CN105461666A - Preparation method of 2-substituted tetrahydrofuran compounds - Google Patents
Preparation method of 2-substituted tetrahydrofuran compounds Download PDFInfo
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- CN105461666A CN105461666A CN201610008889.7A CN201610008889A CN105461666A CN 105461666 A CN105461666 A CN 105461666A CN 201610008889 A CN201610008889 A CN 201610008889A CN 105461666 A CN105461666 A CN 105461666A
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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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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Abstract
The invention discloses biomass 2-substituted tetrahydrofuran compounds and a preparation method thereof. Furfural (FAL) obtained through biomass hydrolysis is used as a raw material, acetal hydrogenation one-pot reaction occurs on a supported palladium catalyst under the condition that a micro-molecule alcohol compound serves as a solvent and a reaction simultaneously, 2-(diethoxy methyl) tetrahydrofuran, 2-(dimethoxy methyl) tetrahydrofuran, 2-(dipropoxy methyl) tetrahydrofuran and other 2-substituted tetrahydrofuran compounds are prepared in a one-step mode. The preparation method has the advantages that the reaction conditions are moderate, the raw material is cheap and easy to obtain, product selectivity is high, operation is simple and convenient, the efficiency is high and the like. The prepared 2-substituted tetrahydrofuran compounds have good stability and oil solubility and can serve as potential green biomass-based fuel oil or additives to be widely used.
Description
Technical field
The present invention relates to biofuel field, be specifically related to a kind of method taking furfural as raw material and prepare 2-substituted tetrahydrofuran class biofuel, and the application of the catalyzer adopted.
Background technology
Be that the Chemicals such as fine chemicals, fuel oil, additive are most important for solution current social energy starved stem reality by Wooden Biomass feedstock conversion.Furfural system acetal product is a kind of important furfuran compound, has the advantage such as high-energy-density, high-octane rating, is a kind of organism meeting petrol and diesel oil and aviation kerosene requirement.Document Catal.Today, 2014,234,233-236 reports in ethanolic soln, use H-USY-6 molecular sieve high-efficient ground that furfural (FAL) is converted into 2-furfural diethyl two acetal (FDA), room temperature lower 1 hour acetal productive rate is 79%.Owing to containing a unsaturated functional group furan nucleus in 2-furfural diethyl two acetal (FDA), if the furan nucleus hydrogenation in 2-furfural diethyl two acetal (FDA) to be generated tetrahydrofuran derivatives material 2-(diethoxymethyl) tetrahydrofuran (THF) (THFDA) replaced, both high molecular chemical stability can be put forward, high molecular H/C ratio can be put forward again, thus can greatly improve its energy density, make it to be more suitable for using as fuel or fuel dope.But because furan nucleus is stable aromatic nucleus, the difficulty be reduced is far longer than carbonyl, in prior art, rarely has the report about synthesis 2-(diethoxymethyl) tetrahydrofuran (THF) (THFDA) operational path.Patent CN103073526B provides a kind of 5 hydroxymethyl furfural and alcoholic solution of using and reacts generation 2, the complicated approach of the dibasic tetrahydrofurans mix products of 5-, the method realizes the conversion of 5 hydroxymethyl furfural to target product by heterogeneous catalyst for etherification and heterogeneous hydrogenation catalyst two-step approach; Use H-Beta zeolite and Pd/Al
2o
3as the first step reaction, Ni/Al
2o
3as second step catalysts, be 1.2min in air speed
-1reaction is 120 DEG C, after reacting 60min under hydrogen pressure 4MPa condition, feed stock conversion is 94%, target mixture product (2,5-two (ethoxyl methyl) tetrahydrofuran (THF), 5-ethoxyl methyl tetrahydrofuran (THF), 2-(diethoxymethyl)-5-ethoxyl methyl tetrahydrofuran (THF) and 5-(diethoxymethyl) tetrahydrofuran-2-methanol (accompanying drawing 1)) selectivity be 81%, but three kinds of products do not have specific selectivity.
In prior art, the technique of quickness and high efficiency ground preparation 2-substituted tetrahydrofuran compounds yet there are no patent and reported in literature.
