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Ruthenium-based catalyst and method for preparing 2,5-furandicarboxylic acid by using same

A technology of ruthenium-based catalyst and furandicarboxylic acid, which is applied in the field of biomass resource utilization, can solve the problems of inappropriate production process and low yield, and achieve the effects of simplified preparation process, high yield and high activity

Pending Publication Date: 2021-07-16
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] In order to solve the problems in the prior art of using 5-hydroxymethylfurfural as a raw material to prepare 2,5-furandicarboxylic acid, the yield is low, and the production process is not suitable for industrialization. The present invention intends to provide a ruthenium-based catalyst and use it to carry out 2 , a method for preparing 5-furandicarboxylic acid, which uses 5-methoxymethylfurfural as a raw material to synthesize 2,5-furandicarboxylic acid under the catalysis of a ruthenium-based catalyst, which has high yield and is easy for industrial production specialty

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Catalyst preparation:

[0026] 0.0388g RuCl 3 ·3H 2 O was added to 50 mL of water and stirred until dissolved to obtain Ru 3+ 0.5 g of HAP with a diameter of 1-100 nm was added to it, stirred and impregnated for 10 min; the solid was separated by filtration, washed three times with deionized water, and dried at 55°C for 12 h to obtain catalyst B1.

[0027] The loading of ruthenium in catalyst B1 was detected by inductively coupled plasma (ICP) to be 2.2% by mass.

[0028] Preparation of 2,5-furandicarboxylic acid (2,5-FDCA) by oxidation of 5-methoxymethylfurfural (MMF) catalyzed by catalyst B1:

[0029] Add catalyst B1, MMF and water into the reactor, and the mass ratio of MMF to catalyst is 1:1. After tightening, add oxygen to 0.5MPa and seal, heat to 100°C and react for 12 hours, take out the reaction kettle and put it in cold water to cool down, after the cooling is completed, open the reaction kettle, wash with methanol aqueous solution, and transfer it to a vol...

Embodiment 2

[0032] Catalyst preparation:

[0033] In addition to changing the RuCl 3 ·3H 2 The mass of O was 0.0647g, and the immersion time was 30min. The preparation of other catalysts was the same as that in Example 1 to obtain catalyst B2 with a ruthenium loading of 4.5%.

[0034] Except that the mass ratio of MMF to catalyst was changed to 1:0.5, the MMF oxidation reaction conditions were the same as in Example 1, the conversion of MMF was 86.7%, the selectivity of 2,5-FDCA was 60.3%, and the yield was 52.3%.

Embodiment 3

[0036] Catalyst preparation:

[0037] In addition to 0.0388g RuCl 3 ·3H 2 O was changed to 0.0050g ruthenium nitrate, and the stirring and impregnating time was changed from 10min to 1h, the preparation of other catalysts was the same as in Example 1 to obtain catalyst B3, and the loading of ruthenium was 0.1%.

[0038] Except that the mass ratio of MMF to catalyst was changed to 1:5, the MMF oxidation reaction conditions were the same as in Example 1, the conversion of MMF was 80.13%, the selectivity of 2,5-FDCA was 50.3%, and the yield was 40.3%.

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PUM

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Abstract

The invention provides a preparation method of a ruthenium-based catalyst, which comprises the following steps: mixing a solution containing Ru3+ with hydroxyapatite, carrying out solid-liquid separation after adsorption is completed, and washing and drying the separated solid to obtain the ruthenium-based catalyst. The ruthenium-based catalyst can be used for catalyzing 5-methoxy methyl furfural to prepare 2,5-furandicarboxylic acid. The preparation method of the ruthenium-based hydroxyapatite catalyst is simple, Ru3+ is used as an active component, the catalyst can be obtained only through adsorption and drying processes, and the preparation process is simplified; in the preparation method of the 2, 5-furandicarboxylic acid, the active components of the ruthenium-based hydroxyapatite catalyst are good in stability and high in activity under the reaction system; and the raw material 5-methoxy methyl furfural stably exists in an aqueous solution system, under the catalysis of ruthenium-based hydroxyapatite, the method has the advantages that the yield is high, and the production process is easy to industrialize, and the defects that the yield of 2, 5-furandicarboxylic acid is low and the industrialization difficulty is large due to the fact that the raw material is unstable in the prior art are overcome.

Description

technical field [0001] The invention relates to the preparation technology of 2,5-furandicarboxylic acid, in particular to a method for selectively oxidizing 5-methoxymethylfurfural with a ruthenium-hydroxyapatite catalyst to prepare 2,5-furandicarboxylic acid. It belongs to the field of utilization of biomass resources. Background technique [0002] The structure and properties of 2,5-furandicarboxylic acid (FDCA) from bio-based sources are similar to terephthalic acid (PTA), therefore, it is considered as a substitute for PTA from petroleum-based sources, thereby replacing bulk polyester materials , such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polytrimethylene terephthalate (PTT). The bio-based polyester PEF developed by Avantium Company in the Netherlands, using FDCA as raw material, not only has the excellent performance of PTA polyester materials, but also has the characteristics of renewable and degradable resources (Zou Bin, Applied ...

Claims

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Application Information

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IPC IPC(8): C07D307/68B01J37/02B01J37/08B01J27/185B01J31/04
CPCC07D307/68B01J37/0201B01J37/0203B01J37/08B01J27/1856B01J31/04
Inventor 马会霞傅杰周峰乔凯张淑梅
Owner CHINA PETROLEUM & CHEM CORP