CN103028424A - Solid acid catalyst for 5-hydroxymethyl furfural synthesis and preparation method thereof - Google Patents
Solid acid catalyst for 5-hydroxymethyl furfural synthesis and preparation method thereof Download PDFInfo
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- CN103028424A CN103028424A CN2013100084036A CN201310008403A CN103028424A CN 103028424 A CN103028424 A CN 103028424A CN 2013100084036 A CN2013100084036 A CN 2013100084036A CN 201310008403 A CN201310008403 A CN 201310008403A CN 103028424 A CN103028424 A CN 103028424A
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Abstract
The invention provides a solid acid catalyst for 5-hydroxymethyl furfural synthesis and a preparation method thereof and relates to a solid acid catalyst. The invention aims to provide the preparation method of the solid acid catalyst for 5-hydroxymethyl furfural synthesis, which has the advantage that a raw material is cheap, easy to obtain, simple in preparation process, and environmentally-friendly, and can be used for synthesizing 5-HMF (Hydroxymethyl Furfural) through carbohydrate dehydration. The solid acid catalyst for 5-hydroxymethyl furfural synthesis is an oxide load sulfate ion or an oxide load chromium ion. The method comprises the following steps: dissolving oxide into deionized water; then completely precipitating the oxide by using a precipitant, aging, washing, filtering and drying; and finally, soaking the precipitant in sulfuric acid solution or chromium solution, dipping, filtering, drying and roasting to obtain the solid acid catalyst for 5-hydroxymethyl furfural synthesis. The 5-hydroxymethyl furfural does not corrode equipment, is easy to separate and can be recycled. The yield of the 5-hydroxymethyl furfural is high. The solid acid catalyst and the preparation method also have the advantages of environmental friendliness, low cost, simple preparation process, easiness in operation, and safe and reliable manufacturing process.
Description
Technical field
The present invention relates to a kind of preparation method of solid catalyst, especially relate to a kind of for synthetic solid acid catalyst of 5 hydroxymethyl furfural and preparation method thereof.
Background technology
5 hydroxymethyl furfural (5-HMF) is the acid catalyzed reaction product of carbohydrate (such as fructose, dextrose plus saccharose etc.), and acid is that the catalyzed carbon hydrate transforms the core catalyst that produces 5-HMF.Traditional acid catalyst mostly is some liquid mineral acid such as HCl, H2SO4, HNO3 and H3PO4 etc., these inorganic acids not only catalytic activity are lower, but also exist etching apparatus, be difficult to reclaim, the shortcomings such as contaminated environment ([1] Watanabe M, Aizawa Y, Iida T, Aida T M, Levy C, K Sue, Inomata H.Glucose reactions with acid and base catalysts in hot compressed water at473K.Carbohydrate Research, 2005,340 (12): 1925-1930.[2] Chheda J N, Roman-Leshkov Y, Dumesic J A.Production of5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono-and poly-saccharides.Green Chemistry, 2007,9 (4): 342-350.).
In recent years, metal chloride especially CrCl2 and CrCl3 also has many reports as the Lewis acid catalyst for the preparation of the research of 5HMF, although CrCl2 and CrCl3 can effectively transform carbohydrate and generate 5HMF, but the toxicity that it is stronger and higher cost have also limited its large-scale application ([3] Zhao H B, Holladay J E, Brown H, Zhang Z C.Metal chlorides ionic l iquid solvents convert sugars to5hydroxymethylfurfural.Science, 2007,316 (5831): 1597-1600.[4] Qi X H, Watanabe M, Aida T M, Smith R L.Fast transformation of glucose and di-/polysaccharides into5hydroxymethylfurfural by microwave heating in an ionicliquid/catalyst system.ChemSusChem, 2010,3 (9): 1071-1077.).
2010, Chareonlimkun etc. have synthesized solid acid catalyst TiO2, ZrO2 and TiO2-ZrO2 are for the preparation of 5-HMF, but the 5-HMF yield only is about 10% ([5] Chareonl imkun A, Champreda V, Shotipruk A, Laosiripojana N.Catalytic conversion of sugarcane bagasse, rice husk and corncob in the presence of TiO2, ZrO2and mixed-oxide TiO2-ZrO2under hot compressed water (HCW) condition.Bioresource Technology, 2010,101 (11): 4179-4186.), be far from reaching the requirement of large-scale production.
Summary of the invention
The purpose of this invention is to provide that raw material is cheap and easy to get, preparation technology is simple, environmentally friendly and can be used for a kind of for synthetic solid acid catalyst of 5 hydroxymethyl furfural and preparation method thereof of the synthetic 5-HMF of carbohydrate dehydration.
