A method for preparing dimethyl furandicarboxylate by combining a gold-based catalyst with an initiator and high efficiency catalysis

Abstract

The invention discloses a method for preparing dimethyl furandicarboxylate by high-efficiency catalysis of a gold-based catalyst and an initiator, and belongs to the technical field of preparing dimethyl furandicarboxylate. The invention first prepares a gold catalyst using an oxide as a carrier by an impregnation method or a deposition precipitation method, and then efficiently catalyzes 5-hydroxymethylfurfural (HMF) or furan dicarboxaldehyde (DFF) to prepare dimethyl furandicarboxylate (FDME) in the presence of initiators such as H2O2, tert-butyl hydroperoxide (TBHP), and isopropylbenzene hydroperoxide (CHPO), thereby greatly improving the efficiency of the catalytic reaction in a short time, achieving high-efficiency output under the action of a low-load catalyst, and the method is conducive to large-scale industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of dimethyl furandicarboxylate preparation, and relates to a method for preparing dimethyl furandicarboxylate by using a gold-based catalyst in combination with an initiator for efficient catalytic preparation, and specifically relates to a method for preparing dimethyl furandicarboxylate (FDME) by using a gold-based catalyst in combination with an initiator for efficient catalytic oxidation of 5-hydroxymethylfurfural (HMF) or furan dicarboxaldehyde (DFF). Background Art

[0002] With the extensive use of fossil energy, environmental pollution, air deterioration, climate warming and energy crisis have seriously affected people's normal life and sustainable development. In this regard, the development of renewable biomass resources has become the top research topic for mankind. How to further transform renewable biomass energy into high-value-added chemicals is the focus and difficulty of today's research, and it is also the bottleneck to solve sustainable development.

[0003] Among them, HMF, as an important biomass platform molecule, is listed by the U.S. Department of Energy as one of the most important biomass platform molecules in the 21st century. HMF can be derived from the hydrolysis of glucose or fructose and has a very important biological substitution value. In particular, the preparation of FDME by catalytic oxidation of HMF is an efficient and environmentally friendly biomass route. Based on the fact that HMF can be obtained by dehydrating raw materials such as cellulose and glucose (CN104250237A). Therefore, the catalytic oxidation synthesis of FDME from HMF obtained from non-petrochemical raw materials is of great significance.

[0004] At present, the catalysts for preparing FDME still revolve around catalysts with precious metals as active components. Based on the literature that has been reported, Au / TiO2 catalytically oxidizes HMF to produce FDME under specific conditions (0.4MPa O2 and 303K for 3 hours), and the selectivity obtained is 98% (ChemSusChem, 2008, 1, 75). The yield of FDME produced by Au / CeO2 catalyst under certain conditions (10bar O2 and 130°C) is 99% (J.Cat. 2009, 265, 109). At present, the strategy for preparing FDME by catalysis of both precious metal and non-precious metal catalysts is to obtain it by extending process parameters such as reaction time. Although the use of cheap metals can efficiently and selectively catalyze the oxidation esterification of HMF to synthesize FDME without the addition of alkali, the reaction time is more than 6 hours (CN 108084123 A, CN 111253353A). Therefore, research and development of a method for efficiently catalyzing 5-hydroxymethylfurfural or furandicarboxaldehyde to prepare dimethyl furandicarboxylate in a short time has become an important topic that needs to be studied urgently. Summary of the invention

[0005] In view of this, the purpose of the present invention is to provide a method for preparing dimethyl furandicarboxylate by combining a gold-based catalyst with an initiator. The method of the present invention greatly improves the efficiency of the catalytic reaction in a short period of time, and can achieve efficient output under the action of a low-loaded catalyst. The method is conducive to large-scale industrial production.