Summary of the invention
In order to overcome the deficiency that above-mentioned prior art exists, the invention provides a kind of at relative mild conditions, namely at lower temperature and lower pressure, realizing by furfural (FAL) is raw material, under load type palladium catalyst catalysis, single stage method prepares described 2-substituted tetrahydrofuran compounds.Preparation method of the present invention has reaction conditions gentleness, and cheaper starting materials is easy to get, and selectivity of product is high, easy and simple to handle, efficiency advantages of higher; 2-substituted tetrahydrofuran compounds prepared by the present invention has good stability and oil soluble, can be used as potential green bio matter base fuel oil or additive and is widely used.
The present invention proposes a kind of preparation method of 2-substituted tetrahydrofuran compounds, take furfural as raw material, in low-carbon (LC) alcohol organic solvent, with load type palladium catalyst catalyzed reaction, be 10-80 DEG C in temperature of reaction, under the condition of hydrogen pressure 0.1-1MPa, there is acetal hydrogenation reaction, after 0.5-5 hour, obtain such as formula the 2-substituted tetrahydrofuran compounds shown in (3), described reaction process is as shown in reaction formula (I);
Wherein, R is saturated hydrocarbyl functional group, comprises methyl, ethyl, propyl group, sec.-propyl and butyl etc.; Preferably, R is methyl, ethyl.
Wherein, described 2-substituted tetrahydrofuran compounds comprises 2-(dimethoxy-methyl) tetrahydrofuran (THF), 2-(diethoxymethyl) tetrahydrofuran (THF), 2-(propoxy methyl) tetrahydrofuran (THF), 2-(dipropoxy methyl) tetrahydrofuran (THF), 2-(Dibutoxymethyl) tetrahydrofuran (THF).
Preparation method's reaction conditions of the present invention is gentle, and the selectivity of raw material is high, the advantage that reaction efficiency is high.Reaction mechanism of the present invention is, under hydroconversion condition, flash hydrogcnation is (as shown in Figure 2 on palladium catalyst for furan nucleus on reactant furfural (FAL), path a1), simultaneously there is rapidly aldolization (as shown in Figure 2 in aldehyde radical and alcoholic solvent on the carrier, path a2), by selecting described carrier realization metal-support interaction under certain condition and the acid intensity of modulation carrier surface, can realize hydrogenation synchronous with the speed of aldolization, thus a step generates 2-substituted tetrahydrofuran compounds.Instant invention overcomes the technical barrier about this compounds in prior art.One of difficult point, if furfural first obtains acetal (Fig. 2, path b1) in the reaction, product furfural acetal is highly stable, can not by hydrogenation., if hydrogenation reaction first occurs furfural obtain furfuryl alcohol (Fig. 2, path c1), then can not there is aldol reaction and obtain product of the present invention in difficult point two.
The present invention proposes a kind of preparation method of 2-substituted tetrahydrofuran compounds, take furfural as raw material, by liquid phase reaction, in organic solvent, under reductive agent existent condition, by molecular screen material catalyst, at 10-80 DEG C, under hydrogen pressure 0.1-1MPa condition, there is the plus hydrogenated reaction of acetal, after 0.5-5 hour, obtain described 2-substituted tetrahydrofuran compounds.
Wherein, described organic solvent is low-carbon (LC) alcohols, comprises one or more in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols; Preferably, described organic solvent is methyl alcohol or ethanol.Wherein, described organic solvent participates in reaction as reactant.
Wherein, described catalyzer accounts for the 1-20% of described furfural and organic solvent quality summation; Described catalyzer is load type palladium catalyst.
Described load type palladium catalyst accounts for the 1-20% of described furfural and organic solvent quality summation;
Described furfural accounts for the 1-20% of furfural and organic solvent quality summation.
The catalyzer that the present invention is used for directly preparing 2-substituted tetrahydrofuran compounds from hydrogenation of furfural is loaded catalyst, and its carrier is oxide material, comprises one or more in aluminum oxide, silicon oxide, titanium oxide and nickel oxide etc.; Preferably, described oxide material is aluminum oxide or silicon oxide.In described loaded catalyst, metal active centres is palladium.Particularly, in described loaded catalyst, on the carrier, palladium nano metal particles is uniformly dispersed the load of palladium nano metal particles, and size is 1-10nm (as shown in Figure 3).
