CN106669655B - Preparation method of solid acid catalyst for preparing 5-hydroxymethylfurfural from biomass - Google Patents
Preparation method of solid acid catalyst for preparing 5-hydroxymethylfurfural from biomass Download PDFInfo
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- CN106669655B CN106669655B CN201610936152.1A CN201610936152A CN106669655B CN 106669655 B CN106669655 B CN 106669655B CN 201610936152 A CN201610936152 A CN 201610936152A CN 106669655 B CN106669655 B CN 106669655B
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Abstract
The present invention relates to a method for preparing a solid acid catalyst for 5-hydroxymethylfurfural production from biomass, which is a composite of carbon and niobium pentoxide and has an amorphous structure. The preparation method comprises the following steps: the niobium-carbon solid acid catalyst is prepared by using a carbohydrate compound and the like as a carbon source, niobium tartrate, niobium oxalate, niobium citrate, niobium pentachloride or other niobium salts and the like as a niobium source and inorganic or organic acid as a catalyst through a hydrothermal method or a solvothermal method, and then carbonizing at a high temperature under nitrogen. The solid acid catalyst is used for the dehydration reaction of saccharides and cellulose, the yield of the product 5-hydroxymethylfurfural is high, the catalyst has good recycling performance, and the catalyst is a very good catalyst for preparing 5-hydroxymethylfurfural by biomass catalytic conversion.
Description
Technical Field
The invention relates to a preparation method of a solid acid catalyst for preparing 5-hydroxymethylfurfural from biomass, and relates to the fields of catalytic chemistry and biomass resource utilization.
Background
With the rapid increase of world economy, fossil fuel (especially petroleum) resources become increasingly short, and the utilization process thereof also brings a series of social and environmental problems to human society, so that the related research of synthesizing fuels and fine chemicals starting from biomass which is one of renewable energy sources and derivatives thereof becomes one of the hot spots of concern to domestic and foreign scientists. Because biomass has the advantages of sustainability, wide sources and the like, and 5-hydroxymethylfurfural is an important furan compound and can be used for preparing liquid fuels such as 2, 5-dimethylfuran, long-chain alkane, drug intermediate 2, 5-diformylfuran, polyester monomer 2, 5-furandicarboxylic acid and the like, biomass and derivatives thereof are converted into 5-hydroxymethylfurfural through dehydration reaction, and the method is an important way for efficiently utilizing biomass.
At present, inorganic liquid acid is generally used as a catalyst in the reaction for synthesizing 5-hydroxymethylfurfural by dehydrating biomass or derivatives thereof, and the problems of difficult product separation, serious equipment corrosion, environmental pollution and the like exist. Researches find that the ionic liquid, namely chloro-1-methyl-3-ethylimidazole, is used as a reaction medium to convert glucose into 5-Hydroxymethylfurfural (HMF), so that the HMF yield of 70% can be obtained (Science, 2007, 316 and 1597); the yield of 5-hydroxymethylfurfural was 58% when converting cellulose (GreenC)hem, 2011, 13, 1503). However, the cost of the ionic liquid is too high at present, and most of the catalysts used are CrCl3And chromium is a serious pollution to the environment, so that the industrial application thereof is greatly limited. However, the new development direction of the solid acid catalyst as a catalyst has the advantages of easy separation and recovery, recycling, environmental friendliness and the like compared with the liquid acid catalyst, and thus the solid acid catalyst is widely applied to biomass conversion. For example, Al-MCM-41 catalyzed glucose by Antonio Jimenez-Lopez et Al produces HMF with a yield of 63%, but the catalyst has poor stability and a greatly reduced reactivity after 3 uses (appl. Catal., B, 2015, 164, 70-76.). Du Yi Guang topic group WO3-Ta2O5The HMF is prepared by catalytic conversion of carbohydrate, the HMF with high yield is obtained, the stability is high (patent number: CN 201110435929.3), but a tantalum source (tantalum chloride, tantalum ethoxide and the like) in the material preparation process is expensive, and the material is not suitable for industrial large-scale production. Therefore, on this basis, we need to find a stable and efficient solid acid catalyst with economical utility for preparing HMF from biomass.
