CN109731596B - Preparation method of modified copper-based catalyst for preparing furfuryl alcohol by furfural hydrogenation - Google Patents

Abstract

A method for preparing a modified copper-based catalyst for furfural hydrogenation to furfuryl alcohol relates to furfuryl alcohol. First, the alkali metal salt modifier is reacted with formic acid to form a solution, and then the complex of copper salt and modifier salt is regenerated by hydrogen and carbon dioxide generated by the decomposition of formic acid to form an alkali metal carbonate modified copper-based catalyst. The prepared modified copper-based catalyst has high furfural conversion rate and furfuryl alcohol selectivity, and under suitable reaction conditions, the furfuryl alcohol yield can reach 80% to 99%. Using cheap carbonate as the carrier or doping into the catalyst, and copper salt as the precursor, a simple in-situ reduction method was used to prepare a highly active modified copper-based catalyst, and the hydrogenation of furfural was prepared under suitable process conditions. furfuryl alcohol. The preparation process of the modified copper-based catalyst for furfural hydrogenation to furfuryl alcohol is simple in operation, short in time, low in cost, high in catalytic reaction activity, good in selectivity to furfuryl alcohol, stable in cycle performance, and has broad application prospects.

Description

A kind of preparation method of modified copper-based catalyst for furfural hydrogenation to furfuryl alcohol

technical field

The invention relates to furfuryl alcohol, in particular to the preparation of a modified copper-based catalyst for furfural hydrogenation to furfuryl alcohol, which can be modified by using formic acid as a dissolving agent and a regenerating agent to regenerate an organic copper salt and an alkali metal modifier salt complex. method.

Background technique

Furfuryl alcohol is an important fine chemical widely used in synthetic fiber, rubber, resin, fragrance, pharmaceutical and pesticide intermediates and other industries. Furfuryl alcohol is the product of the selective hydrogenation of furfural carbonyl group. In industry, Cu-Cr catalysts are mainly used, but the catalysts have high toxicity, short life and unstable activity. The precious metal-supported catalysts developed in recent years are not conducive to large-scale production due to their high price. As a common catalyst, non-precious metal or metal oxide supported catalysts are widely used in industrial production due to their simple composition and moderate price. Furfural hydrogenation catalysts mainly use _SiO2 or porous molecular sieve supported copper-based catalysts. The preparation of these catalysts generally adopts co-precipitation (including co-current, reverse addition, positive addition co-precipitation method) or impregnation method to generate mixed metal salt precursors, The finished catalyst is prepared through the steps of static aging, water washing, drying, roasting, reduction, etc., and the preparation period is long and the cost is high.

At present, the research on catalyst preparation mainly focuses on the optimization and improvement of the preparation method and preparation process, and the catalyst activity is improved by changing the proportion of catalyst components, grain size, specific surface area and pore size distribution. Li Feng et al. disclosed in Chinese patent CN104841436 A (2015) a catalyst preparation for the hydrogenation of furfural to furfuryl alcohol catalyzed by copper-magnesium mixed metal oxides, including precipitation, crystallization, drying, calcination and reduction. 2 to 3 days. Shi Jiangong et al. disclosed in Chinese patent CN 106749120 A (2017) a copper-based catalyst supported by CaCO ₃ and SiO ₂ to catalyze furfural hydrogenation to prepare furfuryl alcohol, and the preparation of the catalyst also includes complex steps such as precipitation, drying, roasting and reduction. In patent CN 107970942 A (2018), Zhu Yuehui et al. disclose a kind of amorphous copper-based catalyst using borohydride as an in-situ reducing agent to catalyze furfural hydrogenation to prepare furfuryl alcohol, but it needs to be dried and calcined between the carrier and the salt solution. The mixture is used to prepare the catalyst precursor, and then the copper-based catalyst is obtained by borohydride reduction.

To sum up, there is currently no method for preparing copper-based catalyst by in-situ reduction of formic acid, and it is used in the reaction of furfural hydrogenation to prepare furfuryl alcohol; especially, there is no method for hydrogenating furfural with doping barium salt or barium salt as carrier and copper as active ingredient. Modified catalyst for furfuryl alcohol. In addition, there is no report that the above catalyst is used for the process conditions for producing furfuryl alcohol.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a method for preparing a modified copper-based catalyst for hydrogenating furfural to furfuryl alcohol by using formic acid as a dissolving agent and a regenerant to regenerate an organic copper salt and an alkali metal modifier salt complex to prepare and modify it. .

