CN113061122B

CN113061122B - Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran

Info

Publication number: CN113061122B
Application number: CN202110277384.1A
Authority: CN
Inventors: 李振宇; 邱建备; 张建; 郝盼盼
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS; Kunming University of Science and Technology
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS; Kunming University of Science and Technology
Priority date: 2021-03-15
Filing date: 2021-03-15
Publication date: 2023-04-07
Anticipated expiration: 2041-03-15
Also published as: CN113061122A

Abstract

The application discloses a preparation method of 2, 5-dihydroxymethyl tetrahydrofuran, which comprises the following steps: in a hydrogen-containing atmosphere, reacting a material containing 5-hydroxymethylfurfural in the presence of a catalyst I to obtain the 2, 5-dimethyloltetrahydrofuran; the catalyst comprises an active component and a carrier; the active component is loaded on the carrier; the active component is selected from transition metals; the transition metal is selected from nickel. The method takes 5-hydroxymethylfurfural as a raw material, realizes the high-efficiency preparation of the 2, 5-dimethyloltetrahydrofuran by adjusting the temperature and the pressure, and has good industrial application prospect.

Description

Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran

Technical Field

The application relates to a preparation method of 2, 5-dihydroxymethyl tetrahydrofuran, belonging to the technical field of chemical production.

Background

Along with the development and progress of society, the demand of human beings on non-renewable fossil resources is increasing, so that the environmental pollution, the energy crisis and the like caused by the increasing demand are more severe, and the green sustainable development provided by the new era is challenged. In order to solve the above problems, it is necessary to find a substitute for non-renewable fossil resources. The biomass is used as a raw material, various platform-based compounds can be obtained through treatment, and various valuable chemicals can be obtained through the easy conversion of the platform-based compounds.

2, 5-dimethyloltetrahydrofuran is commonly used for processing precursors for the production of polyols or some polymers, and since 2, 5-dimethyloltetrahydrofuran is liquid at room temperature, it is also used as a solvent for some interconversion between carbohydrates (Renewable and stable Energy Reviews 74 (2017) 230-257). The liquid obtained by esterifying 2, 5-dihydroxymethyl tetrahydrofuran with acid has good lubricating effect, can be used on heavy equipment such as trucks, tanks and the like, and the solid has the characteristic of good toughness. 2, 5-dihydroxymethyl tetrahydrofuran can get many kinds of etherified products through reacting with alcohol, and can effectively improve the ignition point of gasoline when used as additive in gasoline. In addition, the 2, 5-dihydroxymethyl tetrahydrofuran has certain application potential in the pharmaceutical, sanitary and textile energy industries.

Starting from 5-hydroxymethylfurfural as a raw material, it is difficult to reduce aldehyde groups in the 5-hydroxymethylfurfural into hydroxyl groups and fully reduce double bonds in furan rings, and further hydrogenation reactions such as dehydroxylation, ring opening and the like cannot occur. In order to reduce the aldehyde group in 5-hydroxymethylfurfural to hydroxyl group and completely reduce the double bond in furan ring, noble metal supported carbon carrier or oxide is often used as catalyst in literature, but the yield is not very high, mainly because the noble metal catalyst is very easy to destroy the hydroxymethyl group in 2, 5-dihydroxymethyltetrahydrofuran in the hydrogenation reduction process.

Disclosure of Invention

According to one aspect of the application, the preparation method of the 2, 5-dimethyloltetrahydrofuran is provided, the catalyst taking the transition metal nickel as an active component can efficiently catalyze the 5-hydroxymethylfurfural to reduce and prepare the 2, 5-dimethyloltetrahydrofuran, and the cost of the catalyst is greatly reduced.

The non-noble metal developed in the invention is used as the active component of the catalyst, and can realize the high-efficiency hydrogenation reduction of the 5-hydroxymethylfurfural by directional catalysis to prepare the 2, 5-dihydroxymethyltetrahydrofuran.

According to a first aspect of the present application, there is provided a process for the preparation of 2, 5-dimethyloltetrahydrofuran, the process comprising:

in a hydrogen-containing atmosphere, reacting a material containing 5-hydroxymethylfurfural in the presence of a catalyst to obtain the 2, 5-dihydroxymethyltetrahydrofuran;

the catalyst comprises an active component and a carrier; the active component is loaded on the carrier;

the active component is selected from transition metals; the transition metal is selected from nickel.

Alternatively, the reaction i is carried out under anhydrous conditions.

