CN104478834A - Method for preparing 2,5-furan diformaldehyde recyclable in catalysis system - Google Patents
Method for preparing 2,5-furan diformaldehyde recyclable in catalysis system Download PDFInfo
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- CN104478834A CN104478834A CN201410834527.4A CN201410834527A CN104478834A CN 104478834 A CN104478834 A CN 104478834A CN 201410834527 A CN201410834527 A CN 201410834527A CN 104478834 A CN104478834 A CN 104478834A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
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Abstract
The invention discloses a method for preparing 2,5-furan diformaldehyde recyclable in a catalysis system. The method is characterized by comprising the following steps: adding a piperidine nitric oxide catalyst, a catalyst activating agent and an additive alkali halide into an organic solvent so as to form the catalysis system; adding 5-hydroxymethylfurfural, and stirring in air at the room temperature so as to obtain a reaction mixed solution containing a target product 2,5-furan diformaldehyde; performing solid-liquid separation and pressure reduction concentration on the reaction mixed solution, so as to separate and purify the product and recycle and regenerate the catalysis system. The catalysts used in the method disclosed by the invention are cheap and easy to obtain, short in reaction time and efficient and energy-saving, the yield of a target product is as high as 92%, and a very small amount of byproducts are generated; moreover the catalysis system can be repeatedly used, a small amount of wastes are discharged, thus protecting the environment; the method is very low in equipment requirement and small in equipment investment, and has very important application values.
Description
Technical field
The present invention relates to a kind of catalytic air oxidation to prepare DFF and recycle the method for catalyst system.
Background technology
The important dependence of human development since oil was 20th century, along with the minimizing of prospective oil and people are to the increase of petroleum product demand, finds reproducible oil substitutes quite concerned in recent years.Biomass are subject to extensive concern as the reproducible organic carbon resource of unique one.5 hydroxymethyl furfural (5-HMF) is a kind of important plateform molecules that can obtain from biomass, can be converted into Multi liquid fuel and chemical.By oxidation, 5-HMF can be converted into DFF (2,5-DFF), and the latter is the chemical intermediate with important potential using value, may be used for as multiple fields such as medicine, high polymer monomer, tackiness agents.But there is abundant functional group due to 5-HMF, may occur a series of side reaction as peroxidation, become ether, polymerization and DeR, make the high yield of 2,5-DFF obtain challenging.
Early stage 2,5-DFF is obtain by using permanganate, chromium trioxide or the oxidizing 5-HMF of clorox equivalent.But this preparation method's cost is higher, and environmental pollution is serious.
Amarasekara etc. use Mn (III)-Salen as catalyzer in Catalysis Communications 9 (2008) 286-288, obtain 2, the 5-DFF yields of 89% in methylene dichloride.But this system still employs clorox is oxygenant, Financial cost and Environmental costs are all higher, and catalyst system can not recycle.
Lilga etc. use active γ-MnO in patent US 2008/0103318A1
2as catalyzer, back flow reaction 8h in methylene dichloride, obtains 2, the 5-DFF yields of 80%.But this process employs the active γ-MnO more than 600wt%
2as catalyzer, aftertreatment difficulty; Reaction times is also longer, and activity is very low; The yield of product is also lower.
Xu Jie etc. use Cu (NO in patent CN 101987839A
3)
2and VOSO
4composite catalyst system, utilizes molecular oxygen as oxygen source, is heated to 80 DEG C of reaction 1.5h, obtains 2, the 5-DFF yields of 98% in acetonitrile.This process reaction mild condition, 2,5-DFF yield is high.But this System Catalyst can not reclaim, cannot recycle.
Yadav etc. use Ag load on manganese oxide carrier as catalyzer in patent 3246|MUM|2010, be heated to 145 DEG C of reaction 4h, obtain 2, the 5-DFF yields of 99% in isopropanol solvent.But this process employs noble metal Ag as catalyzer, the charge capacity of Ag is up to 15-20%, and cost compare is high.
Bang superfine in patent CN 102731448B and Fu Yao etc. use in Green Chemistry14 (2012) 2986-2989 and there is the Manganse Dioxide (OMS-2) of octahedron molecular screen structure as catalyzer, use oxygen as oxygenant, react in non-protonic polar solvent, obtain the selectivity more than 99%.This process reaction mild condition, 2,5-DFF yield is high.But the solvent selected due to reaction system is high boiling solvent, cause the segregation ratio of product in this system more difficult.