The present invention firstly reacts the alkali metal salt modifier with formic acid to form a solution, and then regenerates the complex of the copper salt and the modifier salt through hydrogen and carbon dioxide generated by the decomposition of the formic acid to form the alkali metal carbonate modified copper-based catalyst. The prepared modified copper-based catalyst has high furfural conversion rate and furfuryl alcohol selectivity, and under suitable reaction conditions, the furfuryl alcohol yield can reach 80% to 99%.

The present invention includes the following steps:

1) putting alkali metal salt modifier and anhydrous formic acid and reaction solvent into the reactor, stirring reaction to obtain alkali metal salt modifier formate solution;

2) adding a copper salt precursor to the alkali metal salt modifier formate solution obtained in step ₁ ), replacing the air with N , stirring and reacting to obtain a solid-liquid mixture, separating the solid precipitate, and washing and drying, A modified copper-based catalyst for preparing furfural hydrogenation to furfuryl alcohol is obtained.

In step 1), the alkali metal salt modifier can be selected from at least one of MgCO ₃ , CaCO ₃ , BaCO ₃ , Ba(CH ₃ COO) ₂ ·H ₂ O, etc., the alkali metal salt modifier The mass percentage concentration of the solvent can be 0.05% to 1%, preferably 0.1% to 0.5%; the reaction solvent can be selected from at least one of 1,4-dioxane, tetrahydrofuran, methanol, ethanol or water, etc., 1,4-dioxane and tetrahydrofuran are preferred; the mass percentage concentration of the anhydrous formic acid may be 0.1%-10%, preferably 0.5%-5%.

In step 2), the copper salt precursor may be selected from Cu(HCOO) ₂ .4H ₂ O, Cu(CH ₃ COO) ₂ .H ₂ O, Cu(NO ₃ ) ₂ .4H ₂ O and CuSO ₄ At least one of 5H ₂ O, etc., the mass percentage concentration of the copper salt precursor can be 0.1% to 5%, preferably 1% to 3%; the replacement of the exhaust air with N ₂ can be replaced by N ₂ 3～ The air in the reaction kettle is discharged five times; the temperature of the reaction can be 100-200°C, preferably 150-180°C, the reaction time can be 0.1-4h, preferably 0.5-2h, and the rotation speed is 500rpm.

The modified copper-based catalyst for preparing furfuryl alcohol by hydrogenation of furfural is used for the reaction method of furfural liquid-phase hydrogenation to prepare furfuryl alcohol as follows:

The reactants furfural, 1,4-dioxane, anhydrous formic acid and the in-situ Cu _- BaCO catalyst are mixed and placed in a closed autoclave, wherein the mass percentage concentration of the substrate furfural is 0.15% to 10%, The molar ratio of anhydrous formic acid and furfural is 4:1, and the air is replaced by N ₂ (or directly evacuated with H ₂ without adding anhydrous formic acid, and 0.5-3MPa H ₂ replaces anhydrous formic acid as a hydrogen source for the reaction), The reaction temperature is 150-200°C, the reaction time is 0.5-4h, and the rotation speed is 500rpm.

In the invention, cheap carbonate is used as a carrier or doped into the catalyst, and copper salt is used as a precursor, a simple in-situ reduction method is used to prepare a highly active modified copper-based catalyst, and the addition of furfural is catalyzed under suitable process conditions. Hydrogen to furfuryl alcohol. The preparation process of the modified copper-based catalyst for furfural hydrogenation to furfuryl alcohol is simple in operation, short in time, low in cost, high in catalytic reaction activity, good in selectivity to furfuryl alcohol, stable in cycle performance, and has broad application prospects.

Compared with the prior art, the beneficial effects of the present invention are as follows:

1. Using non-precious metal salts as catalyst precursors, the production cost is low;

2. The preparation process of the modified copper-based catalyst for furfural hydrogenation to furfuryl alcohol is simple, time-consuming, and has good catalytic activity and high product selectivity;

3. The in-situ Cu-BaCO ₃ catalyst can use formic acid or H ₂ as the hydrogen source at the same time, the hydrogenation effect is good, the economic benefit is high, and it has industrial application value.

Description of drawings

Figure 1 is the X-ray diffraction (XRD) pattern of the prepared Cu-BaCO ₃ composite catalyst.

Figure 2 is a scanning electron microscope (SEM) image of the prepared Cu-BaCO ₃ composite catalyst.

