CN108129299B - Method for preparing 1, 3-pentadiene from xylitol - Google Patents

Method for preparing 1, 3-pentadiene from xylitol Download PDF

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CN108129299B
CN108129299B CN201611087916.0A CN201611087916A CN108129299B CN 108129299 B CN108129299 B CN 108129299B CN 201611087916 A CN201611087916 A CN 201611087916A CN 108129299 B CN108129299 B CN 108129299B
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CN108129299A (en
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郑明远
孙睿岩
李新生
张涛
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a method for preparing 1, 3-pentadiene from xylitol. The method takes xylitol as a raw material to prepare 1, 3-pentadiene, and comprises the following two steps: the first step is that the 2, 4-pentadiene-1-alcohol formate is prepared by the deoxidation dehydration reaction and the esterification reaction of the xylitol and the formic acid under the condition without a catalyst; the second step is that 2, 4-pentadiene-1-alcohol formate is subjected to deoxidation reaction under the catalysis of a hydrogenation catalyst to prepare the 1, 3-pentadiene. The catalyst and the raw materials used in the invention are cheap and easy to obtain, the preparation process is simple, no additional hydrogen source is needed, and the catalyst has higher activity and selectivity for the deoxidation dehydration reaction of the xylitol and the deoxidation reaction of the 2, 4-pentadiene-1-alcohol formate. The invention provides a cheap and efficient synthesis method for synthesizing 1, 3-pentadiene from lignocellulose-based platform compound xylitol.

Description

Method for preparing 1, 3-pentadiene from xylitol
Technical Field
The invention relates to a method for preparing 1, 3-pentadiene from xylitol. The method takes xylitol as a raw material to prepare the 1, 3-pentadiene, and comprises the following two steps of reactions: the first step is that the 2, 4-pentadiene-1-alcohol formate is prepared by the deoxidation dehydration reaction and the esterification reaction of the xylitol and the formic acid under the condition of no catalyst; the second step is that 2, 4-pentadiene-1-alcohol formate is subjected to deoxidation reaction under the catalysis of a hydrogenation catalyst to prepare the 1, 3-pentadiene. The catalyst and raw materials used in the method are cheap and easy to obtain, the preparation process is simple, no additional hydrogen source is needed, and the product selectivity is high. The invention provides a cheap and efficient synthesis method for synthesizing 1, 3-pentadiene from lignocellulose-based platform compound xylitol.
Background
Due to the rapid development of society, the consumption of fossil resources is increasing day by day, and the environmental problems such as the emission of a large amount of greenhouse gases caused by the combustion of fossil energy are becoming prominent, and in addition, the social demand of energy is continuously increasing, the price of petroleum is continuously rising, and the development of renewable energy sources capable of replacing fossil resources is imperative. The application of biomass as a renewable organic carbon source in the production of carbon materials, fuels and chemicals is a hot research spot at present.
1, 3-pentadiene is one of important chemical raw materials, and is widely applied to synthesis of high molecular materials (resins), pesticides, medicines and other organic synthesis intermediates (ChemCatchem 2014,6, 412-. The 1, 3-pentadiene petroleum resin is prepared by cationic polymerization of piperylene raw material obtained by separating and purifying C5 fraction. The main chain of the petroleum resin is an aliphatic hydrocarbon structure, and has the characteristics of low acid value, good miscibility, good adhesion, water resistance, ethanol resistance, chemical resistance and the like. The 1, 3-pentadiene petroleum resin is widely applied to the fields of pressure-sensitive adhesives, light-color hot melt type marking paints, hot melt coatings, rubber tackifiers, paints, printing ink additives and the like. 1, 3-pentadiene is easy to have Diels-Alder diene synthesis reaction with unsaturated compounds to generate six-membered cyclic compounds, and then the aromatic compounds can be obtained by further dehydrogenation.
