CN105130731A - Method for preparing long-chain alkane from biomass derivativeS 5-HMF (hydroxymethyl furfural) or furaldehyde - Google Patents
Method for preparing long-chain alkane from biomass derivativeS 5-HMF (hydroxymethyl furfural) or furaldehyde Download PDFInfo
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Abstract
The invention discloses a method for preparing long-chain alkane from biomass derivatives 5-HMF (hydroxymethyl furfural) or furaldehyde. According to the method, the biomass derivatives 5-HMF or furaldehyde are used as raw materials; a condensation product is formed after base catalysis and methyl ketone compound condensation; then, ketonic or alcoholic intermediates of tetrahydrofuran rings are obtained through hydrogenation catalysis; finally, the long-chain alkane is prepared through hydrogenation and ring opening dual catalysis preparation. The method has the advantages that the raw materials can be prepared from biological saccharides through hydrolysis and dehydration; the yield of the alkane is high; the consumption of catalysts is low; the reaction condition is mild; the process is clean and simple; in the reaction process of preparing the alkane from the condensation products, other operations and control are not needed except the program temperature rise; a new path for preparing the long-chain alkane from the biomass derivatives 5-HMF or furaldehyde by a one-pot method is opened up.
Description
One, technical field
The present invention relates to a kind of method being prepared long chain alkane by biomass derivatives 5-HMF or furfural.
Two, background technology
Along with the increase of global Energy Consumption total amount, fossil energy resource in short supply has become the very severe restraining factors of of global economic development.Biomass are a kind of clean renewable energy sources always, are that energy conversion and the chemosynthesis of raw material is significant for the Sustainable development of the energy and chemical industry with biomass.5 hydroxymethyl furfural (5-HMF) is the very important biomass-based plateform molecules of a class, it can be prepared by the gluconate dehydratase after fructose or isomerization, chemical property is more active, can, by multiple derivatives of reaction preparation such as oxidation, hydrogenation and condensations, be important fine chemical material.Furfural, also known as 2 furan carboxyaldehyde, is hydrolyzed generation pentose under the action of an acid by piperylene, formed by dehydration of pentoses cyclisation again, chemical property is active, can produce numerous derivatives, be widely used in the industry such as synthetic plastics, medicine, agricultural chemicals by reactions such as oxidation, condensations.
Being mainly contained by the technique of biomass-making for alkane of current report: (1) pyrolysis-microwave cracking-product purification: the method process is simple, but severe reaction conditions (high temperature) and product is very complicated; (2) condensation-hydrogenation-dehydration/hydrogenation: first the method uses biomass derivatives 5-HMF or furfural and methyl ketone compounds to carry out condensation, then to condensation product hydrogenation, prepares long chain alkane finally by dehydration/hydrogenation process.Used high-temperature and high-pressure conditions (~ 250 DEG C, ~ 5MPa) in the method, and selectivity of product is poor.
Three, summary of the invention
The present invention aims to provide a kind of by biomass derivatives 5-HMF (R
1=CH
2oH, R
2=Alkyl, R
3=CH
3) or furfural (R
1=H, R
2=Alkyl, R
3=H) prepare the method for long chain alkane.With biomass derivatives 5-HMF or furfural for raw material, condensation product is formed through base catalysis and methyl ketone compounds condensation, then obtained keto-acid or the alcohol of formula intermediate of tetrahydrofuran (THF) ring by hydrogenation catalyst, prepare long chain alkane finally by hydrogenation and the catalysis of open loop dual catalyst.The method has reaction conditions gentleness, simple to operate, long chain alkane selectivity advantages of higher.
The present invention prepares the method for long chain alkane by biomass derivatives 5-HMF or furfural, comprises the steps:
(1) under 10 ~ 100 DEG C and alkaline catalysts a condition, 5-HMF or furfural and methyl ketone compounds generation aldol condensation, obtain condensation product, described condensation product comprises methyl-5-hydroxymethylfurans vinyl ketone, methyl furan vinyl ketone, ethyl-5-hydroxymethylfurans vinyl ketone, ethyl furan vinyl ketone, isobutyl--5-hydroxymethylfurans vinyl ketone or isobutyl-furans vinyl ketone;
Described methyl ketone compounds comprises acetone, methyl ethyl ketone or methyl iso-butyl ketone (MIBK).