Optionally, the initial 5-hydroxymethylfurfural concentration is an initial reaction concentration of 1g to 30g of feedstock in 500mL of anhydrous ethanol.

Optionally, the support is selected from oxides; the oxide is at least one of silicon dioxide, magnesium oxide, zirconium dioxide, cerium dioxide and aluminum oxide.

Optionally, the silica is selected from at least one of fumed silica, solid phase silica.

Optionally, in the catalyst, the mass content of the active component is 5 to 30%.

Optionally, in the catalyst, the upper limit of the mass content of the active component is independently selected from 30%, 25%, 20%, 15%, 10%, 8%, and the lower limit is independently selected from 5%, 25%, 20%, 15%, 10%, 8%.

Optionally, the conditions of reaction I are: the temperature is 70-130 ℃; the time is 3 to 12 hours; the pressure is 3-8 MPa.

Optionally, the upper temperature limit of reaction I is independently selected from 130 ℃, 120 ℃,110 ℃, 100 ℃, 90 ℃, 80 ℃, and the lower temperature limit is independently selected from 70 ℃, 120 ℃,110 ℃, 100 ℃, 90 ℃, 80 ℃.

Alternatively, the upper time limit of the reaction I is independently selected from 12h, 10h, 8h, 6h, 4h, and the lower time limit is independently selected from 1h, 10h, 8h, 6h, 4h, 3h.

Alternatively, the upper pressure limit of reaction I is independently selected from 8MPa, 7MPa, 6MPa, 5MPa, 4MPa and the lower limit is independently selected from 3MPa, 7MPa, 6MPa, 5MPa, 4MPa.

Optionally, a solvent is also included in the material; the solvent is selected from alcohol compounds.

Optionally, the alcohol compound is selected from at least one of ethanol, methanol and isopropanol.

Optionally, the ethanol is anhydrous ethanol.

Optionally, the mass-to-volume ratio of the 5-hydroxymethylfurfural to the solvent in the material is (1-30) g:500mL.

Optionally, the upper limit of the mass to volume ratio of the 5-hydroxymethylfurfural and the solvent is independently selected from 30g:500mL, 20g:500mL, 10g:500mL, 5g:500mL; the lower limit is independently selected from 1:500mL, 20g:500mL, 10g:500mL, 5g:500mL.

Optionally, the mass ratio of the catalyst to the 5-hydroxymethylfurfural is 0.5-4.8: 1 to 30;

wherein the mass of the catalyst is based on the mass of the transition metal contained therein.

Optionally, the preparation method of the catalyst comprises:

(1) Reacting II and roasting a mixture containing a transition metal source, a carrier and a precipitator to obtain a catalyst precursor;

(2) And reducing the catalyst precursor in a hydrogen-containing atmosphere to obtain the catalyst.

Optionally, the transition metal source is selected from at least one of transition metal salts;

the precipitating agent is selected from urea.

Alternatively, in the step (1), the conditions of the reaction II are: the temperature is 80-90 ℃; the time is 5 to 15 hours;

the roasting conditions are as follows: the temperature is 300-700 ℃; the time is 2 to 12 hours;

in the step (2), the reduction conditions are as follows: the temperature is 300-600 ℃; the time is 2 to 10 hours.

Optionally, the mass ratio of the transition metal source, the carrier and the precipitant is 2-45: 4 to 6:2 to 25;

wherein the mass of the transition metal source is based on the mass of the transition metal.

Alternatively, the catalyst is prepared by adopting the following method:

(1) Uniformly mixing 500mL of solution containing a nickel source with an oxide carrier;

(2) Adding 100mL of precipitant aqueous solution, and decomposing to obtain hydroxide precipitate;

(3) Roasting nickel-containing powder to obtain a precursor;

(4) And reducing the precursor by adopting hydrogen to obtain the catalyst.

Optionally, in the step (1), the mass ratio of the carrier to the nickel in the 100mL of aqueous solution is 0.4 to 15.

Optionally, in the step (2), the mass ratio of the carrier to the urea in the 100mL of aqueous solution is 0.2 to 2.

Optionally, the transition metal nickel salt is selected from at least one of nickel nitrate, nickel chloride and nickel sulfate.

Alternatively, the preparation method of the catalyst comprises the following steps:

s100: the solution containing the nickel source is mixed with the oxide support uniformly.

S200: adding urea aqueous solution, and mixing uniformly.

S300: and roasting the powder containing the nickel to obtain a precursor.