In loaded catalyst of the present invention, the charge capacity of metal active centres is 1-10wt.%.
In the present invention, the preparation of load type palladium catalyst can adopt the deposition sedimentation method of reducing reported in prior art to be prepared by metal-salt and oxide material.
In the present invention, metal-salt can be one or more in muriate, nitrate or acetate or acetyl acetone complex; Particularly, metal-salt can be PdCl
2, Pd (NO
3)
2or Pd (Ac)
2.Preferably, metal-salt is PdCl
2.
In the present invention, described reductive agent can be one or more in sodium borohydride, hydrazine hydrate, formaldehyde or Trisodium Citrate; Preferably, reductive agent is sodium borohydride.
Wherein, preferably, described temperature of reaction is 20-50 DEG C.
Wherein, preferably, described reactive hydrogen atmospheric pressure is 0.1-0.5MPa.
The invention allows for a kind of load type palladium catalyst and preparation method thereof, on the carrier, in described load type palladium catalyst, palladium nano metal particles is dispersed to the load of palladium nano metal particles, and size of particles is between 1-10nm; The deposition sedimentation method of reducing that described load type palladium catalyst was reported by prior art obtains, and the preparation process of described deposition sedimentation method of reducing comprises: get appropriate PdCl
2solution adds Al
2o
3in the aqueous solution, after stirring, regulate pH to Pd
2+precipitation completely, adds filtration drying after sodium borohydride reduction, prepares load type palladium catalyst.In the present invention, carrier in the solution churning time, between 0.2-3 hour, preferably, is 1 hour; After adjust ph, solution continues to stir 0.2-3 hour, preferably, is 1 hour.
The invention allows for described catalyzer and prepare application in 2-substituted tetrahydrofuran compounds at catalysis furfural (FAL).Described application comprises, and is raw material with furfural, by liquid phase reaction, in organic solvent, under reductive agent existent condition, by described load type palladium catalyst catalysis, the plus hydrogenated reaction of a step acetal occurs, prepares described 2-substituted tetrahydrofuran compounds.
Beneficial effect of the present invention is: the preparation method of 2-substituted tetrahydrofuran compounds proposed by the invention can realize acetal and the hydrogenation reaction of furfural simultaneously by single stage method, decrease the generation of unsaturated lipid compounds.Raw material sources of the present invention are extensive, and operation is simple, is conducive to suitability for industrialized production.Gentle reaction conditions to reduce side reaction generation, reduce energy consumption and simplify reaction process there is great advantage.And the present invention adopts Common oxides material load type palladium as catalyzer, and catalytic activity is high, and product selectivity is high, the product 2-substituted tetrahydrofuran compounds obtained has huge application prospect in the field such as organic chemical industry or vehicle fuel.
Accompanying drawing explanation
Fig. 1 is several frequently seen tetrahydrofuran derivatives structural representation.
Fig. 2 is the path schematic diagram of furfural hydrogenation or aldolization in alcoholic solvent
Fig. 3 is Pd/Al
2o
3the transmission electron microscope picture of Pd particle on catalyzer.
Embodiment
In conjunction with following specific embodiment, the present invention is described in further detail.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content mentioned specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
The preparation of embodiment 1 load type palladium catalyst:
Get appropriate PdCl
2solution adds Al
2o
3in the aqueous solution, after stirring, regulate pH to Pd
2+precipitation completely, adds filtration drying after sodium borohydride reduction, prepares load type palladium catalyst.
When adopted oxide material is one or more in silicon oxide, titanium oxide and nickel oxide etc., also same technique effect can be reached
PdCl is adopted in the present embodiment
2, can also be Pd (NO
3)
2or Pd (Ac)
2, all can realize same effect.
Sodium borohydride is adopted to be reductive agent in the present embodiment.In the inventive method, reductive agent can also be hydrazine hydrate, formaldehyde or Trisodium Citrate, all can realize same effect.