(2) condensation product is at 1.0 ~ 6.0MPa, under the effect of 10 ~ 150 DEG C and hydrogenation catalyst b, there is hydrogenation in the outer and ring of the ring of furan nucleus, generate the keto-acid containing tetrahydrofuran (THF) ring or alcohol of formula intermediate, comprise methyl-5-hydroxymethyl tetrahydrofuran ethyl ketone, methyltetrahydrofuran ethyl ketone, ethyl-5-hydroxymethyl tetrahydrofuran ethyl ketone, ethyltetrahydrofuran ethyl ketone, isobutyl--5-hydroxymethyl tetrahydrofuran ethyl ketone, isobutyl-tetrahydrofuran (THF) ethyl ketone, methyl-5-hydroxymethyl tetrahydrofuran ethyl carbinol, methyltetrahydrofuran ethyl carbinol, ethyl-5-hydroxymethyl tetrahydrofuran ethyl carbinol, ethyltetrahydrofuran ethyl carbinol, isobutyl--5-hydroxymethyl tetrahydrofuran ethyl carbinol or isobutyl-tetrahydrofuran (THF) ethyl carbinol,
(3) by the keto-acid that obtains or alcohol of formula intermediate 100 ~ 250 DEG C, under the effect of 1.0 ~ 10.0MPa, hydrogenation catalyst b and ring opening catalyst c dual catalyst, obtain long chain alkane via hydrogenation deoxidation process.
In such scheme, reactions steps (1) (2) (3) all carry out in batch reactor.
The present invention prepares the method for long chain alkane by biomass derivatives 5-HMF or furfural, and detailed process is as follows:
(1) be that the 5-HMF of 1:1 ~ 1:100 (preferred 1:20) or furfural and methyl ketone compounds drop into batch reactor by the ratio of amount of substance, in a solvent or under solvent-free condition, add 0.1 ~ 10% alkaline catalysts a (mass percent of relative 5-HMF or furfural, preferably 2%), in 10 ~ 100 DEG C (preferably 60 DEG C) reaction 10h, after separation, obtain condensation product;
Described solvent is the mixing of one or more in water, methyl alcohol, ethanol, tetrahydrofuran (THF), dioxane, ether.
(2) condensation product is dropped into batch reactor, at 1.0 ~ 6.0MPa hydrogen pressure, (molar weight of hydrogenation catalyst b is 1 ~ 20% of condensation product molar weight for 10 ~ 150 DEG C and hydrogenation catalyst b, preferably 5%) under effect, in solvent, 1 ~ 20h is reacted under room temperature, obtain mixture (the such as methyl-5-hydroxymethyl tetrahydrofuran ethyl ketone and methyl-5-hydroxymethyl tetrahydrofuran ethyl carbinol of keto-acid and alcohol of formula intermediate, methyltetrahydrofuran ethyl ketone and methyltetrahydrofuran ethyl carbinol, ethyl-5-hydroxymethyl tetrahydrofuran ethyl ketone and ethyl-5-hydroxymethyl tetrahydrofuran ethyl carbinol, ethyltetrahydrofuran ethyl ketone and ethyltetrahydrofuran ethyl carbinol, isobutyl--5-hydroxymethyl tetrahydrofuran ethyl ketone and isobutyl--5-hydroxymethyl tetrahydrofuran ethyl carbinol, isobutyl-tetrahydrofuran (THF) ethyl ketone and isobutyl-tetrahydrofuran (THF) ethyl carbinol), described solvent is selected from one or more in octane, normal hexane, hexanaphthene, n-nonane, Skellysolve A, normal heptane.
(3) the batch reactor condition after step (2) reaction being terminated is converted to 100 ~ 250 DEG C (preferably 180 DEG C), 1.0 ~ 10.0MPa (preferred 6.0MPa) hydrogen pressure, keto-acid obtained in direct use step (2) and the mixture of alcohol of formula intermediate react, and at hydrogenation catalyst b and ring opening catalyst c, (hydrogenation catalyst b is without the need to again adding; The molar weight of ring opening catalyst c is 1 ~ 20% of keto-acid and alcohol of formula intermediate mole total amount, preferably 2.5%), under the effect of dual catalyst, reaction 8 ~ 30h (preferred 24h), obtains target product.Wherein, ring opening catalyst c can add in advance in step (2), and it does not have any disadvantageous effect to the carrying out of step (2).