Figure 3 is a scanning electron microscope energy spectrum (SEM-EDS) image of the prepared Cu-BaCO ₃ composite catalyst.

Detailed ways

The present invention will be further described below with reference to the embodiments and the accompanying drawings. It should be noted that the embodiments do not constitute a limitation on the protection scope of the present invention.

Example 1

Accurately weigh 0.2 g of MgCO ₃ , 1 g of anhydrous formic acid and 20 mL of 1,4-dioxane into a 50 mL autoclave, seal it, and stir at 170° C. for 30 min. After cooling, 1 g of Cu(NO ₃ ) ₂ ·4H ₂ O was added to the above reaction solution, the reaction vessel was sealed, replaced with N ₂ for 3 to 5 times and evacuated, and the reaction was carried out at 170° C. for 30 min. After cooling, centrifugation, washing, and vacuum drying at 60° C. to obtain a 57% Cu-MgCO ₃ composite catalyst. In a similar way, change the auxiliary to CaCO ₃ , BaCO ₃ or Ba(CH ₃ COO) ₂ ·H ₂ O, the copper salt precursors are Cu(HCOO) ₂ ·4H ₂ O, Cu(CH ₃ COO) ₂ · H ₂ O or CuSO ₄ ·5H ₂ O can prepare modified Cu-based catalysts supported by different metals or promoters.

Add 0.3 g of the above Cu _- MgCO catalyst, 0.6 g of furfural and 20 mL of 1,4-dioxane into the reaction kettle, then add 1.15 g of anhydrous formic acid, after mixing and sealing, replace the air with N ₃ to 5 times , at 170℃ for 2h, the conversion rate of furfuryl alcohol is 53%, and the selectivity is 96%. Under the same conditions, replacing formic acid with 2MPa _H2 , the conversion of furfural was 70% and the selectivity was 95%.

Example 2

Accurately weigh 0.08 g of BaCO ₃ , 1 g of anhydrous formic acid and 20 mL of 1,4-dioxane into a 50 mL autoclave, seal it, and stir at 200° C. for 30 min. After cooling, 0.43 g of Cu(HCOO) ₂ ·4H ₂ O was added to the above reaction solution, the reaction kettle was sealed, replaced with N ₂ for 3 to 5 times and evacuated, and the reaction was carried out at 170° C. for 30 min. After cooling, centrifuge separation, washing, and vacuum drying at 60° C. to obtain a 60% Cu-BaCO ₃ composite catalyst. In a similar way, the Cu-BaCO ₃ composite catalysts with different mass fractions were prepared by changing the addition amount of Cu(HCOO) ₂ ·4H ₂ O and BaCO ₃ .

Add the above-mentioned Cu _- BaCO catalyst 0.3g, furfural 0.6g and 1,4-dioxane 20mL into the reactor, then add 1.15g anhydrous formic acid, after mixing and sealing, replace the air with N ₂ for 3 to 5 times , at 170 ℃ for 2h, the conversion rate of furfuryl alcohol is 100%, and the selectivity is 99%. Under the same conditions, replacing formic acid with 2MPa _H2 , the furfural conversion was 100% and the selectivity was 99%.

Example 3

Accurately weigh 0.08 g of BaCO ₃ , 0.02 g of anhydrous formic acid and 20 mL of 1,4-dioxane into a 50 mL autoclave, seal it, and stir at 170° C. for 30 min. After cooling, 0.43 g of Cu(HCOO) ₂ ·4H ₂ O was added to the above reaction solution, the reaction vessel was sealed, replaced with N ₂ for 3-5 times and evacuated, and the reaction was carried out at 170° C. for 60 min. After cooling, centrifugal separation, washing, vacuum drying at 60 ° C, to obtain 60% Cu-BaCO ₃ composite catalyst.

Add the above-mentioned Cu _- BaCO catalyst 0.3g, furfural 0.6g and 1,4-dioxane 20mL into the reactor, then add 1.15g anhydrous formic acid, after mixing and sealing, replace the air with N ₂ for 3 to 5 times , at 170℃ for 2h, the conversion rate of furfuryl alcohol is 58%, and the selectivity is 97%. Under the same conditions, replacing formic acid with ₂ MPa H2, the conversion of furfural was 41% and the selectivity was 96%.