Embodiment 2
The catalyzer using embodiment 1 to prepare carries out preparing 2-substituted tetrahydrofuran compounds by furfural (FAL) liquid-phase hydrogenatin, 50mg catalyzer is loaded in round-bottomed flask, add 5g0.2M furfural (FAL) ethanolic soln, temperature of reaction is 20 DEG C, react 1 hour under hydrogen balloon (0.1MPa) condition, furfuryl alcohol (FAL) transformation efficiency 100%, target product 2-(diethoxymethyl) tetrahydrofuran (THF) (THFDA) selectivity 89%.
When catalyzer adopts other oxide material as one or more in silicon oxide, titanium oxide and nickel oxide etc., also same technique effect can be reached.
When metal-salt is Pd (NO
3)
2or Pd (Ac)
2time, all can realize same effect.
Sodium borohydride is adopted to be reductive agent in the present embodiment.When reductive agent is hydrazine hydrate, formaldehyde or Trisodium Citrate, all same effect can be realized.
Embodiment 3
The catalyzer using embodiment 1 to prepare carries out preparing 2-substituted tetrahydrofuran compounds by furfural (FAL) liquid-phase hydrogenatin, 50mg catalyzer is loaded in autoclave, add 5g0.2M furfural (FAL) ethanolic soln, temperature of reaction is 20 DEG C, half hour is reacted under 0.5MPa condition, furfuryl alcohol (FAL) transformation efficiency 100%, target product 2-(diethoxymethyl) tetrahydrofuran (THF) (THFDA) selectivity 83%.
When catalyzer adopts other oxide material as one or more in silicon oxide, titanium oxide and nickel oxide etc., also same technique effect can be reached.
When metal-salt is Pd (NO
3)
2or Pd (Ac)
2time, all can realize same effect.
Sodium borohydride is adopted to be reductive agent in the present embodiment.When reductive agent is hydrazine hydrate, formaldehyde or Trisodium Citrate, all same effect can be realized.
Embodiment 4
The catalyzer using embodiment 1 to prepare carries out preparing 2-substituted tetrahydrofuran compounds by furfural (FAL) liquid-phase hydrogenatin, 50mg catalyzer is loaded in round-bottomed flask, add 5g0.2M furfural (FAL) ethanolic soln, temperature of reaction is 50 DEG C, react 1 hour under hydrogen balloon (0.1MPa) condition, furfuryl alcohol (FAL) transformation efficiency 100%, target product 2-(diethoxymethyl) tetrahydrofuran (THF) (THFDA) selectivity 88%.
When catalyzer adopts other oxide material as one or more in silicon oxide, titanium oxide and nickel oxide etc., also same technique effect can be reached.
When metal-salt is Pd (NO
3)
2or Pd (Ac)
2time, all can realize same effect.
Sodium borohydride is adopted to be reductive agent in the present embodiment.When reductive agent is hydrazine hydrate, formaldehyde or Trisodium Citrate, all same effect can be realized.
Embodiment 5
Silica supported palladium catalyst is used to carry out preparing 2-substituted tetrahydrofuran compounds by furfural (FAL) liquid-phase hydrogenatin, 50mg catalyzer is loaded in autoclave, add 5g0.2M furfural (FAL) ethanolic soln, temperature of reaction is 50 DEG C, react 1 hour under 0.5MPa condition, furfuryl alcohol (FAL) transformation efficiency 100%, target product 2-(diethoxymethyl) tetrahydrofuran (THF) (THFDA) selectivity 77%.
When catalyzer adopts other oxide material as one or more in silicon oxide, titanium oxide and nickel oxide etc., also same technique effect can be reached.
When metal-salt is Pd (NO
3)
2or Pd (Ac)
2time, all can realize same effect.
Sodium borohydride is adopted to be reductive agent in the present embodiment.When reductive agent is hydrazine hydrate, formaldehyde or Trisodium Citrate, all same effect can be realized.
Preparation method of the present invention, when organic solvent is methyl alcohol, propyl alcohol, butanols, Virahol, also can reach same technique effect.
Embodiment 6 ~ 9
Prepare other 2-substituted tetrahydrofuran compounds, reaction conditions and beneficial effect as shown in table 1 below:
Table 1
When catalyzer adopts other oxide material as one or more in silicon oxide, titanium oxide and nickel oxide etc., also same technique effect can be reached.