Described alkaline catalysts a comprises homogeneous catalyst, the aqueous solution of such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, ammoniacal liquor, sodium carbonate, salt of wormwood or pressed powder; Also heterogeneous catalyst is comprised, as basic oxide, oxyhydroxide.
Described one or more comprising in Pt, Pd, Ru, Rh, Ni, Co of hydrogenation catalyst b are carried on the catalyzer on solid carrier, as Pd/C, Pt/Al
2o
3, Ru/ZrO
2, Rh/Ce
2o
3, Ni/MgO, Co/C, Pd-Ru/C.
Described ring opening catalyst c comprises Hf (OTf)
4, Al (OTf)
3, Fe (OTf)
3, Sc (OTf)
3, Yb (OTf)
3, Sm (OTf)
3, Ce (OTf)
3, La (OTf)
3in the fluoroform sulphonate of one or more transition metal.
It is standby that the inventive method raw material can be hydrolyzed Dehydration by biological carbohydrate, alkane yield is high, catalyst levels is few, reaction conditions is gentle, technique is clean, simple, condensation product to be prepared in the reaction process of alkane except temperature programming without the need to other operation and is controlled, and opens one kettle way is prepared long chain alkane new way by biomass derivatives 5-HMF or furfural.
Four, accompanying drawing explanation
Fig. 1 is the HNMR spectrogram (CDCl of condensation product methyl-5-hydroxymethylfurans vinyl ketone in the embodiment of the present invention
3solvent);
Fig. 2 is the CNMR spectrogram (CDCl of condensation product methyl-5-hydroxymethylfurans vinyl ketone in the embodiment of the present invention
3solvent);
Fig. 3 is the HNMR spectrogram (CDCl of keto-acid intermediate methyl-5-hydroxymethyl tetrahydrofuran ethyl ketone in the embodiment of the present invention
3solvent);
Fig. 4 is the CNMR spectrogram (CDCl of keto-acid intermediate methyl-5-hydroxymethyl tetrahydrofuran ethyl ketone in the embodiment of the present invention
3solvent);
Fig. 5 is the HNMR spectrogram (CDCl of alcohol of formula intermediate methyl-5-hydroxymethyl tetrahydrofuran ethyl carbinol in the embodiment of the present invention
3solvent);
Fig. 6 is the CNMR spectrogram (CDCl of alcohol of formula intermediate methyl-5-hydroxymethyl tetrahydrofuran ethyl carbinol in the embodiment of the present invention
3solvent).
Five, embodiment
Embodiment of the present invention provides a kind of method being prepared long chain alkane by biomass derivatives 5-HMF or furfural.Biomass derivatives 5-HMF or furfural is utilized to be raw material, condensation product is formed through base catalysis and methyl ketone compounds condensation, then obtained keto-acid or the alcohol of formula intermediate of tetrahydrofuran (THF) ring by hydrogenation catalyst, prepare long chain alkane finally by hydrogenation and the catalysis of open loop dual catalyst.Below in conjunction with specific embodiment, the invention process process is described further.The following stated is only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto.
Embodiment 1: the preparation of condensation product methyl-5-hydroxymethylfurans vinyl ketone
Added by 10g5-HMF in 500mL round-bottomed flask, then add 150mL acetone wherein, stirring at room temperature is dissolved.After 5-HMF dissolves completely, in flask, add 100mg solid NaOH powder, stirring at room temperature 10h; After reaction terminates, filter, anhydrous magnesium sulfate drying spends the night, after again filtering, be spin-dried for by liquid, acetic acid ethyl dissolution mixes sample, and (elutriant is sherwood oil to column chromatography for separation: ethyl acetate=1:1, volume ratio), obtain 8.3g condensation product methyl-5-hydroxymethylfurans vinyl ketone (NMR is shown in Fig. 1,2).