Disclosure of Invention
The invention aims to provide a preparation method of a solid acid catalyst, and the solid acid catalyst is applied to a reaction for preparing 5-hydroxymethylfurfural from biomass.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
a method for preparing a solid acid catalyst for 5-hydroxymethylfurfural production from biomass, characterized by: one or more of saccharide compounds and niobium precursor are subjected to hydrothermal or solvent heat treatment for a period of time at a certain temperature in the presence of an acid catalyst, washed by deionized water, filtered, dried, ground and further carbonized for a period of time under the conditions of nitrogen atmosphere and a certain temperature to obtain the niobium-carbon solid acid catalyst. The obtained niobium-carbon solid acid catalyst can be used in the reaction of preparing 5-hydroxymethylfurfural from biomass.
The saccharide compound comprises one or more of glucose, sucrose, maltose, fructose, galactose, lactose, cellobiose, raffinose, etc.
The niobium precursor is niobium tartrate, niobium pentachloride, niobium oxalate, niobium citrate, niobium ethoxide, niobium n-propoxide, niobium n-butoxide or other niobium salts and the like.
The acid catalyst is one or more of phosphoric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, citric acid, tartaric acid, oxalic acid and the like.
In the preparation process, the carbohydrate and the niobium precursor are added into the solvent according to the mass ratio of 10:1-1:1, preferably 5:1-2: 1.
In the hydrothermal or solvothermal synthesis, the solvent may be one of water, methanol, ethanol, ethylene glycol and other organic solvents.
The temperature of the hydrothermal or solvent thermal is 140-260 ℃, preferably 160-220 ℃; the time is 4-48h, preferably 6-24 h.
The carbonization temperature is 300-800 ℃, and preferably 400-600 ℃; the time is 2-10h, preferably 4-8 h.
In the reaction for preparing 5-hydroxymethylfurfural from biomass, the biomass raw material is one of cellulose, glucose, fructose, sucrose, inulin, starch and the like; the specific conditions for evaluating the reaction are that 0.2g of the prepared catalyst, 0.2g of biomass raw material, 6ml of tetrahydrofuran and 2ml of saturated sodium chloride aqueous solution are put into a high-pressure magnetic stirring reaction kettle, the reaction is stirred for 8 hours at 180 ℃ under the condition of 0.5MPa of nitrogen, and the purpose of filling nitrogen is to ensure that the reaction is carried out in a liquid phase system.
The invention has the following advantages:
the invention provides a simple preparation method of a solid acid catalyst, which is applied to the reaction of preparing 5-hydroxymethylfurfural by biomass conversion, has a stable structure and good water resistance, and can be used for industrial batch production. In addition, the method can synthesize the solid acid catalyst with different acid amounts and acid strengths by adjusting different carbon sources, the types of niobium precursors and the proportion of the two.
Glucose, fructose, sucrose, inulin and starch are purchased from chemical reagents of national drug group, ltd; cellulose is available from Aladdin Chemicals, Inc.
The reaction mixture was analyzed by high performance liquid chromatography using Agilent 1200 HPLC using XDB-C18 column (4.5 μm, 250 mm, Eclipse USA) maintained at a constant temperature of 35%oC. The liquid chromatography was equipped with an Agilent model G1329A autosampler to increase sample reproducibility. The product HMF was detected using an Agilent model G1314B ultraviolet detector (VWD) with a wavelength of 254 nm, a mobile phase of a mixture of methanol and pure water at a volume ratio of 20:80 and a flow rate of 0.6 mL/min.
The product was quantitatively analyzed by external standard method. Preparing standard solutions of known product standard samples with different concentrations, measuring the liquid chromatogram peak area, and making a standard curve according to the relation between the concentration and the peak area. The standard curve formula of the product HMF is: a =2318557.1 x; wherein A is a peak area value of an HMF signal directly given by chromatography; and x is the mass concentration of HMF. The mass fraction of niobium pentoxide in the solid acid catalyst was measured on a PerkinElmer Pyris Diamond TGA thermogravimeter, and air was introduced at a flow rate of 50ml/min and a temperature rise rate of 10 ℃/min.
The total acid amount of the solid acid catalyst is measured by acid-base titration, and the specific operation steps are as follows: accurately weighed 0.25 g of niobium-carbon solid acid catalyst, uniformly dispersed in 30 mL, with a concentration of 0.05 mol.L-1In the NaOH solution, the mixed solution is subjected to ultrasonic dispersion treatment for 1 hour at normal temperature. After the reaction, the reaction solution was centrifuged, and the supernatant was collected and washed with 0.05 mol/L-1And titrating the hydrochloric acid solution, and calculating to obtain the total acid amount of the solid acid catalyst by using phenolphthalein as an indicator.