1, 3-pentadiene is obtained mainly from the petrochemical route. Crude oil is firstly subjected to primary rectification to obtain corresponding fractions to obtain crude naphtha, the naphtha is subjected to steam cracking at high temperature (900 ℃) to obtain a mixture of olefin and diene with short carbon chains, and finally the 1, 3-pentadiene with higher purity can be obtained through extraction rectification. The current production of 1, 3-pentadiene relies primarily on non-renewable fossil energy sources. Xylitol is one of important biomass platform compounds, and the synthesis of 1, 3-pentadiene by using renewable biomass and the platform compounds thereof as raw materials is reported. Wilson et al prepared renewable 1, 3-pentadiene using furfural as a starting material. This route involves three steps of reactions: hydrogenolysis of furfural to produce methylfuran, hydrogenation of methylfuran to produce methyltetrahydrofuran, and dehydration of methyltetrahydrofuran to produce 1, 3-pentadiene. Due to the long reaction route, the instability of the starting furfural leads to a final yield of 1, 3-pentadiene of only about 30% (Rubber chem. technol.1945,18,284-285; Process for manufacturing synthetic Rubber from furan, U.S. Pat. No. 2273484A). The method for preparing 1, 3-pentadiene from xylitol described in the patent has the advantages of cheap and easily available catalyst and raw materials, shorter reaction route, no need of additional hydrogen source and higher product selectivity. The whole route is green and environment-friendly, and the 1, 3-pentadiene is obtained at high yield by utilizing the renewable biomass platform compound xylitol.
Disclosure of Invention
The invention provides a method for preparing 1, 3-pentadiene from xylitol.
The preparation of 1, 3-pentadiene by taking xylitol as a raw material comprises two steps of reactions:
the first step is that the 2, 4-pentadiene-1-alcohol formate is prepared by the deoxidation dehydration reaction and the esterification reaction of the xylitol and the formic acid under the condition without a catalyst, and the reaction temperature is more than 100 ℃; the second step is that 2, 4-pentadiene-1-alcohol formate is subjected to deoxidation reaction under the catalysis of a hydrogenation catalyst to prepare the 1, 3-pentadiene, wherein the reaction temperature is higher than 20 ℃, and the reaction time is longer than 10 min.
The first step of reaction is carried out in a reactor with distillation function, and the 2, 4-pentadiene-1-alcohol formate generated in the reaction can be separated from reactants from a reaction system through distillation; the reaction system may use no solvent, or one or more than two of the following solvents: caprolactone, 1, 3-dimethyl propylene urea, sulfolane and tetraethylene glycol dimethyl ether are used as reaction solvents, preferably the reaction solvent is tetraethylene glycol dimethyl ether, and the dosage of the reaction solvent added into the reactor is 1/5-2/3 of the volume of the reactor;
the reaction temperature of the first step is 150-300 ℃, and the preferable reaction temperature is 180-280 ℃; the molar ratio of formic acid and xylitol as reactants is 0.1-25, and the preferred molar ratio of formic acid and xylitol is 8-16;
the first step of reaction can adopt an intermittent feeding mode: the method comprises the following steps of (1) putting a solvent, xylitol and formic acid into a reactor for reaction at one time, wherein the total volume of reaction liquid is 1/5-2/3 of the volume of the reactor; or only adding formic acid and xylitol without adding a solvent for reaction; the reaction time is more than 0.1h, and the preferable reaction time is 0.5-20 h;
the first step reaction can also adopt a mode of continuously adding reaction materials in the reaction process: dissolving xylitol in formic acid to prepare solution, pumping into a reaction system with solvent and heating to reaction temperature at a certain speed, wherein the volume space velocity of the reaction material is 0.5-20h-1Wherein the space velocity is a ratio of a volume of the reaction liquid fed to the reactor per hour to a volume of the solvent previously fed to the reactor.
The catalyst for the second step reaction is one or more than two of the following catalysts:
the catalyst is a supported metal catalyst, a commercial Raney nickel catalyst or a commercial amorphous alloy catalyst which takes one or more of active carbon, mesoporous carbon, silicon oxide, aluminum oxide, cerium oxide and titanium oxide as a carrier and one or more of Pt, Pd, Ru, Ir, Rh, Ni, Co and Cu as an active component.
The second reaction step can be carried out without using a solvent, or by using one or a mixture of two or more of the following solvents: methanol, ethanol, cyclohexane, toluene, tetrahydrofuran, dioxane, dimethyl sulfoxide, and N, N-dimethylformamide; the mass concentration of the 2, 4-pentadiene-1-alcohol formate is 0.01-100%, and the preferred mass concentration is 0.1-10%.
The supported metal catalyst for the second step reaction is prepared by adopting an equal volume impregnation method: preparing a metal precursor solution with the mass concentration of 0.01-50%, adding the metal precursor solution into the carrier according to the metering ratio for equal volume impregnation, wherein the mass content of the metal in the catalyst accounts for 0.01-50%, standing for 2h, drying at 80 ℃ for 12h, drying at 120 ℃ for 12h, finally reducing at 200-600 ℃ for 1-6h by using hydrogen, introducing O with the volume concentration of 1% after the temperature is reduced to the room temperature2The nitrogen is passivated for more than 4 hours.