Embodiment 2: the preparation of condensation product methyl furan vinyl ketone
Added by 10g furfural in 500mL round-bottomed flask, then add 150mL acetone wherein, stirring at room temperature is even.Then in flask, 200mgMgO powder is added, stirring at room temperature 20h; After reaction terminates, filter, anhydrous magnesium sulfate drying spends the night, after again filtering, be spin-dried for by liquid, acetic acid ethyl dissolution mixes sample, column chromatography for separation (elutriant is sherwood oil: ethyl acetate=1:1, volume ratio), obtains 7.2g condensation product methyl furan vinyl ketone.
Embodiment 3: the preparation of condensation product isobutyl--5-hydroxymethylfurans vinyl ketone
Added by 10g5-HMF in 500mL round-bottomed flask, then add 100mL methyl iso-butyl ketone (MIBK) wherein, stirring at room temperature is dissolved.After 5-HMF dissolves completely, in flask, add 200mgAl
2o
3powder, stirring at room temperature 20h; After reaction terminates, filter, anhydrous magnesium sulfate drying spends the night, after again filtering, be spin-dried for by liquid, acetic acid ethyl dissolution mixes sample, column chromatography for separation (elutriant is sherwood oil: ethyl acetate=1:1, volume ratio), obtains 7.5g condensation product isobutyl--5-hydroxymethylfurans vinyl ketone.
Embodiment 4: the preparation of condensation product isobutyl-furans vinyl ketone
Added by 10g furfural in 500mL round-bottomed flask, then add 100mL methyl iso-butyl ketone (MIBK) wherein, stirring at room temperature is even.Then in flask, 200mgZrO is added
2powder, stirring at room temperature 10h; After reaction terminates, filter, anhydrous magnesium sulfate drying spends the night, after again filtering, be spin-dried for by liquid, acetic acid ethyl dissolution mixes sample, column chromatography for separation (elutriant is sherwood oil: ethyl acetate=1:1, volume ratio), obtains 8.5g condensation product isobutyl-furans vinyl ketone.
Embodiment 5: the preparation of keto-acid intermediate methyl-5-hydroxymethyl tetrahydrofuran ethyl ketone
2g condensation product methyl-5-hydroxymethylfurans vinyl ketone, 200mgPd/C are thrown in 100mL batch reactor, adds 50mL methyl alcohol and stir, under 5MPa hydrogen pressure, room temperature condition, react 0.5h; Reaction terminates rear filtration, be spin-dried for by liquid, acetic acid ethyl dissolution mixes sample, and (elutriant is sherwood oil to column chromatography for separation: ethyl acetate=1:1, volume ratio), obtain 1.6g keto-acid intermediate methyl-5-hydroxymethyl tetrahydrofuran ethyl ketone (NMR is shown in Fig. 3,4).
Embodiment 6: the preparation of keto-acid intermediate isobutyl-tetrahydrofuran (THF) ethyl ketone
By 2g condensation product isobutyl-furans vinyl ketone, 200mgPt/Al
2o
3throw in 100mL batch reactor, add 50mL ethanol and stir, under 5MPa hydrogen pressure, room temperature condition, react 0.5h; Reaction terminates rear filtration, and be spin-dried for by liquid, acetic acid ethyl dissolution mixes sample, column chromatography for separation (elutriant is sherwood oil: ethyl acetate=1:1, volume ratio), obtains 1.4g keto-acid intermediate isobutyl-tetrahydrofuran (THF) ethyl ketone.
Embodiment 7: the preparation of keto-acid intermediate isobutyl--5-hydroxymethyl tetrahydrofuran ethyl ketone
2g condensation product isobutyl--5-hydroxymethylfurans vinyl ketone, 200mgRu/MgO are thrown in 100mL batch reactor, adds 50mL tetrahydrofuran (THF) and stir, under 5MPa hydrogen pressure, room temperature condition, react 0.5h; Reaction terminates rear filtration, and be spin-dried for by liquid, acetic acid ethyl dissolution mixes sample, column chromatography for separation (elutriant is sherwood oil: ethyl acetate=1:1, volume ratio), obtains 1.5g keto-acid intermediate isobutyl--5-hydroxymethyl tetrahydrofuran ethyl ketone.