Summary of the invention
The object of this invention is to provide one under mild reaction conditions, cheapness, environmental protection, high reactivity, high yield prepare 2 by 5 hydroxymethyl furfural (5-HMF), 5-furans dicarbaldehyde (2, method 5-DFF), by reaction system separating-purifying 2, the method that the method for 5-furans dicarbaldehyde (2,5-DFF) and catalyst system recycle.
Preparation method of the present invention is under the reaction conditions of gentleness, take atmospheric air as oxygenant, makes 5 hydroxymethyl furfural carry out oxidizing reaction, obtain DFF under the katalysis of catalyst activator and piperidines oxynitride.And realize the separating-purifying of product and the cyclic regeneration of catalyst system by solid-liquid separation and concentration technology.
Technical solution problem of the present invention, adopts following technical scheme:
The preparation method of the DFF that catalyst system of the present invention can be recycled, its feature is to carry out as follows:
A, piperidines nitrogen oxide catalyst, catalyst activator and additive basic metal halide are joined in organic solvent, form catalyst system, 5 hydroxymethyl furfural is added in described catalyst system, form raw material mixed solution, raw material mixed solution 12h described in stirred at ambient temperature in atmosphere, oxidizing reaction is carried out under making the oxygenizement of 5 hydroxymethyl furfural under the katalysis of piperidines nitrogen oxide catalyst and catalyst activator, at air, obtain the reaction mixture containing target product DFF; In described reaction mixture, solid phase is catalyst activator and additive basic metal halide, and liquid phase comprises target product DFF, unreacted complete raw material 5 hydroxymethyl furfural, organic solvent and catalyzer;
B, carry out solid-liquid separation obtain solid phase and liquid phase to described reaction mixture by filtration, wherein solid phase is the inorganic reaction residue be made up of catalyst activator and additive basic metal halide;
Evaporation concentration is carried out to described liquid phase, obtain phlegma and concentrated solution, described phlegma is most organic solvent in liquid phase, and described concentrated solution is made up of raw material 5 hydroxymethyl furfural, the organic solvent do not removed completely and the catalyzer that target product DFF, unreacted are complete;
And then to described concentrated solution crystallisation by cooling, gained crystal is product DFF, remaining liq is the mother liquor be made up of raw material 5 hydroxymethyl furfural, the organic solvent do not removed completely and catalyzer that unreacted is complete;
C, by after described mother liquor and the mixing of described inorganic reaction residue, then add described phlegma, reconstitute catalyst system, for step a.
Above-mentioned preparation method, its feature is also:
The ratio of the quality of 5 hydroxymethyl furfural described in step a and described organic solvent volume is 20-300g/L; The amount of substance of described piperidines nitrogen oxide catalyst is the 1%-5% of described 5 hydroxymethyl furfural amount of substance; The amount of substance of described catalyst activator is the 1%-5% of 5 hydroxymethyl furfural amount of substance; The amount of substance of described alkali metal halide is the 1%-10% of described 5 hydroxymethyl furfural amount of substance.
Described piperidines nitrogen oxide catalyst is tetramethyl piperidine oxynitride;
Described catalyst activator is that iron nitrate (is preferably Fe (NO
3)
39H
2o);
Described organic solvent is one or more mixing in ethylene dichloride, methylene dichloride, ethyl acetate, toluene, dioxane, tetrahydrofuran (THF) or acetonitrile;
Described alkali metal halide is one or more mixing in sodium-chlor, Repone K, Sodium Bromide and Potassium Bromide.
The present invention prepares the reaction mechanism of DFF (2,5-DFF) as shown in Figure 2 by 5 hydroxymethyl furfural (5-HMF),
A, tetramethyl piperidine oxynitride (TEMPO) are at iron ion (Fe
3+) 5 hydroxymethyl furfural (5-HMF) is oxidized to DFF (2,5-DFF) under activation.Tetramethyl piperidine oxynitride (TEMPO) is reduced to tetramethyl piperidine azanol form (TEMPOH), iron ion (Fe simultaneously
3+) be reduced to ferrous ion (Fe
2+).