Described a kind of solid acid catalyst that synthesizes for 5 hydroxymethyl furfural is oxide carried sulfate ion or chromium ion.
Described oxide can be selected from TiO
2, ZrO
2, Al
2O
3, SiO
2, SnO
2, Fe
2O
3, WO
3, Ce
2O
3, MO
3Deng at least a.
Described sulfate ion can be selected from H
2SO
4, (NH
4)
2SO
4, H
2S
2O
8Deng in a kind of.
Described chromium ion can be selected from Cr (NO
3)
39H
2O, CrF
3, CrCl
36H
2O, CrBr
3, Cr
2(SO
4)
36H
2A kind of among the O etc.
Described a kind of preparation method for the synthetic solid acid catalyst of 5 hydroxymethyl furfural is as follows:
Oxide is dissolved in the deionized water, then makes its precipitation fully with precipitating reagent, after the ageing, the washing and filtering oven dry, then sediment is immersed in sulfuric acid solution or the chromium solution, behind the dipping, filters, oven dry, roasting namely gets for the synthetic solid acid catalyst of 5 hydroxymethyl furfural.
The precipitating reagent of described oxide precipitation can be selected from NH
3H
2O, CO (NH
2)
2, (NH
4)
2CO
3, a kind of among the NaOH etc.
PH value during described oxide precipitation is 8～12, and digestion time can be 6～48h.
The concentration of described sulfuric acid solution or chromium solution can be 0.1～10mol/L.
Described dip time is 0.5～24h.
Described baking temperature is 50～150 ℃, and be 6～48h drying time.
Described sintering temperature is 400～700 ℃, and roasting time is 2～8h.
The present invention has the following advantages:
(1) solid acid catalyst for preparing of the present invention is heterogeneous catalysis, and etching apparatus is not easy to separate recyclable recycling.
(2) solid acid catalyst for preparing of the present invention has higher catalytic activity to carbohydrate, and the yield of 5-HMF is higher.
What (3) the resulting solid acid catalyst of the present invention not only can efficient catalytic 5-HMF is synthetic, but also has the advantages such as environmentally friendly, cheap, that preparation technology simple, easy operating, manufacturing process are safe and reliable.
Description of drawings
Fig. 1 is SO
4 2-/TiO
2The XRD collection of illustrative plates.In Fig. 1, abscissa be 2 θ (°), ordinate is Intensity (a.u.).
Fig. 2 is SO
4 2-/ ZrO
2The XRD collection of illustrative plates.In Fig. 2, abscissa be 2 θ (°), ordinate is Intensity (a.u.).
Fig. 3 is SO
4 2-/ TiO
2-ZrO
2The XRD collection of illustrative plates.In Fig. 3, abscissa be 2 θ (°), ordinate is Intensity (a.u.).
Fig. 4 is SO
4 2-/ SnO
2-Al
2O
3The XRD collection of illustrative plates.In Fig. 4, abscissa be 2 θ (°), ordinate is Intensity (a.u.).
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
Take by weighing 18.9690g TiCl
4, be diluted to the 100mL deionized water and do not emit white cigarette, then stir with ammoniacal liquor and be titrated to pH=10 and make precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 12h.With the sample grind into powder (being about 100～120 orders) of oven dry, be to powder in to add the H of 0.5mol/L at 1: 15 by solid-to-liquid ratio
2SO
4Solution, 600rpm stir dipping 6h, filter, and 110 ℃ of dry 12h are with the SO that obtains
4 2-/ TiO
2Place Muffle furnace, 600 ℃ of roasting 4h.
Embodiment 2
Take by weighing 32.2250g ZrOCl
28H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 12h.With the sample grind into powder (being about 100～120 orders) of oven dry, be to powder in to add the H of 0.5mol/L at 1: 15 by solid-to-liquid ratio
2SO
4Solution, 600rpm stir dipping 6h, filter, and 110 ℃ of dry 12h are with the SO that obtains
4 2-/ ZrO
2Place Muffle furnace, 600 ℃ of roasting 4h.
Embodiment 3
Take by weighing 9.4845g TiCl
4With 16.1125g ZrOCl
28H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 24h.With the sample grind into powder (being about 100～120 orders) of oven dry, be to powder in to add the H of 0.5mol/L at 1: 15 by solid-to-liquid ratio
2SO
4, 600rpm stirs dipping 4h, filters, and 110 ℃ of dry 12h are with the SO that obtains
4 2-/ TiO
2-ZrO
2Place Muffle furnace, 550 ℃ of roasting 4h.
