CN103285884A - Preparation method of carbon-based solid acid catalyst used for synthesizing 5-hydroxymethylfurfural - Google Patents
Preparation method of carbon-based solid acid catalyst used for synthesizing 5-hydroxymethylfurfural Download PDFInfo
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- CN103285884A CN103285884A CN2013102688740A CN201310268874A CN103285884A CN 103285884 A CN103285884 A CN 103285884A CN 2013102688740 A CN2013102688740 A CN 2013102688740A CN 201310268874 A CN201310268874 A CN 201310268874A CN 103285884 A CN103285884 A CN 103285884A
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Abstract
The invention provides a preparation method of a carbon-based solid acid catalyst used for synthesizing 5-hydroxymethylfurfural, and relates to a solid acid catalyst. The preparation method of the carbon-based solid acid catalyst used for synthesizing 5-hydroxymethylfurfural is simple in preparation process and environmentally-friendly and has the characteristic that raw materials are low in price and easily obtained. The preparation method comprises the following steps of: 1) heating the raw materials through a tubular reacting furnace, wherein nitrogen is charged to protect reactants during reacting; 2) transferring the carbonized material into a reactor, adding acid and heating to react, wherein the nitrogen is charged to protect the reactants during reacting; and 3) washing the reacted mixture through deionized water, and drying to obtain the carbon-based solid acid catalyst used for synthesizing 5-hydroxymethylfurfural.
Description
Technical field
The present invention relates to a kind of solid acid catalyst, especially a kind of preparation method for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural.
Background technology
(5-hydroxymethylfurfural 5-HMF) is the acid catalyzed reaction product of multiple kinds of carbohydrate (as fructose, dextrose plus saccharose etc.) to 5 hydroxymethyl furfural, and acid is that the catalyzed carbon hydrate transforms the core catalyst that generates 5-HMF.Traditional acid catalyst mostly is some liquid mineral acid such as HCl, H
2SO
4, HNO
3And H
3PO
4Deng, these inorganic acids not only catalytic activity are lower, but also exist etching apparatus, are difficult to shortcomings such as recovery, contaminated environment.In recent years, metal chloride CrCl especially
2And CrCl
3For the preparation of the research of 5-HMF many reports are arranged also as the Lewis acid catalyst, though CrCl
2And CrCl
3Can effectively transform carbohydrate and generate 5-HMF, but its stronger toxicity and higher cost have also limited its large-scale application.
In order to overcome the weak point of above-mentioned catalyst, the solid acid acid catalysts such as heteropoly acid of Sulfated metal oxide, H-molecular sieve, cationic ion-exchange resin and support type also by people for the preparation of 5-HMF, but the preparation process of these solid acids is very numerous and diverse, and raw material is mostly relatively more expensive, far can not reach the requirement of large-scale production.Recently, carbon-based solid acid more and more is much accounted of, the poly structure that this new catalyst obtains by incomplete carbonization sulfonic group aromatic hydrocarbons, can be used for multiple catalytic reaction (Okamura M, Takagaki A, Toda M, et al.Acid-catalyzed reactions on flexible polycyclic aromatic carbon in amorphous carbon[J] .Chem Mater, 2006,18 (13): 3039-3045; Budarin V, Clark J H, Hardy J J E, et al.Starbons:new starch derived mesoporous carbonaceous materials with tunable properties[J] .Angewandte Chemie International Edition, 2006,45 (23): 3782-3786; Budarin V L, Clark J H, Luque R, et al.Versatile mesoporous carbonaceous materials for acid catalysis[J] .Chem Commun, 2007, (6): 634-636).
Summary of the invention
The object of the present invention is to provide that raw material is cheap and easy to get, preparation technology is simple, eco-friendly a kind of preparation method for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural.
The present invention includes following steps:
1) raw material is put into tubular react furnace, heating feeds nitrogen reactant is protected in the course of reaction;
2) material after the carbonization is placed reactor, add acid, add thermal response, feed nitrogen in the course of reaction reactant is protected;
3) post reaction mixture is spent deionised water, drying must be used for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural.
In step 1), described raw material can be selected from least a in cellulose, starch, glucose, the sucrose etc.; The condition of described heating can be under 350～700 ℃ temperature and heats 0.5～3h.
In step 2) in, optional a kind of in sulfuric acid, oleum, sulfur trioxide, p-methyl benzenesulfonic acid etc. of described acid, the material after the described carbonization can be 1:(5～20 with the mass ratio of acid); The described condition that adds thermal response can be under 80～250 ℃ reaction temperature and stirs 1～15h.
In step 3), the condition of described drying can be at 60～120 ℃ of drying 12～48h.