B, tetramethyl piperidine azanol form (TEMPOH) and ferrous ion (Fe
2+) at nitrate radical (NO
3 -) be oxidized to tetramethyl piperidine oxynitride (TEMPO) and iron ion (Fe under effect
3+), there is water (H simultaneously
2o) generate, nitrate radical (NO
3 -) be reduced to nitrite anions (NO
2 -).
C, nitrite anions (NO
2 -) by oxygen (O
2) be oxidized to nitrate radical (NO
3 -), and then carry out next round reaction.
5 hydroxymethyl furfural (5-HMF) structural formula as shown in Equation 1, DFF (2,5-DFF) structural formula as shown in Equation 2:
Compared with the prior art, beneficial effect of the present invention is embodied in:
Preparation method of the present invention catalyzer used is cheap and easy to get; Reaction times is short, energy-efficient; Target product yield is up to 92%, and amount of by-products is little; Using air as oxygen source, economy and environment cost is low; By comparative analysis product DFF and raw material 5 hydroxymethyl furfural structure, product DFF molecule has space symmetr structure, and molecular polarization degree is little, and solvability is relatively poor; And raw material 5 hydroxymethyl furfural spatial configuration of molecules is asymmetric, molecular polarization degree is large, and solubility property is more excellent.By freezing and crystallizing, being separated and the purification of product of product and catalyzer can be realized; And catalyst system can be reused, and waste discharge is few, environmental protection; Very low to equipment requirements, facility investment is little, has very important using value.
Accompanying drawing explanation
The last handling process schematic diagram of the reaction mixture containing target product DFF of Fig. 1 prepared by the present invention;
Fig. 2 is the reaction mechanism figure that the present invention prepares DFF (2,5-DFF);
Fig. 3 is the GC spectrogram that the embodiment of the present invention 1 prepares DFF (2,5-DFF);
Specific embodiment
Embodiment 1
The present embodiment prepares the reaction mixture containing DFF (2,5-DFF) as follows by 5-HMF:
By the Fe (NO of 10.1mg
3)
39H
2o (0.025mmol altogether, account for 5% of 5-HMF amount of substance), the TEMPO of 7.8mg (0.025mmol altogether, account for 5% of 5-HMF amount of substance) and 1.5mg NaCl (0.025mol altogether, account for 5% of 5-HMF amount of substance) join in 2mL ethylene dichloride, form catalyst system, the 5-HMF (altogether 0.5mmol) of 63mg is added again in catalyst system, form raw material mixed solution, stirred at ambient temperature raw material mixed solution 12h in atmosphere, obtain the reaction mixture containing target product 2,5-DFF;
As shown in Figure 2, this implementation success obtains product 2,5-DFF (interior mark: 5 methyl furfural) to the GC detected result of reaction mixture as can be seen from Figure 2, and the present embodiment 2,5-DFF yield is 92%.
The condition that GC detects:
Equipment: Shimadzu 2014, configuration fid detector
Chromatographic column: RTX-5 post
Column temperature: 150 DEG C
Embodiment 2
The present embodiment presses preparation raw material shown in table 1, and except the raw material that table 1 is contained, 5-HMF and the 2mL organic solvent dichloromethane also containing 0.5mmol, preparation method is: by catalyst activator (Fe (NO
3)
39H
2o, Cu (NO
3)
23H
2o, AgNO
3, Pd (NO
3)
33H
2o or FeCl
3), TEMPO and additive (NaCl) join in 2mL methylene dichloride, form catalyst system, in catalyst system, add 5-HMF again, form raw material mixed solution, stirred at ambient temperature raw material mixed solution 12h in atmosphere, obtains the reaction mixture containing target product DFF; The yield of products therefrom is in table 1.