[0006] The object of the present invention is to achieve the following:

[0007] A method for efficiently catalyzing the preparation of dimethyl furandicarboxylate by a gold-based catalyst combined with an initiator comprises the following steps:

[0008] (1) preparing a gold-based catalyst by an impregnation method or a deposition precipitation method, wherein the gold loading is 0.01 to 5 wt %;

[0009] (2) placing a mixed solution of methanol and HMF or DFF in a reactor, adding an initiator accounting for 0.1-5% of the molar number of HMF or DFF, adding the gold-based catalyst prepared in step (1), adjusting the pressure of the reactor to 1-3 MPa using a gas with an oxygen concentration of 10-50%, adjusting the reaction temperature to 80-120° C., reacting for 10-60 minutes, and separating and obtaining dimethyl furandicarboxylate.

[0010] Based on the above technical scheme, further, the gold-based catalyst described in step (1) is one or a combination of two or more of Au / TiO2, Au / ZrO2, Au / Al2O3, Au / Fe3O4, Au / CeO2, Au / Co3O4, Au / MgO, and Au / MnO2.

[0011] Based on the above technical solution, further, the gold loading in step (1) is 0.1-1 wt%.

[0012] Based on the above technical solution, further, in step (2), the molar ratio of methanol to HMF or DFF is 5:1-100:1.

[0013] Based on the above technical solution, further, the initiator described in step (2) is one or a combination of two or more of hydrogen peroxide, tert-butyl hydroperoxide (TBHP), and isopropylbenzene hydroperoxide (CHPO).

[0014] Based on the above technical solution, further, the amount of the initiator added in step (2) is 0.1-0.5% of the molar number of HMF or DFF.

[0015] Based on the above technical solution, further, the amount of the gold-based catalyst added in step (2) is 1-100 g / L.

[0016] The beneficial effects of the present invention compared with the prior art are as follows:

[0017] The present invention uses a gold-based catalyst in combination with an initiator, and significantly improves the efficiency of preparing FDME by catalytic oxidation of HMF or DFF in a shorter time. Compared with the prior art, the method of the present invention significantly shortens the reaction time, improves the reaction efficiency, realizes the short-term and efficient preparation of FDME, is conducive to industrial production, and has a strong value for promotion and application. DETAILED DESCRIPTION

[0018] The present invention is described in detail below through specific examples, but these examples do not limit the contents of the present invention.

[0019] Comparative Example 1:

[0020] The gold-based catalyst catalyzes HMF to prepare FDME in the absence of an initiator, comprising the following steps:

[0021] (1) Preparation of gold-based catalysts: 1%-Au / TiO2, 1%-Au / ZrO2, 1%-Au / Al2O3, 1%-Au / MgO, and 1%-Au / MnO2 catalysts were prepared by impregnation method.

[0022] (2) A mixed solution of 12 ml of methanol and HMF (molar ratio of 50:1) was placed in a reactor, and 0.5 g of the gold-based catalyst prepared in step (1) was added thereto; the pressure of the reactor was adjusted to 3 MPa using a gas with an oxygen concentration of 50%, the reaction temperature was adjusted to 110°C, and the reaction was carried out for 30 minutes. After the reaction was completed, the product was analyzed by gas chromatography. The conversion rate of HMF and the selectivity of the product FDME were calculated. The results are shown in Table 1.

[0023] Table 1. Reaction activity of different catalysts in comparative example 1 for catalyzing HMF to FDME without initiator

[0024] Comparative Example 1 Reaction time (min) HMF conversion % FDME selectivity % <![CDATA[1%-Au / TiO2]]> 30 69 51 <![CDATA[1%-Au / ZrO2]]> 30 45 48 <![CDATA[1%-Au / Al2O3]]> 30 39 45 1%-Au / MgO 30 74 80 <![CDATA[1%-Au / MnO2]]> 30 55 61

[0025] Comparative Example 2:

[0026] The gold-based catalyst catalyzes DFF to prepare FDME in the absence of an initiator, comprising the following steps:

[0027] (1) Preparation of gold-based catalysts: 1%-Au / TiO2, 1%-Au / ZrO2, 1%-Au / Al2O3, 1%-Au / MgO, and 1%-Au / MnO2 catalysts were prepared by impregnation method.

