CN102962085A - Preparation method of niobium phosphate solid acid catalyst and application in sugar dehydration - Google Patents
Preparation method of niobium phosphate solid acid catalyst and application in sugar dehydration Download PDFInfo
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- CN102962085A CN102962085A CN2011102570792A CN201110257079A CN102962085A CN 102962085 A CN102962085 A CN 102962085A CN 2011102570792 A CN2011102570792 A CN 2011102570792A CN 201110257079 A CN201110257079 A CN 201110257079A CN 102962085 A CN102962085 A CN 102962085A
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Abstract
The invention relates to a preparation method and application of a niobium phosphate solid acid catalyst. The catalyst has a mesoporous structure, a specific surface area of 160-290m<2>/g, and a pore volume of 0.16-0.29cm<3>/g. The solid acid catalyst provided in the invention can be used to catalyze a plurality of acid catalyzed reactions, especially a sugar dehydration reaction, and has the advantages of high specific surface area, good thermal stability, high activity, simple preparation, low cost, and easy regeneration.
Description
Technical field
The present invention relates to a kind of preparation method and the application in sugared dehydration thereof of niobium phosphate solid acid catalyst, belong to catalytic chemistry and field of chemical engineering.
Background technology
The sugar dehydration is one of reaction important during living beings are utilized, and product furfural or 5 hydroxymethyl furfural (HMF) also are commercial synthetic a series of intermediates commonly used with chemicals of ad hoc structure and performance simultaneously.The general homogeneous liquid acid catalysis sugar dehydration that adopts, for example Dumesic dewaters with HCl catalysis fructose, and the HMF yield can reach (Scinece more than 70%, 2006,312,1933), but have etching apparatus, the later separation cost is high, the shortcoming such as adopt that batch reactor can not be produced continuously.And solid acid is easy to separate the concern that more and more causes people with industrialization with it.
Current people are more and more stricter to the requirement of environmental protection, and the idea of Green Chemistry is rooted in the hearts of the people, and novel, eco-friendly reaction system has caused people's extensive concern.With respect to organic solvent (such as DMSO), aqueous solvent has obvious advantage: non-secondary pollution, and with low cost, product is easy to separate, environmental friendliness, and the temperature operation scope is wide even can react in gas phase, can also make the technical process serialization, improve production capacity.But the most solid acid catalyst is active low in pure aquatic system, utilize the material with carbon element of sulfonation to be catalyst such as Wang Jianjian etc., DMSO is solvent, the yield of the standby HMF of fructose Dehydration is up to 91%, but in aqueous systems HMF yield extremely low (Green Chemistry DOI:10.1039/C1GC15306D).Thomson S.Hansen etc. is in water and methyl iso-butyl ketone (MIBK) (MIBK) mol ratio are 2: 8 mixed solvent for another example, adopting boric acid is that catalyst prepares HMF from fructose, although introduced water as solvent but in order to guarantee that product yield preferably still can not thoroughly abandon use (the Green Chemistry of organic solvent, 2011,13,109-114).Thereby the solid acid that truly can use in pure aquatic system is rare, and wherein most specific areas are smaller.
Summary of the invention
The object of the present invention is to provide a kind of sugared Dehydration of water (can certainly be used for the organic solvent phase) that can be used for for mesoporous niobium phosphate solid acid catalyst and the preparation method of furfural or 5 hydroxymethyl furfural (HMF), it is characterized in that specific area is high, pore-size distribution is narrow, Heat stability is good, active high, applied widely, preparation is simple, characteristics with low cost, as to regenerate easily.
Mesoporous solid acid catalyst of the present invention is niobium phosphate, it is characterized in that having impalpable structure, and specific area is 160～290m
2/ g, pore volume are 0.16～0.29cm
3/G; Aspect acidic character, have simultaneously B acid position and L acid position.
Description of drawings
Fig. 1 is in the nitrogen adsorption desorption curve of intermediary hole niobium phosphate material of the present invention, and inserting figure is the pore size distribution curve that calculates by the BJH method.
Fig. 2 is transmission electron microscope (TEM) photo of intermediary hole niobium phosphate material of the present invention, can clearly see the existence of pore structure among the figure, and the aperture is in the 3-5nm scope.
Concrete technical scheme of the present invention is as follows:
The preparation method of mesoporous niobium phosphate solid acid catalyst of the present invention, its feature may further comprise the steps: soluble-salt (II) or its mixed solution (III) of preparing certain density niobic soluble-salt (I), three valent phosphors acid group; Prepare certain density CTAB solution (VI); The pH value of regulation and control solution.Move into after the vigorous stirring in the band teflon-lined stainless steel cauldron, at a certain temperature crystallization a period of time; Then through centrifugation, the solid that obtains makes mesoporous niobium phosphate solid acid catalyst with deionized water washing, oven dry, grinding finally by crossing roasting.
