL relative to PtCo catalyst at normal temperature in the same time, and due to the existence of S in the alloy, the expected hydrogenation intermediate product can be obtained without carrying out vulcanization treatment in the hydrogenation reaction of cinnamaldehyde by noble metal. In contrast, the conversion rates of the two PtCoS catalysts in the selective hydrogenation reaction of cinnamaldehyde are equivalent, although the products of the two catalysts in the form of the PtCoS catalysts are mainly hydrogenated by C ═ C bonds and have high selectivity to HCAL, 27% to 34% of the C ═ O bond hydrogenation products COL in the hydrogenation products on the cubic catalysts are generated, and the COL content in the products of the linear catalysts is only about 1%, that is, the PtCoS alloy catalyst in the form of the PtCoS catalyst in the form of the cubic catalyst is controlled to be synthesized, so that an unexpected technical effect is achieved on the selective catalysis of cinnamaldehyde hydrogenation to obtain cinnamyl alcohol.

Claims (1)

1. A method for increasing the yield and selectivity of cinnamyl alcohol production, characterized by: the selective hydrogenation reaction of cinnamaldehyde is carried out in a 2ml high-pressure reaction kettle, 2mg of PtCoS alloy nano catalyst with cubic morphology is loaded into a reactor, and 1ml of toluene (solvent) and 0.2mmol of cinnamaldehyde reactant are rapidly added. Checking the tightness of the device, replacing air with hydrogen for 3 times, discharging oxygen in the reactor, pressurizing to 0.8MPa with hydrogen, and reacting the reactor in a temperature-controlled magnetic stirrer, wherein the experimental steps of the preparation method of the PtCoS alloy nano catalyst with the cubic morphology are as follows:

1) will be 100 μ L H₂PtCl₆(0.1M)、100μL CoCl₂(0.1M) and 240. mu.L NaOH (0.2M), 3mL Na₂SO₃(0.02M) was added to 4.56mL of deionized water to prepare a growth solution, which was left to stand and aged overnight;

2) to the growth solution of step 1), 800. mu.L of deionized water, 1mL of PVP (5 wt%), 200. mu.L of HCOOH, and 300mg of glycine were added under magnetic stirring, preferably for 10 min.

3) The solution obtained in step 2) was transferred to a 20mL reaction kettle and placed in an oven at 200 ℃ for 8 h.

4) Centrifuging the solution after the reaction in the step 3), and then adding deionized water: the mixed solution of ethanol 1:1 (mass ratio) was washed 3 times to obtain cubic PtCoS nanocrystals.

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