METHOD FOR PREPARING 2,5-BISHYDROXYMETHYLFURAN USING 5-CHLOROMETHYLFURFURAL

Abstract

A method for preparing 2,5-bishydroxymethylfuran using 5-chloromethylfurfural, the 5-chloromethylfurfural is transformed into the 2,5-bishydroxymethylfuran using a catalyst, a base neutralizer, sodium dithionite, and deionized water.

Claims

1. A method for preparing 2,5-bishydroxymethylfuran using 5-chloromethylfurfural, comprising: adding the 5-chloromethylfurfural, a catalyst, a base neutralizer, sodium dithionite, and deionized water to a closed reactor, filling H.sub.2 into the closed reactor, and reacting by stirring at a speed of 400-800 revolutions per minute (rpm), wherein the catalyst is a ruthenium-based metal oxide.

2. The method according to claim 1, wherein: the catalyst is prepared by the following method: dispersing metal oxide in RuCl.sub.3.Math.3H.sub.2O solution while stirring, adding NaBH.sub.4 solution dropwise while stirring, and obtaining the catalyst by centrifugation, washing with the deionized water, and freeze-drying, wherein the metal oxide is Cu oxide or Co oxide.

3. The method according to claim 2, wherein a weight ratio of the metal oxide, the RuCl.sub.3.Math.3H.sub.2O, and the NaBH.sub.4 is 1:0.05-0.2:0.05-2.

4. The method according to claim 1, wherein a ratio of the 5-chloromethylfurfural and the deionized water is 1:50-250 g/mL.

5. The method according to claim 1, wherein a weight ratio of the 5-chloromethylfurfural and the catalyst is 1:0.5-1.5.

6. The method according to claim 1, wherein a weight ratio of the 5-chloromethylfurfural and the sodium dithionite is 1:0.05-0.2.

7. The method according to claim 1, wherein a molar ratio of the 5-chloromethylfurfural and the base neutralizer is 1:0.5-0.9.

8. The method according to claim 1, wherein: the filling H.sub.2 into the closed reactor comprises filling the H.sub.2 into the closed reactor until an initial pressure of H.sub.2 is 2-5 MPa, and the reacting by stirring at a speed of 400-800 rpm comprises reacting by stirring at the speed of 400-800 rpm at a temperature of 40-80? C. for 0.5-8 hours.

9. The method according to claim 1, wherein the base neutralizer is calcium carbonate, potassium bicarbonate, or sodium bicarbonate.

10. The method according to claim 1, wherein the closed reactor is a stainless steel closed reactor.

11. The method according to claim 1, wherein the catalyst is at least one of Ru/CuO or Ru/Co.sub.3O.sub.4.

12. The method according to claim 1, wherein the catalyst is Ru/CuO.

13. The method according to claim 2, wherein the metal oxide is CuO and Co.sub.3O.sub.4.

14. The method according to claim 1, wherein a ratio of the 5-chloromethylfurfural and the deionized water is 1:50-100 g/mL.

15. The method according to claim 1, wherein a weight ratio of the 5-chloromethylfurfural and the catalyst is 1:1.

16. The method according to claim 1, wherein a weight ratio of the 5-chloromethylfurfural and the sodium dithionite is 1:0.1.

17. The method according to claim 1, wherein a molar ratio of the 5-chloromethylfurfural and the base neutralizer is 1:0.7.

18. The method according to claim 1, wherein the reacting by stirring at a speed of 400-800 rpm comprises reacting by stirring at the speed of 400-800 rpm at a temperature of 60-70? C. for 2-5 hours.

19. The method according to claim 1, wherein the base neutralizer is calcium carbonate.

Description

BRIEF DESCRIPTION OF THE DRAWING

[0016] FIG. 1 illustrates a reaction pathway for preparing 2,5-bishydroxymethylfuran from 5-chloromethylfurfural.

[0017] FIG. 2 illustrates a spectrum of 2,5-bishydroxymethylfuran prepared by Embodiment 16 of the present disclosure with high performance liquid chromatography (HPLC).