S400: and reducing the precursor by adopting hydrogen.

Alternatively, the nickel sources in step S100 are derived from different nickel salts.

Optionally, the urea aqueous solution is added in step S200, and the uniform nickel hydroxide precipitation can be obtained by uniform stirring.

Optionally, the step S300 of calcining the powder containing nickel hydroxide and the carrier to obtain uniformly mixed nickel oxide and oxide.

Optionally, in step S400, the precursor is reduced under high-temperature hydrogen to obtain the catalyst.

The beneficial effects that this application can produce include:

1) The catalyst used in the method takes nickel as an active center, can efficiently catalyze 5-hydroxymethylfurfural to reduce and prepare 2, 5-dimethyloltetrahydrofuran, and greatly reduces the cost of the catalyst.

2) The preparation method of the catalyst provided by the application has the advantages of high catalyst activity, long service life and easiness in separation from a product after use.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.

The analysis method in the examples of the present application is as follows:

the conversion of the reactants and the yield of the products were quantified by means of a High Performance Liquid Chromatograph (HPLC) model Agilent Technologies 1260 Infinity II equipped with a UV-absorption photodetector and an extended-C18 USP L1 column (4.6 mm. Times.250 mm). The liquid chromatograph adopts a mixed solution of methanol and an aqueous ammonium formate solution as a mobile phase, the concentration of the aqueous ammonium formate solution is 5.0mM, and the volume ratio of the methanol to the aqueous ammonium formate solution is 1:9, the total flow rate of the mobile phase was 0.8mL/min.

The actual loading of the elements was quantitatively analyzed using inductively coupled plasma optical emission spectrometer (ICP-OES) with spectra arccos ii.

Due to the limitations of the prior art, the inventor finally provides a technical scheme through a large number of theoretical and practical analyses. The implementation of this solution is partially explained as follows.

The calculation formula of the conversion rate of the 5-hydroxymethylfurfural is as follows:

5-hydroxymethylfurfural conversion = 1-post-reaction 5-hydroxymethylfurfural molar concentration/initial 5-hydroxymethylfurfural molar concentration

The yield of 2, 5-dimethyloltetrahydrofuran is calculated as follows:

5-hydroxymethylfurfural yield = 2, 5-dimethyloltetrahydrofuran molar concentration after reaction/initial 5-hydroxymethylfurfural molar concentration

The nickel salts used in the examples of this application are all hexahydrate.

Example 1

Preparation of catalyst # 1

(1) To a flask, 4g of fumed silica and 500mL of an aqueous solution were added to dissolve nickel nitrate containing 6g of nickel, and the mixture was stirred at 80 ℃ for 1 hour until uniformly dispersed.

(2) 100mL of an aqueous solution containing 10g of urea was added to (1), the temperature was raised to 90 ℃ and the mixture was stirred vigorously for 12 hours, followed by mixing.

(3) Step (2) filtration, 110 ℃ drying 12 hours after the mixture in muffle furnace 500 ℃ calcined for 10 hours.

(4) And (4) reducing the calcined material obtained in the step (3) in a tubular furnace by using hydrogen at 450 ℃ for 5 hours. Is described as Ni/F-SiO ₂ 。

The actual loading of the catalyst was 22.3wt% as determined by ICP-OES.

Example 2

Preparation of catalyst # 2-4 #

The preparation of catalyst # 2-4 # was different from that of catalyst # 1 in that nickel nitrate containing 10g, 3g and 0.8g of nickel was dissolved in 500mL of the aqueous solution in step (1), respectively, and the other preparation was completely identical to that of catalyst # 1. The actual loading of the catalyst was 25.6wt%, 14.6wt% and 6.0wt%, respectively, as determined by ICP-OES.

Example 3

Preparation of catalysts # 5-6

The preparation of catalysts # 5-6 # differs from catalyst # 1 in that the nickel source in step (1) was changed to nickel chloride and nickel sulfate, respectively, and the others were completely identical to the preparation of catalyst # 1.

Example 4

Preparation of catalyst # 7-9

The preparation of catalysts 7# -9# differs from catalyst 1# in that the support in step (1) was changed from fumed silica to solid silica, zirconia and ceria, respectively, and otherwise is identical to the preparation of catalyst 1 #.

Example 5

Preparation of catalyst # 10-12 #

The preparation of catalyst # 10-12 # was different from that of catalyst # 1 in that in step (2), the 100mL aqueous solution in which 10g of urea was dissolved was changed to 18g, 13g and 5g of urea, respectively, and the other preparation was completely identical to that of catalyst # 1.