Embodiment 4
Take by weighing 16.1125g ZrOCl
28H
2O and 18.7565g Al (NO
3)
39H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 24h.With the sample grind into powder (being about 100～120 orders) of oven dry, be to powder in to add the H of 0.5mol/L at 1: 15 by solid-to-liquid ratio
2SO
4, 600rpm stirs dipping 4h, filters, and 110 ℃ of dry 12h are with the SO that obtains
4 2-/ ZrO
2Al
2O
3Place Muffle furnace, 550 ℃ of roasting 4h.
Embodiment 5
Take by weighing 18.7565g Al (NO
3)
39H
2O and 17.53g SnCl
45H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 24h.With the sample grind into powder (being about 100～120 orders) of oven dry, be to powder in to add the H of 0.5mol/L at 1: 15 by solid-to-liquid ratio
2SO
4, 600rpm stirs dipping 4h, filters, and 110 ℃ of dry 12h are with the SO that obtains
4 2-/ SnO
2-Al
2O
3Place Muffle furnace, 550 ℃ of roasting 4h.
Embodiment 6
Take by weighing 16.1125g ZrOCl
28H
2O and 14.21g Na
2SiO
39H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 24h.With the sample grind into powder (being about 100～120 orders) of oven dry, be to powder in to add the H of 0.5mol/L at 1: 15 by solid-to-liquid ratio
2SO
4, 600rpm stirs dipping 4h, filters, and 110 ℃ of dry 12h are with the SO that obtains
4 2-/ SiO
2-ZrO
2Place Muffle furnace, 550 ℃ of roasting 4h.
Embodiment 7
Take by weighing 16.1125g ZrOCl
28H
2O and 13.515g FeCl
36H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 24h.With the sample grind into powder (being about 100～120 orders) of oven dry, be to powder in to add the H of 0.5mol/L at 1: 15 by solid-to-liquid ratio
2SO
4, 600rpm stirs dipping 4h, filters, and 110 ℃ of dry 12h are with the SO that obtains
4 2-/ ZrO
2-Fe
2O
3Place Muffle furnace, 550 ℃ of roasting 4h.
Embodiment 8
Take by weighing 9.4845g TiCl
4With 16.1125g ZrOCl
28H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 24h.With the sample grind into powder (being about 100～120 orders) of oven dry, the Cr4h(Cr source of equal-volume load 5% is CrCl
36H
2O), 110 ℃ of dry 12h are with the Cr/TiO that obtains
2-ZrO
2Place Muffle furnace, 550 ℃ of roasting 4h.
Embodiment 9
Take by weighing 16.1125g ZrOCl
28H
2O and 18.7565g Al (NO
3)
39H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 24h.With the sample grind into powder (being about 100～120 orders) of oven dry, the Cr4h(Cr source of equal-volume load 5% is CrCl
36H
2O), 110 ℃ of dry 12h are with the Cr/ZrO that obtains
2Al
2O
3Place Muffle furnace, 550 ℃ of roasting 4h.
Embodiment 10
Take by weighing 18.7565g Al (NO
3)
39H
2O and 17.53g SnCl
45H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 24h.With the sample grind into powder (being about 100～120 orders) of oven dry, the Cr4h(Cr source of equal-volume load 5% is CrCl
36H
2O), 110 ℃ of dry 12h are with the Cr/SnO that obtains
2-Al
2O
3Place Muffle furnace, 550 ℃ of roasting 4h.
Embodiment 11
Take by weighing 16.1125g ZrOCl
28H
2O and 14.21g Na
2SiO
39H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 24h.With the sample grind into powder (being about 100～120 orders) of oven dry, the Cr4h(Cr source of equal-volume load 5% is CrCl
36H
2O), 110 ℃ of dry 12h are with the Cr/SiO that obtains
2-ZrO
2Place Muffle furnace, 550 ℃ of roasting 4h.
Embodiment 12
Take by weighing 16.1125g ZrOCl
28H
2O and 13.515g FeCl
36H
2O is dissolved in the 100mL deionized water, then is titrated to pH=10 with the ammoniacal liquor stirring and makes precipitation fully.The still aging 24h of room temperature extremely (uses AgNO without chlorion with the deionized water washing behind the sedimentation and filtration
3Detect), be deposited in 110 ℃ of dry 24h.With the sample grind into powder (being about 100～120 orders) of oven dry, the Cr4h(Cr source of equal-volume load 5% is CrCl
36H
2O), 110 ℃ of dry 12h are with the Cr/ZrO that obtains
2-Fe
2O
3Place Muffle furnace, 550 ℃ of roasting 4h.
Embodiment 13～41:
Following examples are estimated the catalytic performance of the solid acid catalyst of the present invention's preparation.