Embodiment 8: the preparation of keto-acid intermediate methyltetrahydrofuran ethyl ketone
By 2g condensation product methyl furan vinyl ketone, 200mgRh/ZrO
2throw in 100mL batch reactor, add 50mL dioxane and stir, under 5MPa hydrogen pressure, room temperature condition, react 0.5h; Reaction terminates rear filtration, and be spin-dried for by liquid, acetic acid ethyl dissolution mixes sample, column chromatography for separation (elutriant is sherwood oil: ethyl acetate=1:1, volume ratio), obtains 1.4g keto-acid intermediate methyltetrahydrofuran ethyl ketone.
Embodiment 9: the preparation of alcohol of formula intermediate methyl-5-hydroxymethyl tetrahydrofuran ethyl carbinol
By 2g condensation product methyl-5-hydroxymethylfurans vinyl ketone, 200mgPd/Al
2o
3throw in 100mL batch reactor, add 50mL methyl alcohol and stir, under 5MPa hydrogen pressure, room temperature condition, react 0.5h; Reaction terminates rear filtration, filtrate is proceeded in 250mL round-bottomed flask, under the condition of ice-water bath, in filtrate, slowly adds 4.0gNaBH
4, then stirring at room temperature 1h; In flask, add 100mL pure water dilute, then use 0.5mol/L sulphuric acid soln adjust pH to neutral, dichloromethane extraction (6 × 50mL), organic phase anhydrous magnesium sulfate drying spends the night.Organic phase is filtered and is spin-dried for, acetic acid ethyl dissolution mixes sample, then column chromatography for separation (elutriant is sherwood oil: ethyl acetate=1:1, volume ratio), obtains 1.4g alcohol of formula intermediate methyl-5-hydroxymethyl tetrahydrofuran ethyl carbinol (NMR is shown in Fig. 5,6).
Embodiment 10: the preparation of alcohol of formula intermediate isobutyl--5-hydroxymethyl tetrahydrofuran ethyl carbinol
2g condensation product isobutyl--5-hydroxymethylfurans vinyl ketone, 200mgNi/C are thrown in 100mL batch reactor, adds 50mL ethanol and stir, under 5MPa hydrogen pressure, room temperature condition, react 1h; Reaction terminates rear filtration, filtrate is proceeded in 250mL round-bottomed flask, under the condition of ice-water bath, in filtrate, slowly adds 4.0gNaBH
4, then stirring at room temperature 1h; In flask, add 100mL pure water dilute, then use 0.5mol/L sulphuric acid soln adjust pH to neutral, dichloromethane extraction (6 × 50mL), organic phase anhydrous magnesium sulfate drying spends the night.Organic phase filtered and be spin-dried for, acetic acid ethyl dissolution mixes sample, then column chromatography for separation (elutriant is sherwood oil: ethyl acetate=1:1, volume ratio), obtains 1.0g alcohol of formula intermediate isobutyl--5-hydroxymethyl tetrahydrofuran ethyl carbinol.
Embodiment 11: the preparation of alcohol of formula intermediate methyltetrahydrofuran ethyl carbinol
2g condensation product methyl furan vinyl ketone, 200mgCo/MgO are thrown in 100mL batch reactor, adds 50mL tetrahydrofuran (THF) and stir, under 5MPa hydrogen pressure, room temperature condition, react 2h; Reaction terminates rear filtration, filtrate is proceeded in 250mL round-bottomed flask, under the condition of ice-water bath, in filtrate, slowly adds 4.0gNaBH
4, then stirring at room temperature 1h; In flask, add 100mL pure water dilute, then use 0.5mol/L sulphuric acid soln adjust pH to neutral, dichloromethane extraction (6 × 50mL), organic phase anhydrous magnesium sulfate drying spends the night.Organic phase filtered and be spin-dried for, acetic acid ethyl dissolution mixes sample, then column chromatography for separation (elutriant is sherwood oil: ethyl acetate=1:1, volume ratio), obtains 0.9g alcohol of formula intermediate methyltetrahydrofuran ethyl carbinol.