Example 4

Accurately weigh 0.08 g of BaCO ₃ , 0.5 g of anhydrous formic acid and 20 mL of 1,4-dioxane into a 50 mL autoclave, seal it, and stir at 170° C. for 30 min. After cooling, 0.43 g of Cu(HCOO) ₂ ·4H ₂ O was added to the above reaction solution, the reaction kettle was sealed, replaced with N ₂ for 3 to 5 times and evacuated, and the reaction was carried out at 170° C. for 60 min. After cooling, centrifuge separation, washing, and vacuum drying at 60° C. to obtain a 60% Cu-BaCO ₃ composite catalyst.

Add the above-mentioned Cu _- BaCO catalyst 0.3g, furfural 0.6g and 1,4-dioxane 20mL into the reactor, then add 1.15g anhydrous formic acid, after mixing and sealing, replace the air with N ₂ for 3 to 5 times , at 170 ℃ for 2h, the conversion rate of furfuryl alcohol is 98%, and the selectivity is 99%. Under the same conditions, replacing formic acid with 2MPa _H2 , the conversion of furfural was 99% and the selectivity was 100%.

Example 5

Accurately weigh 0.08 g of BaCO ₃ , 0.5 g of anhydrous formic acid and 20 mL of 1,4-dioxane into a 50 mL autoclave, seal it, and stir at 200° C. for 30 min. After cooling, 0.43 g of Cu(HCOO) ₂ ·4H ₂ O was added to the above reaction solution, the reaction kettle was sealed, replaced with N ₂ for 3 to 5 times and evacuated, and the reaction was carried out at 100° C. for 60 min. After cooling, centrifuge separation, washing, and vacuum drying at 60° C. to obtain a 60% Cu-BaCO ₃ composite catalyst.

Add the above-mentioned Cu _- BaCO catalyst 0.3g, furfural 0.6g and 1,4-dioxane 20mL into the reactor, then add 1.15g anhydrous formic acid, after mixing and sealing, replace the air with N ₂ for 3 to 5 times , at 170 ℃ for 2h, the conversion rate of furfuryl alcohol is 48%, and the selectivity is 98%. Under the same conditions, replacing formic acid with ₂ MPa H2, the conversion of furfural was 56% and the selectivity was 98%.

Example 6

Accurately weigh 0.08 g of BaCO ₃ , 0.8 g of anhydrous formic acid and 20 mL of 1,4-dioxane into a 50 mL autoclave, seal it, and stir at 100° C. for 30 min. After cooling, 0.43 g of Cu(HCOO) ₂ ·4H ₂ O was added to the above reaction solution, the reaction kettle was sealed, replaced with N ₂ for 3 to 5 times and evacuated, and the reaction was carried out at 200° C. for 60 min. After cooling, centrifuge separation, washing, and vacuum drying at 60° C. to obtain a 60% Cu-BaCO ₃ composite catalyst.

Add the above-mentioned Cu _- BaCO catalyst 0.3g, furfural 0.6g and 1,4-dioxane 20mL into the reactor, then add 1.15g anhydrous formic acid, after mixing and sealing, replace the air with N ₂ for 3 to 5 times , at 170℃ for 2h, the conversion rate of furfuryl alcohol is 100%, and the selectivity is 98%. Under the same conditions, replacing formic acid with 2MPa _H2 , the furfural conversion was 100% and the selectivity was 99%.

Example 7

Accurately weigh 0.08 g of BaCO ₃ , 0.8 g of anhydrous formic acid and 20 mL of 1,4-dioxane into a 50 mL autoclave, seal it, and stir at 170° C. for 10 min. After cooling, 0.43 g of Cu(HCOO) ₂ ·4H ₂ O was added to the above reaction solution, the reaction vessel was sealed, replaced with N ₂ for 3 to 5 times and evacuated, and the reaction was carried out at 180° C. for 6 min. After cooling, centrifuge separation, washing, and vacuum drying at 60° C. to obtain a 60% Cu-BaCO ₃ composite catalyst.

Add the above-mentioned Cu _- BaCO catalyst 0.3g, furfural 0.6g and 1,4-dioxane 20mL into the reactor, then add 1.15g anhydrous formic acid, after mixing and sealing, replace the air with N ₂ for 3 to 5 times , at 170 ℃ for 2h, the conversion rate of furfuryl alcohol is 38%, and the selectivity is 95%. Under the same conditions, replacing formic acid with 2MPa _H2 , the conversion of furfural was 45% and the selectivity was 97%.