The present invention has the following advantages:
(1) preparation technology is simple, easy operating.
(2) carbon-based solid acid catalyst for preparing is heterogeneous catalysis, not only sour density height, Heat stability is good, etching apparatus not, and be easy to separate recyclable recycling.
(3) solid acid catalyst for preparing has advantages of high catalytic activity to carbohydrate, and the yield of 5-HMF is higher.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of CSA.Abscissa be the angle of diffraction (°), ordinate is diffracted intensity (a.u.).
Fig. 2 is the Fourier infrared spectrum figure of CSA.Abscissa is wave number (cm
-1), ordinate is transmissivity (%).
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
Get the dried glucose of 20g at N
2Protect following 400 ℃ of heating 1h, and the black solid that obtains is crushed into powder and dry 24h under 105 ℃.Be to add dense H at 1: 10 with black powder by mass volume ratio
2SO
4, at N
2Protect following 200 ℃ of sulfonation 5h.Can form black precipitate after adding the 1000mL deionized water in the mixture, filter and obtain precipitation, and with being higher than 80 ℃ deionized water washing precipitation to there not being SO
4 2 –Black precipitate is namely obtained the glucosyl group solid acid behind the dry 24h down at 105 ℃, abbreviate GSA1 as.
Embodiment 2
Get the dried glucose of 20g at N
2Protect following 400 ℃ of heating 1h, and the black solid that obtains is crushed into powder and dry 24h under 105 ℃.Be that 1:5 adds p-methyl benzenesulfonic acid with black powder by mass ratio, at N
2Protect following 150 ℃ of sulfonation 10h.Can form black precipitate after adding the 1000mL deionized water in the mixture, filter and obtain precipitation, and with 80 ℃ deionized water washing precipitation is to there not being SO
4 2 –Black precipitate is namely obtained the glucosyl group solid acid behind the dry 24h down at 105 ℃, abbreviate GSA2 as.
Embodiment 3
Get the dried sucrose of 20g at N
2Protect following 400 ℃ of heating 1h, and the black solid that obtains is crushed into powder and dry 24h under 105 ℃.Be that 1:10 adds dense H with black powder by mass volume ratio
2SO
4, at N
2Protect following 180 ℃ of sulfonation 6h.Can form black precipitate after adding the 1000mL deionized water in the mixture, filter and obtain precipitation, and with 80 ℃ deionized water washing precipitation is to there not being SO
4 2 –Black precipitate is namely obtained the glucosyl group solid acid behind the dry 24h down at 105 ℃, abbreviate SUSA as.
Embodiment 4
Get the dried cellulose of 20g at N
2Protect following 400 ℃ of heating 2h, and the black solid that obtains is crushed into powder and dry 24h under 105 ℃.Be that 1:10 adds dense H with black powder by mass volume ratio
2SO
4, at N
2Protect following 200 ℃ of sulfonation 5h.Can form black precipitate after adding the 1000mL deionized water in the mixture, filter and obtain precipitation, and with 80 ℃ deionized water washing precipitation is to there not being SO
4 2 –Black precipitate is namely obtained the glucosyl group solid acid behind the dry 24h down at 105 ℃, abbreviate CSA as.
Embodiment 5
Get the dried starch of 20g at N
2Protect following 400 ℃ of heating 2h, and the black solid that obtains is crushed into powder and dry 24h under 105 ℃.Be that 1:10 adds dense H with black powder by mass volume ratio
2SO
4, at N
2Protect following 200 ℃ of sulfonation 5h.Can form black precipitate after adding the 1000mL deionized water in the mixture, filter and obtain precipitation, and with 80 ℃ deionized water washing precipitation is to there not being SO
4 2 –Black precipitate is namely obtained the glucosyl group solid acid behind the dry 24h down at 105 ℃, abbreviate STSA as.
Carbon-based solid acid catalyst to the present invention's preparation characterizes.Fig. 1 is the x-ray diffraction pattern of the carbon-based solid acid catalyst for preparing of the present invention, as can be seen from Figure 1, carbon-based solid acid catalyst only two wideer and more weak diffraction maximums occurred in 2 θ are the scope of 15～30 ° and 35～50 °, the former is corresponding to the C(002 of multi-aromatic ring amorphous carbon) crystal face, the latter is corresponding to the C(101 of multi-aromatic ring amorphous carbon) crystal face, this explanation carbon-based solid acid is made up of multi-aromatic ring amorphous carbon.Fig. 2 is the Fourier infrared spectrum figure of the carbon-based solid acid catalyst for preparing of the present invention, as can be seen from Figure 2, and 1035cm
-1, 1167cm
-1And 1384cm
-1The absworption peak at place belongs to-SO
3The stretching vibration peak of O=S=O among the H, this explanation-SO
3H successfully has been introduced on the multi-aromatic ring amorphous carbon of these carbon-based solid acid catalysts; In addition, 1620cm
-1The absworption peak at place belongs to the stretching vibration peak of C=C on the multi-aromatic ring amorphous carbon, 1715cm
-1The absworption peak at place belongs to-COOH in the stretching vibration peak of C=O, 3424cm
-1The absworption peak at place belongs to-and COOH and Ph-OH go up the stretching vibration peak of O-H, and this explanation CSAC, GSAC and SSAC go up except containing-SO
3Beyond the H, also contain-COOH and Ph-OH.