[0018] FIG. 3 illustrates a spectrum of 2,5-bishydroxymethylfuran prepared by Embodiment 16 of the present disclosure with gas chromatography-mass spectrometry (GC-MS).

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0019] The present disclosure will be further described below in combination with the accompanying embodiment. Unless otherwise specified, the reagents and instruments used in the following embodiments are commercially available products. The specific embodiments are as follows:

Embodiment 1

[0020] Step 1) 0.103 g of RuCl.sub.3.Math.3H.sub.2O is dissolved in 30 mL of deionized water to obtain a solution, and 1 g of CuO is then added to the aqueous solution and stirred for 2 hours. NaBH.sub.4 solution (in which 0.3 g of NaBH.sub.4 is dissolved in 20 mL of deionized water) is then added dropwise and stirred for 1 hour. A catalyst of Ru/CuO is obtained by centrifugation, washing using 30 mL of deionized water for 3 times, and freeze drying. A loading amount of Ru is 5 wt % Ru relative to a carrier of CuO. Step 2) 0.1 g of 5-chloromethylfurfural, 0.1 g of the catalyst Ru/CuO, 0.05 g of calcium carbonate as a base neutralizer, 0.01 g of sodium dithionite, and 10 mL of deionized water are added to a stainless steel closed reactor, H.sub.2 is filled into the stainless steel closed reactor until an initial H.sub.2 pressure is 4 MPa, heated to 70? C. while stirring at a speed of 500 revolutions per minute (rpm), and reacted for 2 hours to obtain a reaction solution involving 2,5-bishydroxymethylfuran. After the reaction is complete, solid-liquid separation of the reaction solution involving 2,5-bishydroxymethylfuran is performed by a centrifuge machine at a speed of 8000 rpm for 5 minutes, and quantitative analysis is performed by high performance liquid chromatography (HPLC, Agilent 1260). Qualitative analysis is performed using gas chromatography-mass spectrometry (GC-MS, Thermo Scientific). The results are as follows: a molar yield of 2,5-bishydroxymethylfuran is 76%.

Embodiment 2

[0021] Step 1) The catalyst is prepared according to the method of Embodiment 1 for use. This embodiment differs from Embodiment 1 in that the carrier of the catalyst is Co.sub.3O.sub.4, so that a catalyst of Ru/Co.sub.3O.sub.4 is obtained. A loading amount of Ru is 5 wt % Ru relative to the carrier of Co.sub.3O.sub.4.

[0022] Step 2) The step 2 of Embodiment 2 is performed according to the step 2 of the method of Embodiment 1 using the catalyst of Ru/Co.sub.3O.sub.4. The results are as follows: a molar yield of 2,5-bishydroxymethylfuran is 34%.

Embodiments 3-6

[0023] Step 1) Four catalysts are prepared according to the method of Embodiment 1 for use. Embodiments 3-6 differ from Embodiment 1 in that 0.0205 g (1 wt %), 0.0616 g (3 wt %), 0.144 g (7 wt %), or 0.185 g (9 wt %) of RuCl.sub.3-3H.sub.2O are added, respectively. The loading amount of Ru is 1 wt % Ru, 3 wt % Ru, 7 wt % Ru, or 9 wt % Ru relative to the carrier of CuO, respectively.

[0024] Step 2) The step 2 of each of Embodiments 3-6 is performed according to the step 2 of the method of Embodiment 1 using the four catalysts. The results are as follows: molar yields of 2,5-bishydroxymethylfuran are 13%, 39%, 74%, and 55%, respectively.

Embodiments 7-8

[0025] Embodiments 7-8 differ from Embodiment 1 in that the base neutralizer is NaHCO.sub.3 and KHCO.sub.3, respectively. The results are as follows: molar yields of 2,5-Bishydroxymethylfuran are 56% and 47%, respectively.