Example 8

Accurately weigh 0.08 g of BaCO ₃ , 0.5 g of anhydrous formic acid and 20 mL of 1,4-dioxane into a 50 mL autoclave, seal it, and stir at 170° C. for 60 min. After cooling, 0.43 g of Cu(HCOO) ₂ ·4H ₂ O was added to the above reaction solution, the reaction kettle was sealed, replaced with N ₂ for 3 to 5 times and evacuated, and the reaction was carried out at 170° C. for 60 min. After cooling, centrifuge separation, washing, and vacuum drying at 60° C. to obtain a 60% Cu-BaCO ₃ composite catalyst.

Add the above-mentioned Cu _- BaCO catalyst 0.3g, furfural 0.6g and 1,4-dioxane 20mL into the reactor, then add 1.15g anhydrous formic acid, after mixing and sealing, replace the air with N ₂ for 3 to 5 times , at 100 ℃ for 2h, the conversion rate of furfuryl alcohol is 100%, and the selectivity is 99%. Under the same conditions, replacing formic acid with 2MPa _H2 , the furfural conversion was 100% and the selectivity was 99%.

Example 9

Accurately weigh 0.08 g of BaCO ₃ , 0.5 g of anhydrous formic acid and 20 mL of 1,4-dioxane into a 50 mL autoclave, seal it, and stir at 170° C. for 240 min. After cooling, 0.43 g of Cu(HCOO) ₂ ·4H ₂ O was added to the above reaction solution, the reaction vessel was sealed, replaced with N ₂ for 3 to 5 times and evacuated, and the reaction was carried out at 180° C. for 120 min. After cooling, centrifuge separation, washing, and vacuum drying at 60° C. to obtain a 60% Cu-BaCO ₃ composite catalyst.

Add the above-mentioned Cu _- BaCO catalyst 0.3g, furfural 0.6g and 1,4-dioxane 20mL into the reactor, then add 1.15g anhydrous formic acid, after mixing and sealing, replace the air with N ₂ for 3 to 5 times , at 150℃ for 2h, the conversion rate of furfuryl alcohol is 80%, and the selectivity is 99%. Under the same conditions, replacing formic acid with 0.5 MPa _H2 , the conversion of furfural was 45% and the selectivity was 98%.

Example 10

Accurately weigh 0.08 g of BaCO ₃ , 0.5 g of anhydrous formic acid and 20 mL of 1,4-dioxane into a 50 mL autoclave, seal it, and stir at 170° C. for 240 min. After cooling, 0.43 g of Cu(HCOO) ₂ ·4H ₂ O was added to the above reaction solution, the reaction kettle was sealed, replaced with N ₂ for 3 to 5 times and evacuated, and the reaction was carried out at 180° C. for 240 min. After cooling, centrifuge separation, washing, and vacuum drying at 60° C. to obtain a 60% Cu-BaCO ₃ composite catalyst.

Add the above-mentioned Cu _- BaCO catalyst 0.3g, furfural 0.6g and 1,4-dioxane 20mL into the reactor, then add 1.15g anhydrous formic acid, after mixing and sealing, replace the air with N ₂ for 3 to 5 times , at 200 ℃ for 2h, the conversion rate of furfuryl alcohol is 100%, and the selectivity is 95%. Under the same conditions, replacing formic acid with 3 MPa _H2 , the furfural conversion was 100% and the selectivity was 93%.

The X-ray diffraction (XRD) pattern of the prepared Cu _- BaCO3 composite catalyst is shown in _Fig . 1, the scanning electron microscope (SEM) pattern of the prepared Cu-BaCO3 composite catalyst is shown in Fig. 2, and the SEM image of the prepared Cu-BaCO3 composite catalyst is shown in _Fig . 2 The energy spectrum (SEM-EDS) pattern is shown in FIG. 3 .

The present invention does not need to go through complicated steps such as precipitation, calcination, reduction, etc., the technological process is simple, and the preparation time and cost of the catalyst are greatly reduced. The catalyst is used in furfural hydrogenation reaction, the conversion rate can reach 80%-100%, and the selectivity to furfuryl alcohol, the main product, can reach 90%-99%. The preparation method has the advantages of simple operation, short preparation period, good hydrogenation effect of the catalyst, high selectivity of the target product, repeated use for many times, and good stability.