Example 6

Preparation of catalyst # 13-15 #

The preparation of catalyst # 13-15 # was different from that of catalyst # 1 in that the calcination temperatures in the muffle furnace in step (3) were changed to 700 deg.C, 600 deg.C and 400 deg.C, respectively, and the other preparation was completely identical to that of catalyst # 1.

Example 7

Preparation of catalyst # 16-18

The preparation of catalysts # 16-18 # differs from catalyst # 1 in that the hydrogen reduction temperature in the tube furnace in step (4) was changed to 600 ℃, 500 ℃ and 360 ℃, respectively, and otherwise was completely identical to the preparation of catalyst # 1 #.

Example 8

Evaluation of catalyst # 1 Performance

(1) 500mL of anhydrous ethanol and 10g of 5-hydroxymethylfurfural are added into a high-pressure reaction kettle, and after uniform stirring, a No. 1 catalyst containing 1g of nickel is added.

(2) Introducing hydrogen, regulating the pressure of the hydrogen to 5MPa, introducing stirring and refluxing.

(3) The temperature rise was suspended when the temperature rose to 80 ℃.

(4) After 10 hours of reaction, the 5-hydroxymethylfurfural was completely converted, and the yield of 2, 5-dimethyloltetrahydrofuran was 94.2%.

Example 9

Evaluation of catalyst # 1 Performance

Example 9 differs from example 8 in the reaction pressure of catalyst evaluation. Other conditions were the same as in example 8. The evaluation results are shown in table 1 below:

TABLE 1

Example 10

Example 10 evaluates catalyst # 5 and differs from example 8 in the reaction temperature. Other conditions were the same as in example 8. The evaluation results are shown in table 2 below:

TABLE 2

Example 11

Example 11 evaluates catalyst # 10 and differs from example 8 also in the quality of the initial charge of 5-hydroxymethylfurfural. Other conditions were the same as in example 8. The evaluation results are shown in table 3 below:

TABLE 3

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Example 12

Example 12 evaluates catalyst # 10 and differs from example 8 in the reaction length. Other conditions were the same as in example 8. The evaluation results are shown in table 4 below:

TABLE 4

Example 13

Example 13 the catalyst # 7 to # 9 was evaluated, and the other conditions were the same as in example 8. The evaluation results are shown in the following table 5:

TABLE 5

Example 14

Example 14 evaluated catalyst # 17 and differed from example 8 in the content of metallic nickel. Other conditions were the same as in example 8. The evaluation results are shown in table 6 below:

TABLE 6

Example 15

Example 15# 13-15 # catalyst was evaluated and the other conditions were consistent with example 8. The evaluation results are shown in table 7 below:

TABLE 7

Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims

1. A method for preparing 2, 5-dimethyloltetrahydrofuran, the method comprising:

the active component is selected from transition metals; the transition metal is selected from nickel;

in the catalyst, the mass content of the active component is 5-30%;

the conditions of the reaction I are as follows: the temperature is 70 to 130 ℃; the time is 7 to 12h; the pressure is 5 to 8MPa;

the support is selected from fumed silica;

in the material, the mass volume ratio of the 5-hydroxymethylfurfural to the solvent is (1-15) g:500mL.

2. The method according to claim 1, characterized in that in the material, a solvent is further included; the solvent is selected from alcohol compounds.

3. The method according to claim 2, wherein the alcohol compound is at least one selected from the group consisting of ethanol, methanol and isopropanol.

4. The preparation method according to claim 1, wherein the mass ratio of the catalyst to the 5-hydroxymethylfurfural is 0.5 to 4.8:1 to 30;

5. The method according to claim 1, wherein the method for preparing the catalyst comprises:

6. The production method according to claim 5, wherein the transition metal source is at least one selected from transition metal salts; the precipitant is selected from urea.

7. The production method according to claim 5, wherein in the step (1), the conditions of the reaction II are: the temperature is 80-90 ℃; the time is 5 to 15 hours;

the roasting conditions are as follows: the temperature is 600 to 700 ℃; the time is 2 to 12h;

in the step (2), the reduction conditions are as follows: the temperature is 300 to 600 ℃; the time is 2 to 10 hours.

8. The preparation method according to claim 5, wherein the mass ratio of the transition metal source to the carrier to the precipitant is 2 to 45:4 to 6:2 to 25;