CN109776460A - A method of Furfural Production from Xylose is catalyzed using solid acid catalyst - Google Patents
A method of Furfural Production from Xylose is catalyzed using solid acid catalyst Download PDFInfo
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- CN109776460A CN109776460A CN201910238118.0A CN201910238118A CN109776460A CN 109776460 A CN109776460 A CN 109776460A CN 201910238118 A CN201910238118 A CN 201910238118A CN 109776460 A CN109776460 A CN 109776460A
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- acid catalyst
- solid acid
- zeolite
- xylose
- furfural
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Abstract
The invention discloses a kind of methods for preparing furfural using solid acid catalyst catalysis xylan, include the following steps: 1) that xylose is soluble in water；2) rare-earth metal modified zeolite solid acid catalyst is added into reaction system；3) it is warming up to reaction temperature reaction a period of time.The invention uses rare earth metal and is modified to zeolite surface acidity, be conducive to improve the catalytic efficiency that solid acid catalyst prepares xylose degradation in the reaction system that solvent is water in furfural, for the inorganic acid catalysts such as the sulfuric acid used in traditional furfural production technology, due to using zeolite solid acid catalyst, therefore this method is more environmentally-friendly, and catalyst is easy to separate with product, is convenient for subsequent recycling.
Description
Technical field
The invention belongs to chemical products and its preparation fields more particularly to a kind of utilization solid acid catalyst to be catalyzed xylan
The method for preparing furfural.
Background technique
A kind of important organic compound of furfural, the primary raw material for producing furfural is corncob, cotton seed hulls, oil tea shell, rice
The reproducible biomass resource such as shell and bagasse hydrolyzes generation penta using the pentosan in plant fiber under the action of an acid
Sugar, then be cyclized by dehydration of pentoses.Nineteen twenty-two, Quaker Oat company, the U.S. take the lead in realizing the industrialization of furfural, realize
The industrial application of furfural.According to statistics, about 200000 to 210000 tons of global furfural annual output, among these, China is the largest
Furfural production, furfural yield occupies 70% or so of global total output.Current technique is mostly based on inorganic acid catalysis, furfural
Low yield, energy consumption is high, and the waste water and solid waste of generation are difficult to handle, and economy and the feature of environmental protection are in urgent need to be improved.
Solid acid is a kind of solid material with acidic catalytic activity, has environmental-friendly, reusable, separation letter
The advantages that single.Among these, zeolite is widely applied a kind of solid acid catalyst in oil-refinery industry.It is special that zeolite has
Topological structure and flourishing cellular structure, in addition, the acidic site of the feature of zeolite surface can be used as xylose catalytic degradation system
The active site of standby furfural.Zeolite with specific structure be used as solid acid catalyst when, can be conducive to xylose molecule from
It diffuses into zeolite cavity, contacted with zeolite inner surface active site abundant and then reacts in dicyandiamide solution.Simultaneously
The Furfural Molecule of generation diffuses in dicyandiamide solution out of catalyst duct.But often the Acidity of zeolite itself is not sufficient to
The generation of efficient catalytic furfural, it is therefore desirable to zeolite surface Acidity be modified using other metal, to obtain more preferable
Catalytic performance.
Summary of the invention
The present invention is the problems such as using the inorganic acids bring environmental pollutions such as sulfuric acid in being directed to current furfural production method
And the improved method using solid acid catalysis Furfural Production from Xylose of one kind provided.Zeolite is changed using rare earth metal
Property, and be catalyzed xylose degradation in aqueous solution as solid acid catalyst and prepare furfural.
The application reaches above-mentioned purpose by following technical solution.
1) it reacts xylose is soluble in water, the ratio of substrate xylose and solvent is 1:1~1:5 (mol:L)；
2) to the reaction system in 1), be added substrate xylose and solid acid catalyst ratio be 1:20~1:160 (mol:
g)；
3) for the reaction system in 2), reaction temperature is set as 120~200 DEG C；
4) for the reaction system in 3), the reaction time is set as 0.5~8h.
Solid acid catalyst used is rare-earth metal modified zeolite solid acid catalyst in the step 2).
Solid acid catalyst constituent described in the step 2) is zeolite and rare-earth oxide, wherein rare earth
The weight of metal oxide is 1~20wt% of solid acid catalyst weight；Solid acid catalyst carrier type be HY zeolite,
MCM-41 zeolite, USY zeolite, ZSM-5 zeolite；Rare earth metal used be scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr),
Neodymium (Nd), promethium (Pm), samarium (Sm).
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) invention uses rare earth metal and is modified to zeolite surface acidity, is conducive to improve solid acid catalyst
The catalytic efficiency of furfural is prepared to xylose degradation in the reaction system that solvent is water.
(2) for the inorganic acid catalysts such as the sulfuric acid used in traditional furfural production technology, due to using
Zeolite solid acid catalyst, therefore this method is more environmentally-friendly, and catalyst is easy to separate with product, is convenient for subsequent circulation
It uses.
Specific embodiment
Invention is further described With reference to embodiment.These embodiments are only to typical case of the invention
Description, however, the present invention is not limited thereto.Test method as used in the following examples is conventional method unless otherwise specified, institute
The raw material used, unless otherwise specified, being can raw materials and reagents obtained from commercial sources such as regular market purchases.
Embodiment 1
On the one hand, the degradation of synthesis catalytic xylose prepare furfural solid acid catalyst processes it is as follows:
To synthesize the score of solid acid catalyst gross mass shared by 1g rare earth metal praseodymium as the zeolitic solid acid catalysis of 2wt%
For agent.Zeolite is modified using wet impregnation method.By the nitrate hydrate solid Pr of 0.0198g rare earth metal praseodymium
(NO3)3·6H2O is dissolved in 10mL deionized water, and the HY zeolite for weighing 0.98g mixes completely in praseodymium nitrate aqueous solution, overnight
It stands.It is in Rotary Evaporators that aqueous solvent is evaporated, after obtained solid powder dries 2h in 100 DEG C of baking ovens, then move
Enter in 500 DEG C of Muffle furnaces and calcines 2h in air.Obtained solid powder is rare-earth metal modified zeolitic solid acid catalysis
Agent is named as HY-Pr2.