The second step of reaction is carried out in a kettle type reactor or a fixed bed reactor, no additional hydrogen source is needed, the reaction temperature is between 40 and 250 ℃, and the preferable reaction temperature is between 50 and 150 ℃;
when the reaction is carried out in the reaction kettle, the ratio of the mass of the catalyst added in the reaction to the mass of the reaction substrate solution is 0.1-50%, the reaction time is 0.5-10h, and the preferable reaction time is 1-7 h;
when the reaction is carried out in the fixed bed reactor, the volume space velocity of the reaction material is 0.1-20h-1The preferred reaction space velocity is 0.5-10h-1。
The invention has the following advantages:
the method for preparing 1, 3-pentadiene from xylitol described in the patent has the advantages of cheap and easily available catalyst and raw materials, shorter reaction route, no need of additional hydrogen source and higher product selectivity. The whole route is green and environment-friendly, and the 1, 3-pentadiene is obtained at high yield by utilizing the renewable biomass platform compound xylitol.
Drawings
FIG. 1 Process for the deoxygenation and dehydration of xylitol to give the 2, 4-pentadiene-1-ol formate1H-NMR spectrum;
FIG. 2 Process for the deoxygenation and dehydration of xylitol to give the product 2, 4-pentadien-1-ol formate13A C-NMR spectrum;
FIG. 3 production of 2, 4-pentadien-1-ol, a product of deoxygenation and dehydration of xylitol1H-NMR spectrum;
FIG. 4 production of 2, 4-pentadien-1-ol, a product of deoxygenation and dehydration of xylitol13A C-NMR spectrum;
FIG. 5.1, 3-pentadiene1H-NMR spectrum;
FIG. 6.1, 3-pentadiene13C-NMR spectrum.
Detailed Description
The invention will now be illustrated by means of specific examples, without restricting its scope to these examples.
Example 1
Experiment on the preparation of 2, 4-pentadien-1-ol-formate from xylitol (reaction model and solvent Effect)
For the batch reaction, 5g of tetraglyme, 12g of xylitol and a certain amount of formic acid were simultaneously added into a 50mL three-necked flask, the molar ratio of formic acid to xylitol was 12:1, the reaction temperature was 235 ℃, and the reaction time was 12 hours. In the reaction process, the product is heated at the reaction temperature and distilled out of the reactor, condensed and collected. The product yield was calculated using the carbon yield.
For the continuous reaction, 5g of solvent was added into a 50mL three-necked flask, 12g of xylitol was dissolved in a certain amount of formic acid, the molar ratio of formic acid to xylitol was 12:1, the formic acid solution in which xylitol was dissolved was pumped into the three-necked flask at a pump speed of 0.074mL/min when the reaction temperature was raised to 235 ℃, and the total reaction time was extended to 12 hours after the end of the feeding. In the reaction process, the product is heated at the reaction temperature and distilled out of the reactor, condensed and collected. The product yield was calculated using the carbon yield.
TABLE 1 reaction modes and influence of solvents on the Activity of xylitol to prepare 2, 4-pentadiene-1-ol formates
Figure BDA0001168118350000051
As can be seen from the results in Table 1, the yield of 2, 4-pentadiene-1-ol formate in the absence of solvent is much lower than that of 2, 4-pentadiene-1-ol formate when a solvent is added. The addition of the solvent reduces the concentration of xylitol, thereby inhibiting the side reaction of generating 1, 4-dehydrated xylitol by dehydrating xylitol and improving the yield of target products. The yields of 2, 4-pentadiene-1-ol-formate differ among the solvents, with tetraethylene glycol dimethyl ether being the best reaction solvent, and the yield of 2, 4-pentadiene-1-ol-formate being the highest using tetraethylene glycol dimethyl ether as solvent. The yield of the 2, 4-pentadiene-1-alcohol formate obtained by using a continuous feeding mode is obviously higher than that of a batch reaction mode, because the mixed formic acid xylitol solution is pumped to keep the concentration of xylitol in a reaction system at a lower level, the side reaction of xylitol is inhibited, the yield of products is improved, and the continuous reaction mode is the best reaction mode.