When metal-salt is Pd (NO
3)
2time, all can realize same effect.
Adopt sodium borohydride to be reductive agent in the present embodiment, when reductive agent is hydrazine hydrate, formaldehyde or Trisodium Citrate, all can realize same effect.
Above result shows, utilize catalyzer of the present invention to achieve at a lower temperature directly furfural (FAL) and prepare the object of 2-substituted tetrahydrofuran class organic product, and the advantages such as it is high to have feed stock conversion, and selectivity of product is high, non-environmental-pollution.
Protection content of the present invention is not limited to above embodiment.Under the spirit and scope not deviating from inventive concept, the change that those skilled in the art can expect and advantage are all included in the present invention, and are protection domain with appending claims.
Claims (9)
1. the preparation method of a 2-substituted tetrahydrofuran compounds, it is characterized in that, take furfural as raw material, in low-carbon (LC) alcohol organic solvent, with load type palladium catalyst catalyzed reaction, be 10-80 DEG C in temperature of reaction, hydrogen pressure is under the condition of 0.1-1MPa, acetal hydrogenation reaction occurs, after 0.5-5 hour, obtain such as formula the 2-substituted tetrahydrofuran compounds shown in (3), described reaction process is as shown in reaction formula (I);
Wherein,
R is saturated hydrocarbyl functional group, comprises methyl, ethyl, propyl group, sec.-propyl and butyl.
2. preparation method according to claim 1, is characterized in that, described low-carbon (LC) alcohol organic solvent participates in reaction as reactant.
3. preparation method according to claim 1, is characterized in that, described load type palladium catalyst accounts for the 1-20% of described furfural and organic solvent quality summation; Described furfural accounts for the 1-20% of furfural and organic solvent quality summation.
4. preparation method according to claim 1, is characterized in that, the carrier of described load type palladium catalyst is oxide material, for aluminum oxide, silicon oxide, titanium oxide, nickel oxide one or more; On the carrier, in dispersed, palladium nano metal particles size is between 1-10nm for the load of palladium nano metal particles.
5. preparation method according to claim 1, is characterized in that, described temperature of reaction is 10-80 DEG C, and reaction pressure is 0.1-1MPa.
6. preparation method according to claim 1, is characterized in that, the preparation method of described load type palladium catalyst is, utilizes reductive agent to be loaded on described carrier by water-soluble palladium metal-salt by deposition sedimentation method, obtains described load type palladium catalyst.
7. preparation method according to claim 6, is characterized in that, described metal-salt is one or more in muriate, nitrate or acetate or acetyl acetone complex.
8. preparation method according to claim 6, is characterized in that, described reductive agent is one or more in sodium borohydride, hydrazine hydrate, formaldehyde or Trisodium Citrate.
9. load type palladium catalyst prepares the application in 2-substituted tetrahydrofuran compounds at hydrogenation of furfural, it is characterized in that, the carrier of described load type palladium catalyst is oxide material, for aluminum oxide, silicon oxide, titanium oxide, nickel oxide one or more; On the carrier, in dispersed, palladium nano metal particles size is between 1-10nm for the load of palladium nano metal particles.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845402A (en) * | 2021-10-13 | 2021-12-28 | 中国科学院山西煤炭化学研究所 | Method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073526A (en) * | 2012-12-26 | 2013-05-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 2, 5-disubstituted tetrahydrofuran mixture |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103073526A (en) * | 2012-12-26 | 2013-05-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 2, 5-disubstituted tetrahydrofuran mixture |
Non-Patent Citations (3)
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|---|
| PERESADA, V. P.等: "Synthesis and pharmacological activity of some 2,5-dialkoxy-2-(dialkoxymethyl)tetrahydrofurans", 《KHIMIKO-FARMATSEVTICHESKII ZHURNAL》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845402A (en) * | 2021-10-13 | 2021-12-28 | 中国科学院山西煤炭化学研究所 | Method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds |
| CN113845402B (en) * | 2021-10-13 | 2024-02-06 | 中国科学院山西煤炭化学研究所 | Method for preparing 1, 4-butanediol and derivatives thereof from tetrahydrofuran compounds |
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