Mixed solution for described soluble-salt is characterised in that: niobic soluble-salt is oxalates, tartrate, chloride, one or both in the ethylate, and its concentration is 0.05～1 mol/L; The soluble-salt of phosphorus is sodium phosphate, and the phosphate such as ammonium phosphate are preferably (NH
4)
2HPO
4, its concentration is 0.05～1 mol/L.
Be characterised in that for described CTAB solution: dissolving CTAB described solvent is water, methyl alcohol, and ethanol, a kind of in the cyclohexane is preferably deionized water, and the concentration of its aqueous solution is 0.01～1 mol/L.
During Kaolinite Preparation of Catalyst, it is characterized in that: it is characterized in that the CTAB solution with soluble-salt or its mixed solution and 0.01～1 mol/L, the pH value of control mixed solution is at 1-10, after mixing, move in the band teflon-lined stainless steel cauldron, 80～180 ℃ of crystallization 12～96 hours.
The baking temperature of the solid that obtains is 50～120 ℃; Sintering temperature is 300～800 ℃, and heating rate is 1～15 ℃/minute, and roasting time is 2～18 hours.
Catalyst of the present invention can be applicable to the dehydration of wood sugar, glucose and fructose, and wherein the chemical equation of fructose dehydration can be expressed as:
Catalyst of the present invention has the following advantages: this mesoporous niobium phosphate solid acid catalyst specific area is high, and heat endurance is high, and catalytic activity is high.The below illustrates technical scheme of the present invention with example, but protection scope of the present invention is not limited to this.
The specific embodiment
Embodiment 1
With the mixed aqueous solution of deionized water preparation niobium oxalate and dibastic sodium phosphate, wherein Nb
5+Concentration is 0.8 mol/L, PO
4 3-Concentration is 0.8 mol/L; The preparation CTAB aqueous solution, concentration is 0.02 mol/L, with sour adjust pH to 4.Under continuous stirring, with Nb, the P mixed solution drops in the CTAB solution, and pH is about 4 in control.Wait to dropwise, slurries are transferred in the stainless steel pressure still with teflon lined, in 100 ℃ of crystallization 24h.After centrifugation, sediment is washed to pH=7 with deionized water, then 60 ℃ of dried overnight, grind, place again Muffle furnace in 550 ℃ of roastings 6 hours, namely make required catalyst.
Get wood sugar 0.8g, deionized water 10g, catalyst 0.7g puts into batch reactor, 150 ℃ the reaction 3 hours after, the sampling carry out liquid-phase chromatographic analysis, the wood sugar conversion ratio is 85.1%, furfural selectively be 43.3%, yield is 36.9%.
Embodiment 2
With the mixed aqueous solution of deionized water assembled alcoholic drinks stone acid niobium and diammonium hydrogen phosphate, wherein Nb
5+Concentration is 0.5 mol/L, PO
4 3-Concentration is 0.5 mol/L; The preparation CTAB aqueous solution, concentration is 0.01 mol/L, transferring pH is 7.Under continuous stirring, CTAB solution is added drop-wise to Nb, in the P mixed solution, pH is about 3 in control, waits to dropwise, and slurries are transferred in the stainless steel pressure still with teflon lined, in 80 ℃ of crystallization 24h.After centrifugation, sediment is washed to pH=7 with deionized water, then 60 ℃ of dried overnight, grind, place again Muffle furnace in 550 ℃ of roastings 6 hours, namely get required catalyst.
Get glucose 0.8g, DMSO 10ml, catalyst 0.7g puts into batch reactor, after 1.5 hours, liquid-phase chromatographic analysis is carried out in sampling 130 ℃ of reactions, glucose sugar conversion ratio be 11.7%, HMF selectively be 31.4%, yield is 3.67%.
Embodiment 3
With the mixed aqueous solution of deionized water preparation columbium pentachloride and dibastic sodium phosphate, wherein Nb
5+Concentration is 1 mol/L, PO
4 3-Concentration is 1 mol/L; The preparation CTAB aqueous solution, concentration is 0.2 mol/L.Under continuous stirring, with Nb, the P mixed solution drips with CTAB solution and drip and is added in the beaker, and control pH value is waited to dropwise about 7, and slurries are transferred in the stainless steel pressure still with teflon lined, in 160 ℃ of crystallization 24h.After centrifugation, sediment is washed to pH=7 with deionized water, then 60 ℃ of dried overnight, grind, place again Muffle furnace in 550 ℃ of roastings 6 hours, namely make required catalyst.
1.0g 20-40 purpose catalyst is placed on the middle part of fixed bed reactors, and making concentration is that the fructose water solution of 0.75g/L flows through beds with the 0.09mL/min flow velocity, and liquid-phase chromatographic analysis is carried out at set intervals sampling.When reaction temperature is 110 ℃, the fructose conversion ratio be 76.0%, HMF selectively be 42.1%, yield is 32.0%.