Following example is that the catalytic performance of the carbon-based solid acid catalyst of the present invention's preparation is estimated.
Add the carbon-based solid acid catalyst that this examples preparation of 100mg carbohydrate and 40mg obtains in 1g ionic liquid [BMIM] Cl, at 140～160 ℃ of following stirring reaction 15～30min, after reacting completely, be cooled to room temperature.Reactant liquor dilutes with deionized water, and after centrifugation went out catalyst, with the content of HPLC detection 5-HMF, different solid acid catalysts saw Table 1 to the influence of 5-HMF yield.
Table 1
As shown in Table 1, the solid acid catalyst that the present invention prepares has advantages of high catalytic activity, can transform various carbohydrate (as glucose, fructose, sucrose, cellobiose, maltose, starch and cellulose) effectively and generate 5-HMF, have very strong industrial applications prospect.
Claims (7)
1. preparation method who is used for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural is characterized in that may further comprise the steps:
1) raw material is put into tubular react furnace, heating feeds nitrogen reactant is protected in the course of reaction;
2) material after the carbonization is placed reactor, add acid, add thermal response, feed nitrogen in the course of reaction reactant is protected;
3) post reaction mixture is spent deionised water, drying must be used for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural.
2. a kind of preparation method for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural according to claim 1 is characterized in that in step 1), and described raw material is selected from least a in cellulose, starch, glucose, the sucrose.
3. a kind of preparation method for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural according to claim 1 is characterized in that in step 1) the condition of described heating is to heat 0.5～3h under 350～700 ℃ temperature.
4. a kind of preparation method for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural according to claim 1 is characterized in that in step 2) in, described acid is selected from a kind of in sulfuric acid, oleum, sulfur trioxide, the p-methyl benzenesulfonic acid.
5. a kind of preparation method for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural according to claim 1 is characterized in that in step 2) in, the material after the described carbonization is 1 with the mass ratio of acid: (5～20).
6. a kind of preparation method for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural according to claim 1 is characterized in that in step 2) in, the described condition that adds thermal response is to stir 1～15h under 80～250 ℃ reaction temperature.
7. a kind of preparation method for the synthetic carbon-based solid acid catalyst of 5 hydroxymethyl furfural according to claim 1 is characterized in that in step 3) the condition of described drying is at 60～120 ℃ of drying 12～48h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503669A (en) * | 2016-02-17 | 2016-04-20 | 南通大学 | Preparation method for 1,4-butanediol polyoxyethylene ether (7) sec-sodium bi-sulfosuccinic diester surfactant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011011201A (en) * | 2008-09-12 | 2011-01-20 | Kanagawa Acad Of Sci & Technol | Carbon-based solid acid and method for producing the same |
| CN102125874A (en) * | 2011-01-07 | 2011-07-20 | 华南理工大学 | Method for preparing carbon based solid acid catalyst by using waste biomass as raw material |
| CN102399201A (en) * | 2011-11-24 | 2012-04-04 | 中国科学院西双版纳热带植物园 | Method for preparing 5-hydroxymethylfurfural by solid acid catalysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011011201A (en) * | 2008-09-12 | 2011-01-20 | Kanagawa Acad Of Sci & Technol | Carbon-based solid acid and method for producing the same |
| CN102125874A (en) * | 2011-01-07 | 2011-07-20 | 华南理工大学 | Method for preparing carbon based solid acid catalyst by using waste biomass as raw material |
| CN102399201A (en) * | 2011-11-24 | 2012-04-04 | 中国科学院西双版纳热带植物园 | Method for preparing 5-hydroxymethylfurfural by solid acid catalysis |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503669A (en) * | 2016-02-17 | 2016-04-20 | 南通大学 | Preparation method for 1,4-butanediol polyoxyethylene ether (7) sec-sodium bi-sulfosuccinic diester surfactant |
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Application publication date: 20130911 |