Embodiment 12: the preparation of alcohol of formula intermediate isobutyl-tetrahydrofuran (THF) ethyl carbinol
By 2g condensation product isobutyl-furans vinyl ketone, 200mgPd-Ru/Ce
2o
3throw in 100mL batch reactor, add 50mL dioxane and stir, under 5MPa hydrogen pressure, room temperature condition, react 0.5h; Reaction terminates rear filtration, filtrate is proceeded in 250mL round-bottomed flask, under the condition of ice-water bath, in filtrate, slowly adds 4.0gNaBH
4, then stirring at room temperature 1h; In flask, add 100mL pure water dilute, then use 0.5mol/L sulphuric acid soln adjust pH to neutral, dichloromethane extraction (6 × 50mL), organic phase anhydrous magnesium sulfate drying spends the night.Organic phase filtered and be spin-dried for, acetic acid ethyl dissolution mixes sample, then column chromatography for separation (elutriant is sherwood oil: ethyl acetate=1:1, volume ratio), obtains 1.3g alcohol of formula intermediate isobutyl-tetrahydrofuran (THF) ethyl carbinol.
Embodiment 13: the preparation of n-nonane
By methyl-5-hydroxymethylfurans vinyl ketone (2mmol), Hf (OTf)
4(0.05mmol), Pd/C (0.1mmolPd) throws in 30mL tank reactor, add 10mL solvent octane, and reactor is charged to 5MPa hydrogen pressure, and carry out reacting (60 DEG C of reaction 16h are warming up to 180 DEG C of reaction 24h subsequently) under the heating schedule set; Be cooled to room temperature after reaction, add 10mL ethyl acetate and interior mark dodecane, vapor detection nonane yield reaches 92%.
Concrete testing conditions is as follows: gas phase instrument: GC-FID, ShimadzuGC-2014; Capillary column: Rtx-5 (30m × 0.32mm × 0.25 μm).
Embodiment 14: the preparation of octane
By methyl furan vinyl ketone (2mmol), Al (OTf)
3(0.05mmol), Ru/Al
2o
3(0.1mmolRu) throw in 30mL tank reactor, add 10mL solvent hexane, and reactor is charged to 4MPa hydrogen pressure, and carry out reacting (60 DEG C of reaction 20h are warming up to 180 DEG C of reaction 24h subsequently) under the heating schedule set; Be cooled to room temperature after reaction, add 10mL ethyl acetate and interior mark dodecane, vapor detection octane yield reaches 90%.
The preparation of embodiment 15:2-methyldecane
By isobutyl-furans vinyl ketone (2mmol), Fe (OTf)
3(0.05mmol), Rh/ZrO
2(0.1mmolRh) throw in 30mL tank reactor, add 10mL solvent hexanaphthene, and reactor is charged to 6MPa hydrogen pressure, and carry out reacting (60 DEG C of reaction 12h are warming up to 180 DEG C of reaction 20h subsequently) under the heating schedule set; Be cooled to room temperature after reaction, add 10mL ethyl acetate and interior mark dodecane, vapor detection 2-methyldecane yield reaches 87%.
The preparation of embodiment 16:2-methylundecane
By isobutyl--5-hydroxymethylfurans vinyl ketone (2mmol), Sc (OTf)
3(0.05mmol), Pt/Ce
2o
3(0.1mmolPt) throw in 30mL tank reactor, add 10mL solvent n-nonane, and reactor is charged to 3MPa hydrogen pressure, and carry out reacting (60 DEG C of reaction 20h are warming up to 180 DEG C of reaction 30h subsequently) under the heating schedule set; Be cooled to room temperature after reaction, add 10mL ethyl acetate and interior mark dodecane, vapor detection 2-methylundecane yield reaches 75%.
In sum, the invention provides a kind of method being prepared long chain alkane by biomass derivatives 5-HMF or furfural.Biomass derivatives 5-HMF or furfural is utilized to be raw material, condensation product is formed through base catalysis and methyl ketone compounds condensation, then obtained keto-acid or the alcohol of formula intermediate of tetrahydrofuran (THF) ring by hydrogenation catalyst, prepare long chain alkane finally by hydrogenation and the catalysis of open loop dual catalyst.The method has reaction conditions gentleness, simple to operate, long chain alkane selectivity advantages of higher, provides a kind of new way preparing long chain alkane.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; also not because the succession between each embodiment causes any restriction to the present invention; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (10)
1. prepared the method for long chain alkane by biomass derivatives 5-HMF or furfural for one kind, it is characterized in that: with biomass derivatives 5-HMF or furfural for raw material, condensation product is formed through base catalysis and methyl ketone compounds condensation, then obtained keto-acid or the alcohol of formula intermediate of tetrahydrofuran (THF) ring by hydrogenation catalyst, prepare long chain alkane finally by hydrogenation and the two catalysis of open loop.