Example 2
Experiment on the preparation of 2, 4-pentadien-1-ol-formate from xylitol (influence of the molar ratio of formic acid to xylitol)
3g of tetraethylene glycol dimethyl ether is added into a 50mL three-neck flask, 12g of xylitol is dissolved in a certain amount of formic acid, when the reaction temperature is increased to 235 ℃, the formic acid solution in which the xylitol is dissolved is pumped into the three-neck flask at the pump speed of 0.074mL/min, the feeding is continued for 15h, and then the reaction time is prolonged for 1 h.
TABLE 2 influence of different xylitol formate molar ratios on the activity of preparing 2, 4-pentadiene-1-ol formate from xylitol
Figure BDA0001168118350000061
As can be seen from the results in Table 2, the yield of 2, 4-pentadien-1-ol formate increases and decreases with increasing formic acid/xylitol molar ratio, reaching a maximum at a formic acid/xylitol molar ratio of 12, and the yield of 2, 4-pentadien-1-ol formate remains at a high level when the formic acid/xylitol molar ratio is between 8 and 16. While the yield of 2, 4-pentadien-1-ol decreases continuously with increasing formic acid/xylitol molar ratio, the increase in formic acid dosage facilitates the further esterification of 2, 4-pentadien-1-ol to 2, 4-pentadien-1-ol formate. The optimum molar ratio formic acid/xylitol is 12.
Example 3
Experiment on the preparation of 2, 4-pentadien-1-ol-formate from xylitol (reaction temperature influence)
Adding 4g of tetraethylene glycol dimethyl ether into a 50mL three-neck flask, dissolving 12g of xylitol in a certain amount of formic acid, wherein the molar ratio of the formic acid to the xylitol is 10:1, pumping the formic acid solution in which the xylitol is dissolved into the three-neck flask when the reaction temperature is raised to a preset temperature, wherein the pumping speed is 0.1mL/min, feeding for 8 hours, and prolonging the reaction time for 0.5 hour.
TABLE 3 influence of different temperatures on the activity of xylitol to prepare 2, 4-pentadien-1-ol formate
Figure BDA0001168118350000071
As can be seen from Table 3, the yield of 2, 4-pentadien-1-ol-formate increases and then decreases with increasing reaction temperature, reaching a maximum at 235 ℃ which is the optimum reaction temperature.
Example 4
Experiment on the preparation of 2, 4-pentadien-1-ol-formate from xylitol (influence of Pump speed)
In a 50mL three-necked flask, 7g of tetraethylene glycol dimethyl ether was added, 12g of xylitol was dissolved in a certain amount of formic acid at a molar ratio of formic acid to xylitol of 14:1, and when the reaction temperature rose to 235 ℃, the formic acid solution in which xylitol was dissolved was pumped into the three-necked flask for a feeding time of 30 hours.
TABLE 4 influence of different pump speeds on the Activity of xylitol to prepare 2, 4-pentadiene-1-ol formates
Figure BDA0001168118350000072
Figure BDA0001168118350000081
As can be seen from the data in Table 4, as the pump speed increases, the yield of 2, 4-pentadien-1-ol formate increases and then decreases, reaching a maximum at 0.074mL/min, with an optimum pump speed of 0.074 mL/min.
Example 5
Deoxygenation of 2, 4-pentadien-1-ol formate to 1, 3-pentadiene (catalyst screening)
In a 50mL reaction vessel, 20g of 0.33% ethanol solution of 2, 4-pentadien-1-ol formate and 0.1g of a catalyst were added, and the reaction time was 2 hours and the reaction temperature was 80 ℃.
TABLE 5 Deoxidation of 2, 4-pentadien-1-ol formate to 1, 3-pentadiene over different metal catalysts results
Figure BDA0001168118350000082
Figure BDA0001168118350000091
As can be seen from the data in Table 5, almost all of the common hydrogenation catalysts are catalytically active for the deoxygenation of 2, 4-pentadien-1-ol formate to 1, 3-pentadiene, with the highest selectivity for 1, 3-pentadiene over Pd/C; the highest conversion of 2, 4-pentadiene-1-ol formate on Raney Ni.
Example 6
Deoxygenation of 2, 4-pentadien-1-ol formate to 1, 3-pentadiene (influence of reaction temperature)
In a 50mL reaction vessel, 20g of 0.63% ethanol solution of 2, 4-pentadien-1-ol formate, 0.2g of 5% Pd/C, and a reaction time of 5 hours were added.