[0028] (2) A mixed solution of 12 ml of methanol and DFF (molar ratio of 50:1) was placed in a reactor, and 0.5 g of the gold-based catalyst prepared in step (1) was added thereto; the pressure of the reactor was adjusted to 3 MPa using a gas with an oxygen concentration of 50%, the reaction temperature was adjusted to 110°C, and the reaction was carried out for 15 minutes. After the reaction was completed, the product was analyzed by gas chromatography, and the conversion rate of DFF and the selectivity of the product FDME were calculated. The results are shown in Table 2.

[0029] Table 2. Reaction activity of different catalysts in comparative example 2 in catalyzing DFF to FDME without initiator:

[0030] Comparative Example 2 Reaction time (min) DFF conversion % FDME selectivity % <![CDATA[1%-Au / TiO2]]> 15 72 77 <![CDATA[1%-Au / ZrO2]]> 15 56 67 <![CDATA[1%-Au / Al2O3]]> 15 50 74 1%-Au / MgO 15 88 90 <![CDATA[1%-Au / MnO2]]> 15 67 82

[0031] Embodiment 1:

[0032] The gold-based catalyst catalyzes HMF to prepare FDME in the presence of initiator H2O2, comprising the following steps:

[0033] (1) Preparation of gold-based catalysts: 0.1%-Au / TiO2 and 0.2%-Au / ZrO2 catalysts were prepared by impregnation method.

[0034] (2) 12 ml of a mixed solution of methanol and HMF (molar ratio of 50:1) was placed in a reactor, and hydrogen peroxide (30%) accounting for 0.1% of the molar number of DFF was added. 1.0 g of the gold-based catalyst prepared in step (1) was added thereto. The pressure of the reactor was adjusted to 3 MPa using a gas with an oxygen concentration of 50%, and the reaction temperature was adjusted to 110° C. The reaction was carried out for 30 minutes. After the reaction was completed, the product was analyzed by gas chromatography, and the conversion rate of HMF and the selectivity of the product FDME were calculated. The results are shown in Table 3.

[0035] Table 3. Reaction activity of different catalysts in Example 1 for catalyzing HMF to FDME under the action of initiator H2O2

[0036] Example 1 Reaction time (min) HMF conversion % FDME selectivity % <![CDATA[0.1%-Au / TiO2]]> 30 61 48 <![CDATA[0.2%-Au / ZrO2]]> 30 40 45

[0037] Embodiment 2:

[0038] The gold-based catalyst catalyzes DFF to prepare FDME in the presence of initiator H2O2, comprising the following steps:

[0039] (1) Preparation of gold-based catalysts: 0.1%-Au / TiO2 and 0.2%-Au / ZrO2 catalysts were prepared by impregnation method.

[0040] (2) Place 12 ml of a mixed solution of methanol and DFF (molar ratio of 50:1) in a reactor, add 0.1% of the molar number of DFF in hydrogen peroxide (30%), and add 1.0 g of the gold-based catalyst prepared in step (1). Use a gas with an oxygen concentration of 50% to adjust the pressure of the reactor to 3 MPa, adjust the reaction temperature to 110°C, and react for 15 minutes. After the reaction is completed, the product is analyzed by gas chromatography. Calculate the conversion rate of DFF and the selectivity of the product FDME. The results are shown in Table 4.

[0041] Table 4. The activity of different catalysts in Example 2 in catalyzing DFF to FDME under the action of initiator H2O2

[0042] Example 2 Reaction time (min) DFF conversion % FDME selectivity % <![CDATA[0.1%-Au / TiO2]]> 15 77 83 <![CDATA[0.2%-Au / ZrO2]]> 15 48 65

[0043] Embodiment 3:

[0044] The gold-based catalyst catalyzes HMF to prepare FDME in the presence of an initiator, tert-butyl hydroperoxide (TBHP), comprising the following steps:

[0045] (1) Preparation of gold-based catalyst: 0.1%-Au / Al2O 3, 0.1%-Au / MgO catalyst;

[0046] (2) A mixed solution of 12 ml of methanol and HMF (molar ratio of 50:1) was placed in a reactor, 0.1% of the molar number of DFF in TBHP was added, and 1.0 g of the gold-based catalyst prepared in step (1) was added thereto. The pressure of the reactor was adjusted to 3 MPa using a gas with an oxygen concentration of 20%, and the reaction temperature was adjusted to 110°C, and the reaction was carried out for 30 minutes. After the reaction was completed, the product was analyzed by gas chromatography. The conversion rate of HMF and the selectivity of the product FDME were calculated. The results are shown in Table 5.

[0047] Table 5. Reaction activity of different catalysts in Example 3 for catalyzing HMF to FDME under the action of initiator TBHP

[0048] Example 3 Reaction time (min) HMF conversion % FDME selectivity % <![CDATA[0.1%-Au / Al2O3]]> 30 45 53 0.1%-Au / MgO 30 23 37

[0049] Embodiment 4:

[0050] The gold-based catalyst catalyzes DFF to prepare FDME in the presence of initiator TBHP, comprising the following steps:

[0051] (1) Preparation of gold-based catalyst: 0.1%-Au / Al2O 3, 0.1%-Au / MgO catalyst.

[0052] (2) A mixed solution of 12 ml of methanol and DFF (molar ratio of 50:1) was placed in a reactor, 0.1% of the molar number of DFF was added to TBHP, and 1.0 g of the gold-based catalyst prepared in step (1) was added thereto. The pressure of the reactor was adjusted to 3 MPa using a gas with an oxygen concentration of 20%, and the reaction temperature was adjusted to 110°C. The reaction was carried out for 15 minutes. After the reaction was completed, the product was analyzed by gas chromatography to calculate the conversion rate of DFF and the selectivity of the product FDME. The results are shown in Table 6.

[0053] Table 6. Reaction activity of different catalysts in Example 4 for catalyzing DFF to FDME under the action of initiator TBHP

[0054] Example 4 Reaction time (min) HMF conversion % FDME selectivity % <![CDATA[0.1%-Au / Al2O3]]> 15 56 71 0.1%-Au / MgO 15 21 45

[0055] Embodiment 5:

[0056] The gold-based catalyst catalyzes HMF to prepare FDME in the presence of an initiator, cumene hydroperoxide (CHPO), comprising the following steps:

[0057] (1) Preparation of gold-based catalysts: 0.1%-Au / MgO and 0.1%-Au / MnO2 catalysts were prepared by impregnation method.

[0058] (2) A mixed solution of 12 ml of methanol and HMF (molar ratio of 50:1) was placed in a reactor, and CHPO accounting for 0.1% of the molar number of DFF was added. 1.0 g of the gold-based catalyst prepared in step (1) was added thereto, and the pressure of the reactor was adjusted to 3 MPa using a gas with an oxygen concentration of 50%, and the reaction temperature was adjusted to 110°C. The reaction was carried out for 30 minutes. After the reaction was completed, the product was analyzed by gas chromatography, and the conversion rate of HMF and the selectivity of the product FDME were calculated. The results are shown in Table 7.

[0059] Table 7. Reaction activity of different catalysts in Example 5 for catalyzing HMF to FDME under the action of initiator CHPO

[0060] Example 5 Reaction time (min) HMF conversion % FDME selectivity % 0.1%-Au / MgO 30 16 45 <![CDATA[0.1%-Au / MnO2]]> 30 45 64

[0061] Embodiment 6:

[0062] The gold-based catalyst catalyzes DFF to prepare FDME in the presence of CHPO as an initiator, comprising the following steps:

[0063] (1) Preparation of gold-based catalysts: 0.1%-Au / MgO and 0.1%-Au / MnO2 catalysts were prepared by impregnation method.