2. method according to claim 1, is characterized in that comprising the steps:
(1) under 10 ~ 100 DEG C and alkaline catalysts a condition, 5-HMF or furfural and methyl ketone compounds generation aldol condensation, obtain condensation product; Described methyl ketone compounds comprises acetone, methyl ethyl ketone or methyl iso-butyl ketone (MIBK);
(2) condensation product is under the effect of 1.0 ~ 6.0MPa, 10 ~ 150 DEG C and hydrogenation catalyst b, hydrogenation in the outer and ring of the ring of furan nucleus occurs, generates the keto-acid containing tetrahydrofuran (THF) ring and alcohol of formula intermediate;
(3) by the keto-acid that obtains and alcohol of formula intermediate 100 ~ 250 DEG C, under the effect of 1.0 ~ 10.0MPa, hydrogenation catalyst b and ring opening catalyst c dual catalyst, obtain long chain alkane via hydrogenation deoxidation process.
3. method according to claim 2, is characterized in that comprising the steps:
(1) be that the 5-HMF of 1:1 ~ 1:100 or furfural and methyl ketone compounds drop into batch reactor by the ratio of amount of substance, in a solvent or under solvent-free condition, add the alkaline catalysts a of 5-HMF or furfural quality 0.1 ~ 10%, in 10 ~ 100 DEG C of reaction 10h, after separation, obtain condensation product; Described solvent is one or more in water, methyl alcohol, ethanol, tetrahydrofuran (THF), dioxane, ether;
(2) condensation product is dropped into batch reactor, under the effect of 1.0 ~ 6.0MPa hydrogen pressure, 10 ~ 150 DEG C and hydrogenation catalyst b, in solvent, react 1 ~ 20h under room temperature, obtain the mixture of keto-acid and alcohol of formula intermediate; Described solvent is selected from one or more in octane, normal hexane, hexanaphthene, n-nonane, Skellysolve A, normal heptane;
(3) the batch reactor condition after step (2) reaction being terminated is converted to 100 ~ 250 DEG C, 1.0 ~ 10.0MPa hydrogen pressure, keto-acid obtained in direct use step (2) and the mixture of alcohol of formula intermediate react, under the effect of hydrogenation catalyst b and ring opening catalyst c dual catalyst, reaction 8 ~ 30h, obtains target product.
4. method according to claim 3, is characterized in that comprising the steps:
(1) be that the 5-HMF of 1:20 or furfural and methyl ketone compounds drop into batch reactor by the ratio of amount of substance, in a solvent or under solvent-free condition, add the alkaline catalysts a of 5-HMF or furfural quality 2%, in 60 DEG C of reaction 10h, after separation, obtain condensation product;
(2) condensation product is dropped into batch reactor, under the effect of 1.0 ~ 6.0MPa hydrogen pressure, 10 ~ 150 DEG C and hydrogenation catalyst b, in solvent, react 1 ~ 20h under room temperature, obtain the mixture of keto-acid and alcohol of formula intermediate;
(3) the batch reactor condition after step (2) reaction being terminated is converted to 180 DEG C, 6.0MPa hydrogen pressure, keto-acid obtained in direct use step (2) and the mixture of alcohol of formula intermediate react, under the effect of hydrogenation catalyst b and ring opening catalyst c dual catalyst, reaction 24h, obtains target product.
5. the method according to claim 2,3 or 4, is characterized in that:
Described alkaline catalysts a comprises homogeneous catalyst or heterogeneous catalyst.
6. method according to claim 5, is characterized in that:
Described homogeneous catalyst comprises sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, ammoniacal liquor, sodium carbonate or salt of wormwood; Described heterogeneous catalyst comprises basic oxide, oxyhydroxide.
7. the method according to claim 2,3 or 4, is characterized in that:
Described one or more comprising in Pt, Pd, Ru, Rh, Ni, Co of hydrogenation catalyst b are carried on the catalyzer on solid carrier; The molar weight that in step (2), hydrogenation catalyst b adds is the 1-20% of condensation product molar weight.