An X-ray diffraction (XRD) spectrum of the solid acid catalyst is measured on a Bruker diffractometer (D8 Focus) X-ray diffractometer, a Cu target Ka (lambda =0.154056 nm) source is adopted, the test voltage is 40 kV, the test current is 40 mA, the scanning range is 10-80 degrees, the scanning speed is 6 degrees/min, and whether the obtained catalyst is in an amorphous structure or not is judged according to the XRD spectrum.
The specific surface area and the average pore diameter of the solid acid catalyst are measured on a static nitrogen adsorber of ASAP2020M of Micromeritics, a sample is pretreated under the vacuum condition of 180 ℃, after the pretreatment, the analysis is carried out at the liquid nitrogen temperature (77K), and the pore structure and the specific surface area of the catalyst are measured by taking nitrogen as an adsorbate.
Drawings
FIG. 1 is an XRD spectrum of the niobium-carbon solid acid catalyst prepared in example 1.
FIG. 2 shows the niobium-carbon solid acid catalysts synthesized under different conditions in Table 1.
FIG. 3 shows the physical properties of different niobium-carbon solid acid catalysts shown in Table 2 and the performance of the catalysts in catalyzing cellulose to prepare 5-hydroxymethylfurfural.
FIG. 4 shows the different biomass feedstocks of Table 3 as reaction substrates.
FIG. 5 shows the cycle stability of the solid acid niobium carbon catalyst used in the hydrolysis and dehydration of cellulose to produce HMF of example 49.
Detailed Description
For the convenience of understanding the present invention, the present invention will be described below with reference to examples, which are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Examples 1 to 18
Weighing a certain amount of carbon source and 2g of niobium source in a beaker, adding the carbon source and 2g of niobium source into 20mL of acidic solution, continuously stirring for 2 hours, transferring the obtained solution into a stainless steel pressure kettle with a polytetrafluoroethylene lining, and crystallizing at a certain temperature for a period of time to obtain a dark brown solid. The niobium-carbon solid acid catalyst is prepared by washing with deionized water, drying, placing in a tubular furnace, and carbonizing for a certain time under the conditions of nitrogen atmosphere and a certain temperature (the specific specification of carbon source, niobium source, mass ratio, synthetic solvent and carbonization temperature is shown in table 1, and the physicochemical parameter characterization results of the solid acid catalysts are shown in table 2).
Adding 0.2g of catalyst, 0.2g of cellulose, 6mL of tetrahydrofuran and 2mL of saturated sodium chloride aqueous solution into a high-pressure magnetic stirring batch reaction kettle, charging 0.5MPa nitrogen, and heating to 180 DEGoCAfter the reaction was carried out at a constant temperature for 8 hours, the reaction system was cooled to room temperature (25 ℃ C.), and the catalyst was separated by centrifugation. Analyzing the reaction solution by high performance liquid chromatography, and calculating 5-hydroxymethylThe yield of furfural is shown in table 2.
Examples 34 to 48
0.2g of the catalyst in the above example, 0.2g of the biomass raw material, 6mL of tetrahydrofuran, and 2mL of a saturated aqueous sodium chloride solution were added to a high-pressure magnetic stirring batch reactor, and 0.5MPa of nitrogen was charged, the mixture was heated to 180 ℃ and reacted at a constant temperature for 8 hours, and then the reaction system was cooled to room temperature (25 ℃) and centrifuged to separate the catalyst. The reaction solution was analyzed by high performance liquid chromatography, and the yield of 5-hydroxymethylfurfural was calculated and shown in table 3.
Example 49
0.2g of the catalyst of example 1, 0.2g of cellulose, 6ml of tetrahydrofuran and 2ml of a saturated aqueous sodium chloride solution were charged into a high-pressure magnetically stirred batch reactor, and then 0.5MPa of nitrogen was charged into the reactor, the reactor was heated to 180 ℃ and reacted at a constant temperature for 8 hours, and then the reaction system was cooled to room temperature (25 ℃) and centrifuged to separate the catalyst. And analyzing the reaction liquid by using a high performance liquid chromatography, and calculating to obtain the yield of the 5-hydroxymethylfurfural. The catalyst is washed by deionized water and then put into the next reaction, and the reaction is recycled for 8 times, the result of each reaction is shown in figure 2, and the niobium-carbon solid acid catalyst shows good recycling stability.