TABLE 6 influence of temperature on the reactivity of 2, 4-pentadien-1-ol formate deoxygenation to 1, 3-pentadiene
Figure BDA0001168118350000092
Figure BDA0001168118350000101
As can be seen from the data in Table 6, as the reaction temperature increases, the conversion of 2, 4-pentadien-1-ol formate increases, while the selectivity of 1, 3-pentadiene continues to decrease while taking into account the activity and selectivity of the reaction, and 80 ℃ is selected as the optimum reaction temperature.
Example 7
Deoxygenation of 2, 4-pentadien-1-ol formate to 1, 3-pentadiene (influence of reaction solvent)
20g of 0.12 percent 2, 4-pentadiene-1-alcohol formic ether solution prepared from different solvents and 0.1g of Raney Ni are added into a 50mL reaction kettle, the reaction time is 5h, and the reaction temperature is 80 ℃.
TABLE 7 Effect of different solvents on the reactivity of 2, 4-pentadien-1-ol formate deoxygenation to 1, 3-pentadiene
Figure BDA0001168118350000102
As can be seen from the data in Table 7, the solvent has little effect on the deoxidation of 2, 4-pentadiene-1-ol formate to 1, 3-pentadiene, and 1, 3-pentadiene with higher selectivity can be obtained in various solvents. Among these, the highest selectivity for 1, 3-pentadiene was obtained on ethanol and cyclohexane.
Example 8
Deoxygenation of 2, 4-pentadien-1-ol formate to 1, 3-pentadiene (influence of reactant concentration)
20g of a cyclohexane solution of 2, 4-pentadiene-1-ol formate with a certain concentration and 0.3g of Raney Cu are added into a 50mL reaction kettle, the reaction time is 3h, and the reaction temperature is 80 ℃.
TABLE 8 influence of the concentration of the reactants on the reactivity of the 2, 4-pentadien-1-ol formate deoxygenation to 1, 3-pentadiene
Figure BDA0001168118350000111
As can be seen from the data in Table 8, increasing substrate concentration results in a decrease in 1, 3-pentadiene selectivity. At substrate concentrations below 0.63%, the selectivity for 1, 3-pentadiene remained around 90%, and at substrate concentrations above 0.63%, the selectivity for 1, 3-pentadiene began to decrease significantly, with an optimal concentration of 0.63% for 2, 4-pentadiene-1-ol formate.
Example 9
Deoxygenation of 2, 4-pentadien-1-ol formate to 1, 3-pentadiene (reaction time influence)
In a 50mL reaction vessel, 20g of a 0.63% solution of 2, 4-pentadien-1-ol formate dioxane, 0.2g of 5% Pt/C, was added at 100 ℃.
TABLE 9 Effect of reaction time on the reactivity of 2, 4-pentadien-1-ol formate deoxygenation to 1, 3-pentadiene
Figure BDA0001168118350000121
As can be seen from the data in Table 9, the conversion of 2, 4-pentadien-1-ol formate increases with increasing reaction time, with better reaction selectivity within 1-7h, 5h being the optimum reaction time, and the selectivity starts to decrease significantly after 7 h.
Example 10
Deoxygenation of 2, 4-pentadien-1-ol formate to 1, 3-pentadiene (influence of catalyst amount)
20g of 0.63% 2, 4-pentadiene-1-alcohol formate tetrahydrofuran solution with a certain mass of 5% Pd/C is added into a 50mL reaction kettle, the reaction time is 3h, and the reaction temperature is 100 ℃.
TABLE 10 influence of the amount of catalyst used on the reactivity of 2, 4-pentadien-1-ol formate deoxygenation to 1, 3-pentadiene
Figure BDA0001168118350000122
Figure BDA0001168118350000131
As can be seen from the data in Table 10, as the amount of catalyst used increases, the conversion of 2, 4-pentadien-1-ol formate increases gradually, while the selectivity to 1, 3-pentadiene increases and then decreases, reaching a maximum at 0.3g, with 0.3g being the optimum amount of catalyst.
As can be seen from the above examples, the high selectivity production of 1, 3-pentadiene from xylitol can be achieved by a two-step process. The catalyst and the raw materials are cheap and easy to obtain, the reaction route is shorter, no additional hydrogen source is needed, the product selectivity is higher, the whole process is green and environment-friendly, and the method is a very efficient method for synthesizing the 1, 3-pentadiene from the renewable biomass platform compound.