Add the solid acid catalyst that this example of 100mg carbohydrate and 20～40mg prepares in 1g ionic liquid [BMIM] Cl, at one 130～140 ℃ of lower stirring reaction 60～100min, after reacting completely, be cooled to room temperature.Reactant liquor dilutes with deionized water, after centrifugation goes out catalyst, detects the content of 5HMF at the 284nm place with UV-Vis spectrophotometer, and concrete outcome sees Table 1.
The different solid acid catalysts of table 1 are on the impact of 5-HMF yield
As shown in Table 1, the solid acid catalyst that the present invention prepares has higher catalytic activity, can effectively transform various carbohydrate (such as glucose, fructose and sucrose) and generate 5-HMF, has very strong industrial applications prospect.
Claims (10)
1. be used for the synthetic solid acid catalyst of 5 hydroxymethyl furfural, it is characterized in that being oxide carried sulfate ion or chromium ion.
2. as claimed in claim 1 for the synthetic solid acid catalyst of 5 hydroxymethyl furfural, it is characterized in that described oxide is selected from TiO
2, ZrO
2, Al
2O
3, SiO
2, SnO
2, Fe
2O
3, WO
3, Ce
2O
3, MO
3In at least a.
3. as claimed in claim 1 for the synthetic solid acid catalyst of 5 hydroxymethyl furfural, it is characterized in that described sulfate ion is selected from H
2SO
4, (NH
4)
2SO
4, H
2S
2O
8In a kind of.
4. as claimed in claim 1 for the synthetic solid acid catalyst of 5 hydroxymethyl furfural, it is characterized in that described chromium ion is selected from Cr (NO
3)
39H
2O, CrF
3, CrCl
36H
2O, CrBr
3, Cr
2(SO
4)
36H
2A kind of among the O.
5. be used for as claimed in claim 1 the preparation method of the synthetic solid acid catalyst of 5 hydroxymethyl furfural, it is characterized in that concrete steps are as follows:
Oxide is dissolved in the deionized water, then makes its precipitation fully with precipitating reagent, after the ageing, the washing and filtering oven dry, then sediment is immersed in sulfuric acid solution or the chromium solution, behind the dipping, filters, oven dry, roasting namely gets for the synthetic solid acid catalyst of 5 hydroxymethyl furfural.
6. be used for as claimed in claim 5 the preparation method of the synthetic solid acid catalyst of 5 hydroxymethyl furfural, it is characterized in that the precipitating reagent of described oxide precipitation is selected from NH
3H
2O, CO (NH
2)
2, (NH
4)
2CO
3, a kind of among the NaOH.
7. be used for as claimed in claim 5 the preparation method of the synthetic solid acid catalyst of 5 hydroxymethyl furfural, the pH value when it is characterized in that described oxide precipitation is 8～12, and digestion time is 6～48h.
8. be used for as claimed in claim 5 the preparation method of the synthetic solid acid catalyst of 5 hydroxymethyl furfural, the concentration that it is characterized in that described sulfuric acid solution or chromium solution is 0.1～10mol/L.
9. be used for as claimed in claim 5 the preparation method of the synthetic solid acid catalyst of 5 hydroxymethyl furfural, it is characterized in that described dip time is 0.5～24h, baking temperature is 50～150 ℃, and be 6～48h drying time.
10. be used for as claimed in claim 5 the preparation method of the synthetic solid acid catalyst of 5 hydroxymethyl furfural, it is characterized in that described sintering temperature is 400～700 ℃, roasting time is 2～8h.
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| CN103949273A (en) * | 2014-04-02 | 2014-07-30 | 云南师范大学 | Method for preparing solid acid esterification catalyst by utilizing zinc smelting water quenching slag |
| CN104437632A (en) * | 2014-11-03 | 2015-03-25 | 江苏大学 | Macro-porous acid-base dual-functional organic solid catalyst as well as preparation method and application thereof |
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| CN110152743A (en) * | 2019-06-19 | 2019-08-23 | 中国科学院大连化学物理研究所 | A kind of solid acid catalyst and its in supercritical CO2The application of 5 hydroxymethyl furfural is synthesized in methanol system |
| CN110152743B (en) * | 2019-06-19 | 2020-06-09 | 中国科学院大连化学物理研究所 | Solid acid catalyst and application thereof in supercritical CO2Application of synthesizing 5-hydroxymethylfurfural in methanol system |
| CN110586114A (en) * | 2019-09-19 | 2019-12-20 | 天津大学 | Preparation method of copper-chromium-aluminum hydrotalcite catalyst and application of catalyst in catalytic oxidation of 5-hydroxymethylfurfural |
| CN114870832A (en) * | 2022-05-25 | 2022-08-09 | 山东科技大学 | Solid acid catalyst of 5-hydroxymethylfurfural and preparation method and application thereof |
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