Grafted solid acid catalyst, preparation method thereof and application of grafted solid acid catalyst in saccharification process of lignocellulose

A lignocellulosic and catalyst technology, applied in chemical instruments and methods, chemical/physical processes, physical/chemical process catalysts, etc., can solve the problem that the catalytic activity needs to be further improved, the density of acidic active sites is small, and the catalyst efficiency is limited, etc. problem, to achieve good catalytic effect, high selectivity, good catalytic effect

Active Publication Date: 2017-01-25
GUANGZHOU INST OF ENERGY CONVERSION - CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] (1) Chinese patent 201310268739.6 discloses a carbon-based biomass as raw material, adding absolute ethanol and concentrated sulfuric acid successively, mixing evenly, heating and stirring the mixture at a certain temperature, washing and drying the carbon-based biomass Solid acid catalyst, which has the advantages of simplifying process equipment and preparation process, but also has the disadvantage of low catalytic activity;
[0007] (2) Chinese patent 201010101049.5 discloses a kind of easily carbonized sugar compound and a functional compound containing sulfonic acid group as raw materials, a catalyst prepared by one-step hydrothermal carbonization synthesis, the catalyst has the advantages of low cost and green, but the catalytic The activity needs to be further improved;
[0008] In the prior art, the preparation of biomass carbon-based solid acid is usually based on carbon materials such as glucose, fructose, sucrose, bamboo charcoal, pine charcoal, and fruit shells, and is mixed with concentrated sulfuric acid, oleum, or organic sulfonic acid ester sulfonic acid. chemical, grafted active group-SO 3 Catalysts are prepared by methods such as H, but these methods inevitably have disadvantages such as low density of acidic active sites or complicated preparation process, which limits the efficiency of these catalysts in the catalytic reaction process.

Method used

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  • Grafted solid acid catalyst, preparation method thereof and application of grafted solid acid catalyst in saccharification process of lignocellulose
  • Grafted solid acid catalyst, preparation method thereof and application of grafted solid acid catalyst in saccharification process of lignocellulose

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preparation example Construction

[0037]A kind of preparation method of graft type carbon-based solid acid catalyst that the application proposes, comprises the following steps:

[0038] (1) Preparation of crude carbon-based solid acid catalyst: mix lignocellulosic biomass carbon-based material and sulfonating agent with a mass ratio of 1 / 10 to 10, place the uniformly mixed material in a reaction vessel, Carbonize at a reaction temperature of 120-240°C for 1-36 hours, put the carbonized black solid at high temperature, grind, wash and dry, and the dried black solid is the crude carbon-based solid acid catalyst;

[0039] (2) Oxidative modification of the crude carbon-based solid acid catalyst: the crude carbon-based solid acid catalyst obtained in step (1) and the oxidant are mixed at a solid-to-liquid ratio of 1 / 100 to 1 / 10, at 50 to 60 The reaction is carried out at a temperature of 0.5° C. for 0.5 to 3 hours. After the reaction is completed, a black solid is obtained by filtering and isolating. The black sol...

Embodiment 1

[0041] Glucose and p-toluenesulfonic acid with a mass ratio of 3:1 were ball-milled in a ball mill for 2 hours to mix thoroughly, and then hydrothermally carbonized in a 100mL polytetrafluoroethylene-lined autoclave at 120°C for 24 hours to obtain black For the solid, put it in a muffle furnace at 180°C for 24 hours to remove the small molecular compounds adsorbed on the surface, grind it, wash it repeatedly with deionized water higher than 80°C until the washing liquid is neutral, and collect the solid in an oven at 105°C After drying for 4 hours, a crude carbon-based solid acid catalyst was prepared.

[0042] In the thick-walled pressure-proof bottle of 150mL, add 2g above-mentioned and make crude carbon-based solid acid catalyst and 100mL mass fraction be 30% H 2 o 2 (The density is approximately 1g·cm -3 ) aqueous solution in an oil bath at 50°C for 1 hour, after the oxidation reaction was completed, filter and separate, collect the filter residue, and dry it in an oven ...

Embodiment 2

[0045] Starch and p-toluenesulfonic acid with a mass ratio of 1:10 were ball-milled in a ball mill for 2 hours to mix thoroughly, and then hydrothermally carbonized in a 100mL polytetrafluoroethylene-lined autoclave at 240°C for 1 hour to obtain black For the solid, put it in a muffle furnace at 180°C for 24 hours to remove the small molecular compounds adsorbed on the surface, grind it, wash it repeatedly with deionized water higher than 80°C until the washing liquid is neutral, and collect the solid in an oven at 105°C After drying for 4 hours, a crude carbon-based solid acid catalyst was prepared.

[0046] Add 1g of the crude carbon-based solid acid catalyst and 100mL of 30% H 2 o 2 The aqueous solution was heated in an oil bath at 50°C for 0.5h. After the oxidation reaction was completed, it was separated by filtration, and the filter residue was collected and dried overnight in an oven at 105°C to obtain a modified grafted carbon-based solid acid catalyst.

[0047] Add ...

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Abstract

The invention relates to a grafted solid acid catalyst. A preparation method of the grafted solid acid catalyst comprises the following steps: taking lignocelluloses biomass carbon-based material as a raw material, taking a sulfonating agent as an active molecule, and carrying out carbonization reaction for 1-36 hours at the temperature of 120-240 DEG C, wherein the mass ratio of the raw material and the sulfonating agent is 1/10-10; standing black solid obtained by carbonization at high temperature, drying to obtain black solid which is a rough carbon-based solid acid catalyst; and mixing the rough carbon-based solid acid catalyst with an oxidizing agent according to the solid-liquid ratio of 1/10-0-1/10, reacting for 0.5-3 hours at the temperature of 50-60 DEG C, after reaction, filtering and separating to obtain black solid, and washing and drying the black solid to obtain the grafted carbon-based solid acid catalyst. Cellulose-based glucose is used as the raw material of the catalyst, the structural characteristics of the raw material are similar to the structural characteristics of the raw material of lignocelluloses biomass, therefore, catalyzing effect is excellent, and the catalyzing effect of the grafted solid acid catalyst is similar to the catalyzing effect of liquid acid.

Description

technical field [0001] The invention belongs to the technical field of solid acid catalysts, and in particular relates to a grafted solid acid catalyst, a preparation method thereof and an application in a lignocellulose hydrolysis and saccharification process. Background technique [0002] Biomass is the only renewable carbon source on earth and a renewable clean resource that can be directly converted into gas, liquid and solid energy. The development and utilization of biomass resources provides a feasible way out to comprehensively solve the problems of energy-environment-urbanization development, and has received widespread attention from all over the world. my country is a large agricultural country, and the output of biomass resources is huge every year. If it is industrialized and applied, it can effectively replace the use of fossil fuels, and has important practical significance for reducing carbon emissions and protecting the ecological environment. [0003] The ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/02B01J31/04C13K13/00C13K1/02
CPCB01J27/02B01J31/04C13K1/02C13K13/002
Inventor 亓伟徐艳王闻王琼谭雪松余强庄新姝袁振宏王忠铭
Owner GUANGZHOU INST OF ENERGY CONVERSION - CHINESE ACAD OF SCI
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