Embodiment 4
With the mixed aqueous solution of deionized water preparation niobium oxalate and dibastic sodium phosphate, wherein Nb
5+Concentration is 0.5 mol/L, PO
4 3-Concentration is 0.5 mol/L; The preparation CTAB aqueous solution, concentration is 0.15 mol/L.Under continuous stirring, with Nb, the P mixed solution drips with CTAB solution and drip and is added in the beaker, and control procedure is waited to dropwise about 2, and slurries are transferred in the stainless steel pressure still with teflon lined, in 80 ℃ of crystallization 24h.Through 100 ℃ of crystallization 12h, after centrifugation, sediment is washed to pH=7 with deionized water again, then 60 ℃ of dried overnight, grind, place again Muffle furnace in 550 ℃ of roastings 6 hours, namely make required catalyst.
Get fructose 0.8g, deionized water and DMSO mixed solvent 10ml (volume ratio 8: 2), catalyst 0.7g, put into batch reactor, after 1 hour, liquid-phase chromatographic analysis is carried out in sampling 130 ℃ of reactions, the fructose conversion ratio be 73.9%, HMF selectively be 63.4%, yield is 46.9%.
1, the regeneration of catalyst
Catalyst is with embodiment 1.
The renovation process of catalyst is: centrifugation went out catalyst after reaction finished, and 100 ℃ of dried overnight, placed Muffle furnace 600 ℃ of roastings 10 hours again.
Get wood sugar 0.8g, deionized water 10g, catalyst 0.7g puts into batch reactor, 150 ℃ the reaction 3 hours after, the sampling carry out liquid-phase chromatographic analysis, the wood sugar conversion ratio is 80.2%, furfural selectively be 41.1%, yield is 32.9.%.
2. catalyst stability test
Catalyst is with embodiment 4
Get fructose 0.8g, deionized water and DMS0 mixed solvent 10ml (volume ratio 8: 2), catalyst 0.7g, put into batch reactor, 130 ℃ the reaction 1 hour after, liquid-phase chromatographic analysis is carried out in sampling. and react complete, filtration, washing obtain directly carrying out second, third secondary response behind the catalyst, the results are shown in Table 1.
Table 1 catalyst regeneration result of the test
| Access times | Conversion ratio | Selectively | Yield |
| 1 | 73.9％ | 63.4％ | 46.9％ |
| 2 | 67.2％ | 60.6％ | 40.7％ |
| 3 | 56.2％ | 65.9％ | 37.0％ |
Claims (5)
1. niobium phosphate solid acid catalyst is characterized by: have impalpable structure, have simultaneously B acid position and L acid, specific area is 160～290m
2/ g, pore volume are 0.16～0.29cm
3/ g, and have meso-hole structure.
2. the preparation method of solid acid catalyst according to claim 1, its feature may further comprise the steps: soluble-salt (II) or its mixed solution (III) of preparing certain density niobic soluble-salt (I), three valent phosphors acid group; Prepare certain density CTAB solution (VI); The pH value of regulation and control mentioned solution, adopt coprecipitation or sol-gel process to be prepared, and control simultaneously the pH value of synthesis mother liquid, synthesis mother liquid moves into after vigorous stirring in the band teflon-lined stainless steel cauldron, reacts a period of time at a certain temperature; Then through centrifugation, the sediment that obtains obtains presoma with deionized water washing, oven dry, grinding, makes mesoporous niobium phosphate solid acid catalyst finally by crossing roasting.
3. the mixed solution of soluble-salt according to claim 2, it is characterized in that: niobic soluble-salt is one or both in oxalates, tartrate, the chloride, its concentration is 0.05～1 mol/L; The soluble-salt of phosphorus is phosphate, and its concentration is 0.05～1 mol/L.
4. among the preparation method of catalyst according to claim 2, it is characterized in that soluble-salt or its mixed solution are mixed with the CTAB solution of 0.01～1 mol/L, and the pH value of control soluble-salt or its mixed solution is at 1-10, after mixing, move in the band teflon-lined stainless steel cauldron, wore out 48～96 hours at 80～180 ℃, after filtering, washing, 50～120 ℃ of dried overnight, again 300～800 ℃ of roastings 2～10 hours in horse still stove.