Claims (7)
1. A method for preparing a solid acid catalyst for 5-hydroxymethylfurfural production from biomass, characterized by:
carrying out hydrothermal or solvent heat treatment on one or more of carbohydrate and a niobium precursor at a certain temperature for a period of time in the presence of an acid catalyst, washing with deionized water, then carrying out suction filtration, drying, grinding, and further carbonizing at a certain temperature and under a nitrogen atmosphere for a period of time to obtain a niobium-carbon solid acid catalyst, wherein the obtained niobium-carbon solid acid catalyst is used in a reaction for preparing 5-hydroxymethylfurfural from biomass;
wherein the mass ratio of the saccharide compound to the niobium precursor is 10:1-1: 1;
the acid catalyst is one or more of phosphoric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, citric acid, tartaric acid and oxalic acid;
the hydrothermal or solvothermal solvent is water, methanol, ethanol or ethylene glycol, the temperature is 140-260 ℃, and the time is 4-48 h;
the carbonization temperature is 300-800 ℃, and the time is 2-10 h.
2. The method for producing a solid acid catalyst according to claim 1, characterized in that: the saccharide compound comprises one or more of glucose, sucrose, maltose, fructose, galactose, lactose, cellobiose, and raffinose.
3. The method for producing a solid acid catalyst according to claim 1, characterized in that: the niobium precursor is niobium tartrate, niobium pentachloride, niobium oxalate, niobium citrate, niobium ethoxide, niobium n-propoxide or niobium n-butoxide.
4. The method for producing a solid acid catalyst according to claim 1, characterized in that: the mass ratio of the saccharide compound to the niobium precursor is 5:1-2: 1.
5. The method for producing a solid acid catalyst according to claim 1, characterized in that: the temperature of the hydrothermal or solvent heating is 160-220 ℃, and the time is 6-24 h.
6. The method for producing a solid acid catalyst according to claim 1, characterized in that: the carbonization temperature is 400-600 ℃, and the time is 4-8 h.
7. The preparation method of the solid acid catalyst according to claim 1, wherein the obtained niobium carbon solid acid catalyst is used in a reaction for preparing 5-hydroxymethylfurfural from biomass, and the biomass raw material is one or more of cellulose, glucose, fructose, sucrose, inulin and starch.
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| CN109536194B (en) * | 2017-09-21 | 2023-03-10 | 北京市环境保护科学研究院 | Preparation method of biofuel |
| CN108484540B (en) * | 2018-06-12 | 2021-11-19 | 西北工业大学 | Method for preparing 5-hydroxymethylfurfural by degrading cellulose in formic acid/acetic acid system |
| CN109092309B (en) * | 2018-09-06 | 2021-06-25 | 青岛科技大学 | Preparation method of catalyst for preparing 5-hydroxymethylfurfural from cellulose |
| CN109485622A (en) * | 2018-12-10 | 2019-03-19 | 北京化工大学 | A method of synthesis 5 hydroxymethyl furfural |
| CN110229125B (en) * | 2019-07-25 | 2022-04-19 | 广西科学院 | Low-cost preparation method of sucrose-based 5-hydroxymethylfurfural |
| CN113845497B (en) * | 2021-11-01 | 2023-09-15 | 沈阳化工大学 | Method for synthesizing 5-hydroxymethylfurfural at low temperature |
| CN114736175B (en) * | 2022-03-09 | 2023-09-26 | 常州大学 | Method for preparing 5-hydroxymethylfurfural by catalyzing glucose in aqueous phase |
| CN117466844B (en) * | 2023-10-30 | 2024-08-09 | 合肥利夫生物科技有限公司 | Preparation method of 5-hydroxymethylfurfural |
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| "Tuning the Location of Niobia/Carbon Composites in a Biphasic Reaction: Dehydration of D-Glucose to 5-Hydroxymethylfurfural";Haifeng Xiong等;《Catal Lett》;20130410;第143卷;第2.1节，第2.3.2节，表3 * |
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