[0064] (2) Place 12 ml of a mixed solution of methanol and DFF (molar ratio of 50:1) in a reactor, and add CHPO accounting for 0.1% of the molar number of DFF. Add 1.0 g of the gold-based catalyst prepared in step (1) thereto. Use a gas with an oxygen concentration of 50% to adjust the reactor pressure to 3 MPa, adjust the reaction temperature to 110°C, and react for 15 minutes. After the reaction is completed, the product is analyzed by gas chromatography. Calculate the conversion rate of DFF and the selectivity of the product FDME. The results are shown in Table 8.

[0065] Table 8. Activity of different catalysts in Example 6 for DFF-catalyzed FDME under the action of initiator CHPO

[0066] Example 6 Reaction time (min) DFF conversion % FDME selectivity % 0.1%-Au / MgO 15 24 56 <![CDATA[0.1%-Au / MnO2]]> 15 57 71

[0067] Embodiment 7:

[0068] The gold-based catalyst catalyzes DFF to prepare FDME in the presence of initiator H2O2, comprising the following steps:

[0069] (1) Preparation of gold-based catalysts: 0.5%-Au / TiO2, 0.5%-Au / ZrO2, 0.5%-Au / Al2O3, 0.5%-Au / MgO, and 0.5%-Au / MnO2 were prepared by impregnation method.

[0070] (2) A mixed solution of 12 ml of methanol and DFF (molar ratio of 50:1) was placed in a reactor, and hydrogen peroxide (30%) accounting for 0.1% of the molar number of DFF was added. 1.0 g of the gold-based catalyst prepared in step (1) was added thereto. The pressure of the reactor was adjusted to 3 MPa using a gas with an oxygen concentration of 50%, and the reaction temperature was adjusted to 110° C. The reaction was carried out for 15 minutes. After the reaction was completed, the product was analyzed by gas chromatography, and the conversion rate of HMF and the selectivity of the product FDME were calculated. The results are shown in Table 9.

[0071] Table 9. Reaction activity of different catalysts in Example 7 for catalyzing DFF to FDME under the action of initiator H2O2

[0072] Example 6 Reaction time (min) DFF conversion % FDME selectivity % <![CDATA[0.5%-Au / TiO2]]> 15 83 88 <![CDATA[0.5%-Au / ZrO2]]> 15 72 91 <![CDATA[0.5%-Au / Al2O3]]> 15 81 89 0.5%-Au / MgO 15 57 91 <![CDATA[0.5%-Au / MnO2]]> 15 88 93

[0073] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing dimethyl furandicarboxylate by using a gold-based catalyst in combination with an initiator with high efficiency catalysis, characterized in that: The following steps are involved: (1) preparing a gold-based catalyst by an impregnation method or a deposition precipitation method, wherein the gold loading is 0.01 to 5 wt %; (2) placing a mixed solution of methanol and HMF or DFF in a reactor, adding an initiator accounting for 0.1-5% of the molar number of HMF or DFF, adding the gold-based catalyst prepared in step (1), adjusting the pressure of the reactor to 1-3 MPa using a gas with an oxygen concentration of 10-50%, adjusting the reaction temperature to 80-120° C., reacting for 10-60 minutes, and separating and obtaining dimethyl furandicarboxylate; The gold-based catalyst described in step (1) is one or a combination of two or more of Au / TiO2, Au / ZrO2, Au / Al2O3, and Au / MnO2; The initiator described in step (2) is one or a combination of two or more of hydrogen peroxide, tert-butyl hydroperoxide, and isopropylbenzene hydroperoxide.

2. The method according to claim 1, characterized in that: The gold loading in step (1) is 0.1 to 1 wt%.

3. The method according to claim 1, characterized in that In step (2), the molar ratio of methanol to HMF or DFF is 5:1-100:

1.

4. The method according to claim 1, characterized in that The amount of the initiator added in step (2) is 0.1-0.5% of the molar number of HMF or DFF.

5. The method according to claim 1, characterized in that The amount of the gold-based catalyst added in step (2) is 1-100 g / L.