5. solid acid catalyst claimed in claim 1 can be used in many acid catalyzed reactions, such as esterification, and alkylated reaction, sugar dehydration etc., it preferably reacts is sugared dehydration, sugared dehydration can be at batch still, also can in fixed bed reactors, carry out, solvent can be DMSO, DMF, THF, MIBK, ionic liquid, ethyl acetate, the 2-butanols, ethanol, acetone, the mixed solvent of deionized water or above-mentioned solvent, wherein deionized water is preferred solvent.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104248974A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst, preparation method and application thereof, and cyclohexanone glyceryl ketal preparation method |
| CN105536832A (en) * | 2015-12-10 | 2016-05-04 | 大连交通大学 | Method for preparing mesoporous niobium phosphate catalyst and application of mesoporous niobium phosphate catalyst in preparation of isosorbitol from sorbitol |
| CN106732701A (en) * | 2017-01-11 | 2017-05-31 | 贵州大学 | A kind of Fe2O3 doping niobium phosphate solid acid catalyst |
| CN107337657A (en) * | 2017-07-20 | 2017-11-10 | 中国科学院广州能源研究所 | A kind of method for preparing 5 hydroxymethylfurfurals using monose green |
| CN107473266A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | A kind of niobium phosphate Porous materials and its production and use |
| CN109569677A (en) * | 2018-12-18 | 2019-04-05 | 北京化工大学 | It is used to prepare solid acid catalyst and its preparation and application of biology base paraxylene |
| CN110002416A (en) * | 2019-03-16 | 2019-07-12 | 复旦大学 | A kind of acid phosphate niobium oxygen monoatomic layer preparation of sections method |
| CN110152698A (en) * | 2018-02-13 | 2019-08-23 | 北京石油化工学院 | The phosphate niobium catalyst of metal oxide modified, and its preparation method and application |
| CN114736175A (en) * | 2022-03-09 | 2022-07-12 | 常州大学 | Method for preparing 5-hydroxymethylfurfural by catalyzing glucose in aqueous phase |
| CN114853777A (en) * | 2022-06-14 | 2022-08-05 | 华北电力大学 | Catalytic pyrolysis method for preparing LGO |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104248974A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst, preparation method and application thereof, and cyclohexanone glyceryl ketal preparation method |
| CN105536832A (en) * | 2015-12-10 | 2016-05-04 | 大连交通大学 | Method for preparing mesoporous niobium phosphate catalyst and application of mesoporous niobium phosphate catalyst in preparation of isosorbitol from sorbitol |
| CN105536832B (en) * | 2015-12-10 | 2017-12-29 | 大连交通大学 | The preparation method of mesoporous phosphate niobium catalyst and its application in sorbierite isobide |
| CN107473266A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | A kind of niobium phosphate Porous materials and its production and use |
| CN107473266B (en) * | 2016-06-08 | 2019-08-16 | 中国石油化工股份有限公司 | A kind of niobium phosphate Porous materials and its preparation method and application |
| CN106732701A (en) * | 2017-01-11 | 2017-05-31 | 贵州大学 | A kind of Fe2O3 doping niobium phosphate solid acid catalyst |
| CN106732701B (en) * | 2017-01-11 | 2020-01-31 | 贵州大学 | solid acid catalyst of iron-doped niobium phosphate |
| CN107337657A (en) * | 2017-07-20 | 2017-11-10 | 中国科学院广州能源研究所 | A kind of method for preparing 5 hydroxymethylfurfurals using monose green |
| CN107337657B (en) * | 2017-07-20 | 2019-07-12 | 中国科学院广州能源研究所 | A method of 5 hydroxymethyl furfural is prepared using monosaccharide green |
| CN110152698B (en) * | 2018-02-13 | 2022-06-24 | 北京石油化工学院 | Metal oxide modified niobium phosphate catalyst, preparation method and application thereof |
| CN110152698A (en) * | 2018-02-13 | 2019-08-23 | 北京石油化工学院 | The phosphate niobium catalyst of metal oxide modified, and its preparation method and application |
| CN109569677A (en) * | 2018-12-18 | 2019-04-05 | 北京化工大学 | It is used to prepare solid acid catalyst and its preparation and application of biology base paraxylene |
| CN110002416A (en) * | 2019-03-16 | 2019-07-12 | 复旦大学 | A kind of acid phosphate niobium oxygen monoatomic layer preparation of sections method |
| CN110002416B (en) * | 2019-03-16 | 2022-06-21 | 复旦大学 | Preparation method of niobium oxygen acid phosphate monoatomic layer sheet |
| CN114736175A (en) * | 2022-03-09 | 2022-07-12 | 常州大学 | Method for preparing 5-hydroxymethylfurfural by catalyzing glucose in aqueous phase |
| CN114736175B (en) * | 2022-03-09 | 2023-09-26 | 常州大学 | Method for preparing 5-hydroxymethylfurfural by catalyzing glucose in aqueous phase |
| CN114853777A (en) * | 2022-06-14 | 2022-08-05 | 华北电力大学 | Catalytic pyrolysis method for preparing LGO |
| CN114853777B (en) * | 2022-06-14 | 2024-03-01 | 华北电力大学 | Catalytic pyrolysis method for preparing LGO |
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Application publication date: 20130313 |