Embodiments 9-13

[0026] Embodiments 9-13 differ from Embodiment 1 in that the reaction for obtaining 2,5-bishydroxymethylfuran using 5-chloromethylfurfural is performed for 1 hour, 3 hours, 4 hours, 5 hours, and 6 hours, respectively. The results are as follows: molar yields of 2,5-Bishydroxymethylfuran are 51%, 78%, 81%, 76%, and 75%, respectively.

Embodiments 14-16

[0027] Embodiments 14-16 differ from Embodiment 1 in that the reaction for obtaining 2,5-bishydroxymethylfuran using 5-chloromethylfurfural is performed for 4 hours at 40? C., 50? C., and 60? C., respectively. The results are as follows: molar yields of 2,5-bishydroxymethylfuran are 28%, 73%, and 91%, respectively.

Embodiments 17-19

[0028] Embodiments 17-19 differ from Embodiment 1 in that the reaction for obtaining 2,5-bishydroxymethylfuran using 5-chloromethylfurfural is performed at 60? C. with the initial H.sub.2 pressure of 2 MPa, 3 MPa, and 5 MPa for 4 hours. The results are as follows: molar yields of 2,5-bishydroxymethylfuran are 39%, 58%, and 84%, respectively.

[0029] The above-mentioned results are summarized in the following table:

TABLE-US-00001 TABLE 1 Effects of different types of catalysts and process variables on the hydrogenation yield of 5-chloromethylfurfural Loading BHMF amount yield of Ru Base Temperature Time Pressure rate Embodiment Catalyst (wt %) neutralizer (? C.) (hour) (MPa) (%) 1 Ru/CuO 5 CaCO.sub.3 70 2 4 76 2 Ru/Co.sub.3O.sub.4 5 CaCO.sub.3 70 2 4 34 3 Ru/CuO 1 CaCO.sub.3 70 2 4 13 4 Ru/CuO 3 CaCO.sub.3 70 2 4 39 5 Ru/CuO 7 CaCO.sub.3 70 2 4 74 6 Ru/CuO 9 CaCO.sub.3 70 2 4 55 7 Ru/CuO 5 NaHCO.sub.3 70 2 4 56 8 Ru/CuO 5 KHCO.sub.3 70 2 4 47 9 Ru/CuO 5 CaCO.sub.3 70 1 4 51 10 Ru/CuO 5 CaCO.sub.3 70 3 4 78 11 Ru/CuO 5 CaCO.sub.3 70 4 4 81 12 Ru/CuO 5 CaCO.sub.3 70 5 4 76 13 Ru/CuO 5 CaCO.sub.3 70 6 4 75 14 Ru/CuO 5 CaCO.sub.3 40 4 4 28 15 Ru/CuO 5 CaCO.sub.3 50 4 4 73 16 Ru/CuO 5 CaCO.sub.3 60 4 4 91 17 Ru/CuO 5 CaCO.sub.3 60 4 2 39 18 Ru/CuO 5 CaCO.sub.3 60 4 3 58 19 Ru/CuO 5 CaCO.sub.3 60 4 5 84

[0030] Based on the results of the above-mentioned embodiments, it is shown that the catalyst (Ru/CuO, especially when the loading amount of Ru is 5 wt % relative to carrier CuO) and the base neutralizer (especially CaCO.sub.3) provided by the present disclosure can be effectively used in a preparation of 2,5-bishydroxymethylfuran (a high value-added fine chemical product) by hydrogenation of 5-chloromethylfurfural. The molar yield of 2,5-bishydroxymethylfuran is 91% under an optimal reaction condition, i.e., a temperature of the reaction is 60? C., a time of the reaction is 4 hours, and the initial pressure of H.sub.2 is 4 MPa.

[0031] The embodiments are merely used for an objective of providing exemplary illustrations, and the protective scope of the present disclosure is not limited thereto in any way. Thus, it is intended that the protective scope of the present disclosure cover improvements and modifications provided they are improved or modified based on the aforementioned illustrations by person skilled in the art.