On the other hand, the method for the method that catalysis xylose degradation prepares furfural in aqueous solution is as follows.
The reaction of xylose degradation production furfural is catalyzed in aqueous phase system in the hydro-thermal reaction for being furnished with 20mL polyparaphenylene liner
It is carried out in kettle.10mL deionized water is measured as reaction dissolvent, weighs 0.375g (2.5mmol) xylose as reaction substrate, with
After the catalyst of 0.1g is mixed into deionized water, packaged reaction kettle is placed in heater, is risen to set temperature with temperature and is started
Timing reacts 6h at 140 DEG C.Reaction kettle is taken out after reaction, its fast cooling is made under cold water stream.
Liquid after reaction is detected through high performance liquid chromatograph, and furfural yield is 15%.
Embodiment 2-4
Difference from Example 1 is that used rare-earth metal nitrate hydrate is respectively Ce (NO3)3·
6H2O、Y(NO3)3·6H2O、Sm(NO3)3·6H2O。
Liquid after reaction is detected through high performance liquid chromatograph, and acquired results are as follows.
| Solid acid catalyst | Furfural yield (%) |
| HY-Ce2 | 9 |
| HY-Y2 | 11 |
| HY-Sm2 | 10 |
Embodiment 5-8
Difference from Example 1 is, during synthesizing rare-earth metal-modified zeolite solid acid catalyst, rare earth
The score of zeolite solid acid catalyst gross mass shared by metal praseodymium (Pr) is different.
Liquid after reaction is detected through high performance liquid chromatograph, as a result as shown in the table:
| Solid acid catalyst | Furfural yield (%) |
| HY-Pr4 | 6 |
| HY-Pr8 | 12 |
| HY-Pr12 | 25 |
| HY-Pr16 | 12 |
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, rather than be to this
The restriction of the embodiment of invention.It for those of ordinary skill in the art, on the basis of the above description can be with
It makes other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all in this hair
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within bright spirit and principle
Within protection scope.
Claims (3)
1. a kind of method using solid acid catalyst catalysis Furfural Production from Xylose, which is characterized in that include the following steps:
1) it reacts xylose is soluble in water, the ratio of substrate xylose and solvent is 1:1~1:5 (mol:L)；
2) to the reaction system in 1), the ratio that substrate xylose and solid acid catalyst is added is 1:20~1:160 (mol:g)；
3) for the reaction system in 2), reaction temperature is set as 120~200 DEG C；
4) for the reaction system in 3), the reaction time is set as 0.5~8h.
2. the method according to claim 1, wherein solid acid catalyst used changes in step 2) for rare earth metal
The zeolite solid acid catalyst of property.
3. the method according to claim 1, wherein solid acid catalyst constituent described in step 2) is boiling
Stone and rare-earth oxide, wherein the weight of rare-earth oxide is 1~20wt% of solid acid catalyst weight；Gu
Body acid catalyst carrier is HY zeolite, MCM-41 zeolite, USY zeolite, ZSM-5 zeolite；Rare earth metal used be scandium (Sc),
Yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm).
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Cited By (4)
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| CN110642813A (en) * | 2019-09-09 | 2020-01-03 | 山东省化工研究院 | Preparation process of furfural |
| CN113289692A (en) * | 2021-05-06 | 2021-08-24 | 北京林业大学 | Magnetic biomass solid catalyst and preparation and application thereof |
| CN114768828A (en) * | 2022-05-31 | 2022-07-22 | 陕西科技大学 | Carbon-based solid acid catalyst CS-SO3H, preparation method and application in preparation of furfural by biomass raw material conversion |
| CN115178275A (en) * | 2022-06-09 | 2022-10-14 | 中国科学院青岛生物能源与过程研究所 | Core-shell structure M X O y @mSiO 2 -SO 3 H-type catalyst, preparation thereof and method for preparing furfural by catalyzing corncobs |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110642813A (en) * | 2019-09-09 | 2020-01-03 | 山东省化工研究院 | Preparation process of furfural |
| CN113289692A (en) * | 2021-05-06 | 2021-08-24 | 北京林业大学 | Magnetic biomass solid catalyst and preparation and application thereof |
| CN113289692B (en) * | 2021-05-06 | 2023-06-23 | 北京林业大学 | Magnetic biomass solid catalyst and preparation and application thereof |
| CN114768828A (en) * | 2022-05-31 | 2022-07-22 | 陕西科技大学 | Carbon-based solid acid catalyst CS-SO3H, preparation method and application in preparation of furfural by biomass raw material conversion |
| CN114768828B (en) * | 2022-05-31 | 2023-11-17 | 陕西科技大学 | Carbon-based solid acid catalyst CS-SO 3 H, preparation method and application thereof in preparing furfural by converting biomass raw materials |
| CN115178275A (en) * | 2022-06-09 | 2022-10-14 | 中国科学院青岛生物能源与过程研究所 | Core-shell structure M X O y @mSiO 2 -SO 3 H-type catalyst, preparation thereof and method for preparing furfural by catalyzing corncobs |
| CN115178275B (en) * | 2022-06-09 | 2024-02-27 | 中国科学院青岛生物能源与过程研究所 | Core-shell structure M X O y @mSiO 2 -SO 3 H-type catalyst and preparation method thereof and method for preparing furfural by catalyzing corncob |
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Application publication date: 20190521 |