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Method of low metal loading catalyst for preparing glycol from carbohydrate

A carbohydrate and catalyst technology, applied in the field of polyol preparation, can solve the problems of sintering and loss of catalyst active components, and achieve the effects of high dispersion, low cost and good stability

Active Publication Date: 2013-12-04
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] However, in the actual industrial application of catalytic technology, a more important issue is how to make the catalyst have good stability and reusability, so as to avoid sintering or loss of the active components of the catalyst during use.

Method used

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  • Method of low metal loading catalyst for preparing glycol from carbohydrate
  • Method of low metal loading catalyst for preparing glycol from carbohydrate
  • Method of low metal loading catalyst for preparing glycol from carbohydrate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Metal catalyst Ru / AC, Ru / SiO 2 ,Ru / ZnO,Ru / SBA-15, Ru / CaO,Ru / Al 2 O 3 ,Ru / TiO 2 Preparation: impregnate the activated carbon support with a mixed solution of 15wt% ruthenium trichloride aqueous solution and 20wt% sugar, dry at 120°C for 1 hour, then dry at 180°C for 6 hours, and finally roast in 350°C nitrogen atmosphere for 1 hour, respectively A Ru / AC catalyst with a loading amount of 0.05% Ru / C, 0.1% Ru / C, 0.2%, 0.5%, 0.7%, and 0.9% was obtained. The activated carbon carrier is replaced by alumina, silica, SBA-15, zinc oxide, titanium dioxide, calcium oxide, and the same method can be used to prepare catalysts supported by different carriers.

Embodiment 2

[0026] Catalytic conversion experiment: add 1.0g carbohydrates, 0.3g catalyst A, 0.03g catalyst B and 100ml water into a 300ml reactor, pass hydrogen to replace the gas three times, fill with hydrogen to 5MPa, heat up to 245°C and react for 30min. After the reaction, the temperature was lowered to room temperature, and the supernatant liquid after centrifugation was taken, separated on a calcium-type ion exchange column of high performance liquid chromatography and detected by a differential refractive index detector. In the product yield, only the target products ethylene glycol, propylene glycol, and hexahydric alcohols (including sorbitol, mannitol) are calculated. Other liquid products include butane erythritol, ethanol, unknown components, and gas products (CO 2 , CH 4 , C 2 H 6 Etc.) The yield was not calculated.

[0027] Ruthenium catalyst circulation reaction method: After the reaction, the ruthenium catalyst is separated by centrifugation and other methods, and used for t...

Embodiment 3

[0029] In the composite catalyst, the catalyst A was a Ru catalyst supported on different carriers, the loading amount was 0.9%, and the catalyst B was tungstic acid, and the reaction conditions were the same as in Example 2. Results of catalytic conversion of cellulose on various composite catalysts (Table 1 and Table 2).

[0030] Table 1 Results of catalytic conversion of cellulose during the first use of various catalysts

[0031]

[0032] Table 2 Results of catalytic conversion of cellulose after multiple cycles of various catalysts

[0033] Catalyst

[0034]

[0035] As shown in Table 1 and Table 2, cellulose can be converted into ethylene glycol with high yield on different composite catalysts in the catalytic process involved in the present invention and can be recycled for multiple times. Among them, the Ru / AC+tungstic acid combination can be recycled at least three times more than other catalyst combinations, reaching 45 times without significant reduction in activity...

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Abstract

The invention provides a method of applying a low metal loading catalyst for preparing glycol and propylene glycol from carbohydrate, including cellulose, starch, semi-cellulose, cane sugar, glucose, fructose, fructosan, xylose, and soluble xylo oligosaccharide. In the method, carbohydrate is taken as the raw material, the compound catalyst is composed of catalytic active components selected from one or more components from following components: highly-disperse and low-loading ruthenium, inorganic compounds, organic compounds, and complex of tungsten, or simple substance tungsten, then one-step catalytic conversion process is carried out under the hydrothermal conditions: temperature of 60 to 350 DEG C, and hydrogen pressure 0.1 to 15 MPa, and the high-efficient, high-selective and high yield preparation of glycol and propylene glycol from carbohydrate is achieved. The method takes highly-disperse and high stability low loading Ru-based catalyst as the reaction catalyst, so the usage amount of value metals is reduced, the loss of catalyst carrier is slowed down, and the recycle rate of Ru-base catalyst is increased. The catalyst has the prominent advantages of high activity, high selectivity, and very high cyclicity. Compared to other technologies, which prepare polyol from carbohydrate, the method has the advantages of simple reaction process, high efficiency, good stability of catalyst, and multi-circulation, and has very vast industrial application value.

Description

Technical field [0001] The invention relates to a preparation method of polyols such as ethylene glycol and propylene glycol, in particular to a reaction process of preparing ethylene glycol and propylene glycol through one-step catalytic hydrogenation degradation of carbohydrates under hydrothermal conditions. Background technique [0002] Ethylene glycol is an important energy liquid fuel and a very important raw material for polyester synthesis. For example, it is used in polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and can also be used As antifreeze, lubricant, plasticizer, surface active agent, etc., it is an organic chemical raw material with a wide range of uses. [0003] At present, the industrial production of ethylene glycol mainly adopts the route of petroleum raw materials, that is, ethylene oxide is obtained after epoxidation of ethylene, and then hydrated to obtain ethylene glycol. Industry, 2007, 25, (4), 15-21. Literature 2: Process for prepari...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C31/20C07C29/00B01J23/46B01J23/652B01J23/60B01J29/03B01J23/58
CPCY02P20/50Y02P20/52
Inventor 张军营张涛郑明远庞纪峰姜宇邰志军王爱琴
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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