Raw materials used and the products therefrom yield table of table 1 embodiment 2
Productive rate as can be seen from table, does not add TEMPO (example 2) or does not add Fe(NO3)39H2O (example 3) and all can not get target compound.Add a small amount of sodium-chlor (example 4) and relatively basic control group experiment (example 1) 2,5-DFF yield can be improved further.And Fe(NO3)39H2O cationic (ferric ion) is replaced by cupric ion (example 5), silver ions (example 6) or palladium ion (example 7) and negatively charged ion in Fe(NO3)39H2O (nitrate ion) is replaced by chlorion (example 8) and all make relatively basic control group experiment (example 1) of 2,5-DFF yields reduce.As shown in Table 1, in catalyzer composition, TEMPO is necessary component, and nitrate anion and ferric iron positively charged ion are optimum combinations.
Embodiment 3
The present embodiment presses the group of preparation raw material shown in table 2, and except the raw material that table 2 is contained, 5-HMF and the 2mL organic solvent dichloromethane also containing 0.5mmol, preparation method is: by TEMPO, catalyst activator (Fe (NO
3)
39H
2and additive (NaBr, KCl, NaF or NaCl) O), join in 2mL methylene dichloride, form catalyst system, 5-HMF is added again in catalyst system, form raw material mixed solution, stirred at ambient temperature raw material mixed solution 12h in atmosphere, obtains the reaction mixture containing target product DFF; The yield of products therefrom is in table 2.
The raw materials used table of table 2 embodiment 3
Yield as can be seen from table, adding a small amount of alkali metal halide all can affect 2,5-DFF yield, fluorion faint reduction by 2,5-DFF yield in halogen ion, and chlorion significantly improves 2,5-DFF yields, and bromide anion appropriateness improves 2,5-DFF yield.The change of alkalimetal ion improves impact not quite to 2,5-DFF yield.
Embodiment 4
The present embodiment prepares 2 by the mode that embodiment 1 is identical, 5-DFF, difference only with by increasing the quality of 5-HMF, make the quality of raw material 5-HMF and the ratio of organic solvent volume change 25g/L, 50g/L, 100g/L, 120g/L, 140g/L, 160g/L, 180g/L, 200g/L, 250g/L, 300g/L into successively.Increase Fe (NO simultaneously
3)
39H
2the quality of O, TEMPO and NaCl, make its amount of substance accounting for 5-HMF all keep 5%, after different concns raw material carries out oxidizing reaction, the yield of products therefrom is as shown in table 3.
Table 3 material concentration is on the impact of product yield:
Yield as can be seen from table, along with the concentration of substrate 5-HMF increases, the yield of 2,5-DFF reduces gradually, even if but the concentration of 5-HMF is at 200g/L, 2,5-DFF preferably yield still can be obtained, 5-HMF, under 300g/L High Concentration Situation, also can obtain 2,5-DFF medium yields.This embodies the high technological advantage of unit of the present invention production capacity.
Embodiment 5
The present embodiment prepares DFF as follows:
A, by TEMPO (0.62g, 4mmol, 5mol%), Fe (NO
3)
39H
2o (1.6g, 4mmol, 5mol%) and NaCl (23mg, 4mmol, 5mol%) joins in 50mL ethylene dichloride, forms catalyst system;
B, in catalyst system, add 5-HMF (10g, 80mmol) again, form raw material mixed solution, stirred at ambient temperature raw material mixed solution 12h in atmosphere, the red suspension liquid of gained is the reaction mixture containing target product DFF; In reaction mixture, solid phase is catalyst activator Fe (NO
3)
39H
2o and additive NaCl, liquid phase comprises target product 2,5-DFF, unreacted complete raw material 5-HMF, organic solvent ethylene dichloride and catalyzer TEMPO;
C, carry out solid-liquid separation obtain solid phase and liquid phase to reaction mixture by filtration, wherein solid phase is by Fe (NO
3)
39H
2the inorganic reaction residue that O and NaCl is formed;
Evaporation concentration is carried out to about 10mL to liquid phase, obtain phlegma and concentrated solution, phlegma is most ethylene dichloride in reaction solution, and concentrated solution is made up of raw material 5-HMF, the ethylene dichloride do not removed completely and the TEMPO that target product 2,5-DFF, unreacted are complete;
And then to concentrated solution crystallisation by cooling, separate out 7.8g crystal and be product 2,5-DFF, remaining liq is the mother liquor be made up of raw material 5 hydroxymethyl furfural, the organic solvent do not removed completely and TEMPO that unreacted is complete;
D, by after mother liquor and the mixing of inorganic reaction residue, then add phlegma, reconstitute catalyst system, repeating step b, c, obtain 7.2g product 2,5-DFF.