8. method according to claim 7, is characterized in that:
The molar weight that in step (2), hydrogenation catalyst b adds is 5% of condensation product molar weight.
9. the method according to claim 2,3 or 4, is characterized in that:
Described ring opening catalyst c comprises Hf (OTf)
4, Al (OTf)
3, Fe (OTf)
3, Sc (OTf)
3, Yb (OTf)
3, Sm (OTf)
3, Ce (OTf)
3, La (OTf)
3in one or more; The molar weight that in step (3), ring opening catalyst c adds is the 1-20% of keto-acid and alcohol of formula intermediate mole total amount.
10. method according to claim 7, is characterized in that:
The molar weight that in step (3), ring opening catalyst c adds is 2.5% of keto-acid and alcohol of formula intermediate mole total amount.
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| CN107445819A (en) * | 2017-08-31 | 2017-12-08 | 合肥利夫生物科技有限公司 | A kind of preparation method of n-capric acid |
| CN107602372A (en) * | 2017-08-31 | 2018-01-19 | 中国科学技术大学 | The method for preparing aliphatic acid |
| CN108409560A (en) * | 2018-04-11 | 2018-08-17 | 合肥利夫生物科技有限公司 | A kind of preparation method of 1,13- tridecane diols ester and its 1,13- tridecane diols |
| CN108484394A (en) * | 2018-04-11 | 2018-09-04 | 合肥利夫生物科技有限公司 | A kind of preparation method of n-octyl alcohol ester and its n-octyl alcohol |
| CN109486535A (en) * | 2017-09-15 | 2019-03-19 | 华东理工大学 | A method of high-quality fuel is prepared by biomass derivatives |
| CN111040802A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Method and device for preparing long-chain alkane from sugar platform compound |
| CN111040801A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Method and device for processing intermediate product of sugar platform compound for preparing long-chain alkane |
| CN111040800A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Method and device for processing intermediate product of sugar platform compound for preparing long-chain alkane |
| CN111470927A (en) * | 2020-04-15 | 2020-07-31 | 华东师范大学 | Method for preparing high-melting-point wax from furfural |
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| CN107602372A (en) * | 2017-08-31 | 2018-01-19 | 中国科学技术大学 | The method for preparing aliphatic acid |
| CN107602372B (en) * | 2017-08-31 | 2020-08-25 | 中国科学技术大学 | Process for producing fatty acid |
| CN107445819A (en) * | 2017-08-31 | 2017-12-08 | 合肥利夫生物科技有限公司 | A kind of preparation method of n-capric acid |
| CN109486535A (en) * | 2017-09-15 | 2019-03-19 | 华东理工大学 | A method of high-quality fuel is prepared by biomass derivatives |
| CN108484394A (en) * | 2018-04-11 | 2018-09-04 | 合肥利夫生物科技有限公司 | A kind of preparation method of n-octyl alcohol ester and its n-octyl alcohol |
| CN108409560A (en) * | 2018-04-11 | 2018-08-17 | 合肥利夫生物科技有限公司 | A kind of preparation method of 1,13- tridecane diols ester and its 1,13- tridecane diols |
| CN111040802A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Method and device for preparing long-chain alkane from sugar platform compound |
| CN111040801A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Method and device for processing intermediate product of sugar platform compound for preparing long-chain alkane |
| CN111040800A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Method and device for processing intermediate product of sugar platform compound for preparing long-chain alkane |
| CN111040801B (en) * | 2018-10-15 | 2021-12-17 | 中国石油化工股份有限公司 | Method and device for processing intermediate product of sugar platform compound for preparing long-chain alkane |
| CN111040802B (en) * | 2018-10-15 | 2022-04-08 | 中国石油化工股份有限公司 | Method and device for preparing long-chain alkane from sugar platform compound |
| CN111470927A (en) * | 2020-04-15 | 2020-07-31 | 华东师范大学 | Method for preparing high-melting-point wax from furfural |
| CN111470927B (en) * | 2020-04-15 | 2022-12-30 | 华东师范大学 | Method for preparing high-melting-point wax from furfural |
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