Claims (4)

1. A method for preparing 1, 3-pentadiene from xylitol is characterized by comprising the following steps:
the preparation of 1, 3-pentadiene by taking xylitol as a raw material comprises two steps of reactions:
the first step is that the 2, 4-pentadiene-1-alcohol formate is prepared by the deoxidation dehydration reaction and the esterification reaction of the xylitol and the formic acid under the condition without a catalyst;
the second step is that 2, 4-pentadiene-1-alcohol formate is subjected to deoxidation reaction under the catalysis of a hydrogenation catalyst to prepare 1, 3-pentadiene;
the first step of reaction is carried out in a reactor with distillation function, and 2, 4-pentadiene-1-alcohol formate generated in the reaction is separated from reactants from a reaction system through distillation; no solvent is adopted in the reaction system, or one or more than two of the following solvents are adopted: caprolactone, 1, 3-dimethyl propylene urea, sulfolane and tetraethylene glycol dimethyl ether are used as reaction solvents, and the dosage of the reaction solvents added into the reactor is 1/5-2/3 of the volume of the reactor;
the second step reaction does not use a solvent, or adopts one or more than two of the following solvents for mixing: methanol, ethanol, cyclohexane, toluene, tetrahydrofuran, dioxane, dimethyl sulfoxide, and N, N-dimethylformamide; the mass concentration of the 2, 4-pentadiene-1-alcohol formate is 0.01-100%;
the first step reaction temperature was 150 deg.CoC-300 oC; the molar ratio of the reactants formic acid and xylitol is 0.1-25;
the first step of reaction adopts an intermittent material adding mode: the method comprises the following steps of (1) putting a solvent, xylitol and formic acid into a reactor for reaction at one time, wherein the total volume of reaction liquid is 1/5-2/3 of the volume of the reactor; or only adding formic acid and xylitol without adding a solvent for reaction; the reaction time is more than 0.1 h;
or, the first step reaction adopts a mode of continuously adding reaction materials in the reaction process: dissolving xylitol in formic acid to prepare solution, pumping into a reaction system with solvent and heating to reaction temperature at a certain speed, wherein the volume space velocity of the reaction material is 0.5-20h-1Wherein the space velocity is the ratio of the volume of the reaction liquid added into the reactor per hour to the volume of the solvent added into the reactor in advance;
the catalyst for the second step reaction is one or more than two of the following catalysts:
a supported metal catalyst and a commercial Raney nickel catalyst which take one or more of active carbon, mesoporous carbon, silicon oxide, aluminum oxide, cerium oxide and titanium oxide as a carrier and one or more of Pt, Pd, Ru, Ir, Rh, Ni, Co and Cu as an active component;
the second step reaction is carried out in a kettle type reactor or a fixed bed reactor, no additional hydrogen source is needed, and the reaction temperature is 40 DEGoC-250 oC is between;
when the reaction is carried out in the reaction kettle, the ratio of the mass of the catalyst added in the reaction to the mass of the reaction substrate solution is between 0.1 and 50 percent, and the reaction time is between 0.5 and 10 hours;
when the reaction is carried out in the fixed bed reactor, the volume space velocity of the reaction material is 0.1-20h-1。
2. The method of claim 1, wherein:
the first reaction step is at 180oC- 280 oC, performing; the molar ratio of formic acid to xylitol in the reaction materials is 8-16; when the intermittent feeding mode is adopted, the reaction time is 0.5-20 h; when a mode of continuously adding reaction materials in the reaction process is adopted, the reaction solvent added in the reactor is tetraethylene glycol dimethyl ether.
3. The method of claim 1, wherein:
the supported metal catalyst for the second step reaction is prepared by adopting an equal volume impregnation method: preparing a metal precursor solution with the mass concentration of 0.01-50%, adding the metal precursor solution into the carrier according to the metering ratio, soaking the carrier in a medium volume, wherein the mass content of the metal in the catalyst accounts for 0.01-50%, standing for 2h, and standing for 80 hoDrying for 12h at C, and then drying at 120 deg.CoDrying for 12h at C, and finally drying at 200-oReducing with hydrogen for 1-6h at C, cooling to room temperature, and introducing O with volume concentration of 1%2The nitrogen is passivated for more than 4 hours.
4. The method of claim 1, wherein:
the second reaction stage is at 50oC- 150 oC, the mass concentration of the 2, 4-pentadiene-1-alcohol formate in the reactant is 0.1% -10%;
when the reaction is carried out in the kettle type reactor, the reaction time is between 1h and 7 h;
when the reaction is carried out in the fixed bed reactor, the volume space velocity of the reaction material is 0.5-10h-1。
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