E, again with catalyst system repeating step b and c that newly obtain totally 3 times, obtain 7.7g, 7.0g and 6.5g product 2,5-DFF respectively.
All batches of 2,5-DFF products are analyzed through HPLC, the equal > 98% of purity.
Claims (3)
1. the preparation method of DFF that can be recycled of catalyst system, is characterized in that carrying out as follows:
A, piperidines nitrogen oxide catalyst, catalyst activator and additive basic metal halide are joined in organic solvent, form catalyst system, 5 hydroxymethyl furfural is added in described catalyst system, form raw material mixed solution, raw material mixed solution 12h described in stirred at ambient temperature in atmosphere, oxidizing reaction is carried out under making the oxygenizement of 5 hydroxymethyl furfural under the katalysis of piperidines nitrogen oxide catalyst and catalyst activator, at air, obtain the reaction mixture containing target product DFF; In described reaction mixture, solid phase is catalyst activator and additive basic metal halide, and liquid phase comprises target product DFF, unreacted complete raw material 5 hydroxymethyl furfural, organic solvent and catalyzer;
B, carry out solid-liquid separation obtain solid phase and liquid phase to described reaction mixture by filtration, wherein solid phase is the inorganic reaction residue be made up of catalyst activator and additive basic metal halide;
Evaporation concentration is carried out to described liquid phase, obtain phlegma and concentrated solution, described phlegma is most organic solvent in liquid phase, and described concentrated solution is made up of raw material 5 hydroxymethyl furfural, the organic solvent do not removed completely and the catalyzer that target product DFF, unreacted are complete;
And then to described concentrated solution crystallisation by cooling, gained crystal is product DFF, remaining liq is the mother liquor be made up of raw material 5 hydroxymethyl furfural, the organic solvent do not removed completely and catalyzer that unreacted is complete;
C, by after described mother liquor and the mixing of described inorganic reaction residue, then add described phlegma, reconstitute catalyst system, for step a.
2. preparation method according to claim 1, is characterized in that:
The ratio of the quality of 5 hydroxymethyl furfural described in step a and described organic solvent volume is 20-300g/L; The amount of substance of described piperidines nitrogen oxide catalyst is the 1%-5% of described 5 hydroxymethyl furfural amount of substance; The amount of substance of described catalyst activator is the 1%-5% of 5 hydroxymethyl furfural amount of substance; The amount of substance of described alkali metal halide is the 1%-10% of described 5 hydroxymethyl furfural amount of substance.
3. preparation method according to claim 1 and 2, is characterized in that:
Described piperidines nitrogen oxide catalyst is tetramethyl piperidine oxynitride;
Described catalyst activator is iron nitrate;
Described organic solvent is one or more mixing in ethylene dichloride, methylene dichloride, ethyl acetate, toluene, dioxane, tetrahydrofuran (THF) or acetonitrile;
Described alkali metal halide is one or more mixing in sodium-chlor, Repone K, Sodium Bromide and Potassium Bromide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452193A (en) * | 2019-07-29 | 2019-11-15 | 中国科学技术大学 | The method that 2,5- furans dicarbaldehyde is prepared by 5 hydroxymethyl furfural |
| CN112778231A (en) * | 2021-01-29 | 2021-05-11 | 杭州凯方科技有限公司 | Novel synthesis method of 4-methylthiazole-5-formaldehyde |
| CN113480504A (en) * | 2021-06-08 | 2021-10-08 | 烟台联众化工原料有限公司 | Preparation method of hexafluoro dianhydride |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452193A (en) * | 2019-07-29 | 2019-11-15 | 中国科学技术大学 | The method that 2,5- furans dicarbaldehyde is prepared by 5 hydroxymethyl furfural |
| CN112778231A (en) * | 2021-01-29 | 2021-05-11 | 杭州凯方科技有限公司 | Novel synthesis method of 4-methylthiazole-5-formaldehyde |
| CN113480504A (en) * | 2021-06-08 | 2021-10-08 | 烟台联众化工原料有限公司 | Preparation method of hexafluoro dianhydride |
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