Claims (14)

1. a modified copper-based catalyst preparation method for furfural hydrogenation to furfuryl alcohol is characterized in that comprising the following steps: 1) put basic metal modifier and anhydrous formic acid and reaction solvent into the reactor, airtight, stirring reaction to obtain alkali metal salt modifier formate solution; Described basic metal modifier is selected from MgCO _3. At least one of CaCO ₃ , BaCO ₃ , and Ba(CH ₃ COO) ₂ ·H ₂ O; 2) Add the copper salt precursor to the alkali metal salt modifier formate solution obtained in step 1), replace the air with N ₂ , and after stirring the reaction, a solid-liquid mixture is obtained, the solid precipitate is separated out, and washed and dried , to prepare an in-situ modified copper-based catalyst for furfural hydrogenation to furfuryl alcohol. 2. a kind of modified copper-based catalyst preparation method of furfural hydrogenation to furfuryl alcohol as claimed in claim 1 is characterized in that in step 1), the mass percentage concentration of described alkali metal salt modifier is 0.05%～ 1%. 3. a kind of modified copper-based catalyst preparation method of furfural hydrogenation to furfuryl alcohol as claimed in claim 2 is characterized in that in step 1), the mass percentage concentration of described alkali metal salt modifier is 0.1%～ 0.5%. 4. a kind of modified copper-based catalyst preparation method of furfural hydrogenation to furfuryl alcohol as claimed in claim 1 is characterized in that in step 1), described reaction solvent is selected from 1,4-dioxane, tetrahydrofuran, At least one of methanol, ethanol or water. 5. a kind of modified copper-based catalyst preparation method of furfural hydrogenation to furfuryl alcohol as claimed in claim 4 is characterized in that in step 1), described reaction solvent is 1,4-dioxane and tetrahydrofuran. 6 . The method for preparing a modified copper-based catalyst for hydrogenating furfural to furfuryl alcohol as claimed in claim 1 , wherein in step 1), the mass percentage concentration of the anhydrous formic acid is 0.1% to 10%. 7 . 7 . The method for preparing a modified copper-based catalyst for hydrogenating furfural to furfuryl alcohol according to claim 6 , wherein in step 1), the mass percentage concentration of the anhydrous formic acid is 0.5% to 5%. 8 . 8. a kind of modified copper-based catalyst preparation method of furfural hydrogenation to furfuryl alcohol as claimed in claim 1 is characterized in that in step 2), described copper salt precursor is selected from Cu(HCOO) ₂ ·4H ₂ O , at least one of Cu(CH ₃ COO) ₂ ·H ₂ O, Cu(NO ₃ ) ₂ ·4H ₂ O and CuSO ₄ ·5H ₂ O. 9. a kind of modified copper-based catalyst preparation method of furfural hydrogenation to furfuryl alcohol as claimed in claim 1 is characterized in that in step 2), the mass percentage concentration of described copper salt precursor is 0.1%～5% . 10. The method for preparing a modified copper-based catalyst for hydrogenating furfural to furfuryl alcohol as claimed in claim 9, wherein in step 2), the mass percentage concentration of the copper salt precursor is 1% to 3% . 11. a kind of modified copper-based catalyst preparation method of furfural hydrogenation to furfuryl alcohol as claimed in claim 1, is characterized in that in step 2), described with N ₂ Replacing the exhaust air is to use N ₂ Replacing 3～5 The air in the reactor was exhausted. 12. a kind of modified copper-based catalyst preparation method of furfural hydrogenation to furfuryl alcohol as claimed in claim 1, is characterized in that in step 2), the temperature of described reaction is 100～200 ℃, and the time of reaction is 0.1～ 4h, rotating speed 500rpm. 13. a kind of modified copper-based catalyst preparation method of furfural hydrogenation to furfuryl alcohol as claimed in claim 12, is characterized in that in step 2), the temperature of described reaction is 150～180 ℃, and the time of reaction is 0.5～ 2h. 14. a kind of modified copper-based catalyst preparation method of furfural hydrogenation to furfuryl alcohol as claimed in claim 1, it is characterized in that the product prepared by described method is in-situ Cu _- BaCO Catalyst, it is used for furfural liquid phase hydrogenation The reaction method for preparing furfuryl alcohol is as follows: The reactant furfural, 1,4-dioxane solution, anhydrous formic acid and in-situ Cu _- BaCO catalyst are mixed and placed in a closed autoclave, wherein the mass percentage concentration of furfural is 0.15% to 10%, no The molar ratio of water formic acid and furfural is 4:1, replace the air with _N2 , or directly use _H2 without adding anhydrous formic acid, 0.5～3MPa _H2 replaces anhydrous formic acid as the hydrogen source for the reaction, the reaction temperature 150～200℃, the reaction time is 0.5～4h, and the rotating speed is 500rpm.

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