CN109867642A - A kind of method that boehmite efficient catalytic cellulose prepares 5 hydroxymethyl furfural - Google Patents
A kind of method that boehmite efficient catalytic cellulose prepares 5 hydroxymethyl furfural Download PDFInfo
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Abstract
The invention discloses a kind of methods that boehmite efficient catalytic cellulose prepares 5 hydroxymethyl furfural, specifically boehmite and cellulose are added in the mixed system of ionic liquid, dimethyl sulfoxide and a small amount of water, it is transferred in Conventional glass reactor after mixing evenly, it is stirred to react under the conditions of 120 ~ 210 DEG C, deionized water is added into reaction solution after reaction to be quenched, centrifugation collects supernatant liquid to get the degradation solution comprising 5 hydroxymethyl furfural is arrived.When producing 5 hydroxymethyl furfural using method catalytic cellulose of the invention, have the characteristics that efficient catalytic (5 hydroxymethyl furfural yield and selectivity high), catalyst it is easily separated it is reusable, easy to operate and cost is relatively low (equipment is simple, catalyst and reaction are can be recycled), it can avoid a large amount of side reactions to generate, improve selectivity of product, product separation costs are reduced, there is high application value.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of boehmite efficient catalytic cellulose preparation 5- hydroxyl first
The method of base furfural.
Background technique
As petroleum resources are increasingly depleted and its demand of the people to chemical products, environmentally safe and sustainable development
It is required that continuous improvement, how using reproducible, recyclable and clean living resources to produce biomass platform chemicals
To mitigate or reduce the dependence of people's fossil energy, environment is protected, is the problem of becoming increasingly conspicuous at present.With other biomass platforms
Compound is compared, and 5 hydroxymethyl furfural (HMF) is considered as a kind of platform chemicals with preferable development prospect, has synthesis
The ability of a variety of fine chemicals, medical presoma, bio-fuel, high-performance polymer, such as 2,5- diformyl furans
(DFF), 2,5- furan dicarboxylic acid (FDA), 2,5- dihydroxymethyl furans (BHMF), 2,5- dimethyl furan (DMF), levulic acid
(LA) etc., the value with highly important research and industrial application, is the hot spot studied at present.With it is edible, price compared with
High monosaccharide compares such as glucose, and fructose, xylose, cellulose is with non-consumption, and from a wealth of sources, lower-price characteristic is
Prepare the more ideal raw material of HMF.But since cellulose is to pass through β-Isosorbide-5-Nitrae glycosidic bond and intermolecular by glucose unit
There is the closelypacked high-molecular compound being chained up with intramolecular hydrogen bond high-crystallinity, low solubility (water and common to have
Solvent) and it is difficult to degrade the features such as, therefore at present efficient degradation cellulose produce the difficult of HMF, there are many technologies
Problem has larger challenge.
Current study show that acidic catalyst, including homogeneous and heterogeneous phase, be conducive to catalytic cellulose degradation.But with
Homogeneous catalyst is compared, and heterogeneous catalysis has catalyst easily recycles, product is easily separated, corrosivity is small, easy realization industrializes etc.
Advantage is considered the more ideal method for producing HMF, and development trend and research hotspot at present.Recent decades, it is countless non-equal
Phase catalyst is developed and is applied to cellulose degradation and produced in the research of HMF, such as metal oxide, zeolite molecular sieve, sulfonation
Carbon based material, dopant material, multifunctional polymer, fused salt, metal organic framework compound, resin etc..Due to metal oxide
Necessary acidic site and cheap and easy to get can be provided, therefore, metal oxide is current most study, also most extensively and most
There is a kind of heterogeneous catalysis of industrial application future, is current research hotspot and direction.Aluminium oxide is one of common gold
Belong to oxide, and since its is cheap, obtain aspect, is catalyzed carbohydrate (Portugal frequently as catalyst or catalytic carrier
Grape sugar, fructose, polysaccharide) produce HMF.For example, Sampath (Appl. Catal. A-Gen. 2017;533:75-80) with
Aluminium oxide is catalyst, is aided with a small amount of copper chloride, in dimethyl sulfoxide (DMSO) reaction system, reacts 3h at 130 DEG C, urges
Change glucose and obtains 56% HMF yield.Garc í a-Sanchoa(Appl. Catal. B-Environ. 2017;206:
617-625；Appl. Catal. B-Environ. 2014;152: 1-10) investigation is using aluminium oxide as catalyst or catalysis
Agent carrier is catalyzed the case where Dextrose production HMF, again shows that aluminium oxide is a kind of with sugar such as good catalysis glucose, fructose
Hydrate produces the catalyst of HMF ability.But the hydrothermally stable of aluminium oxide is poor, in 150 DEG C of hot water, will be slow
Ground is converted into its presoma boehmite (γ-AlOOH).Simultaneously as HMF is to be dehydrated to produce by fructose, and therefore, carbon aquation
Closing during object produces HMF necessarily has water to participate in.And during producing HMF for cellulose degradation, remove the above process
Outside the water of generation, since cellulose degradation first is hydrolysis, also need to add additional water.Meanwhile most of fibres
The temperature for tieing up plain degradation reaction is both greater than 150 DEG C, therefore the poor hydrothermal stability of aluminium oxide certainly will influence its catalytic
Can, lower catalytic stability.It is based on the consideration of this viewpoint, Takagaki(RSC Adv. 2014:43785-43791) benefit
It is directly catalyzed Dextrose production HMF in water phase with the presoma boehmite (γ-AlOOH) of aluminium oxide, obtains about 18%HMF
Yield illustrates that γ-AlOOH has the ability that the carbohydrate such as catalysis glucose, fructose produce HMF.But currently, with regard to us
Known, no γ-AlOOH catalytic cellulose produces the report of HMF.Simultaneously and at present with the catalysis of cellulose catalytic performance
Agent is compared, if sulfonation carbon based material, dopant material, multifunctional polymer, metal organic framework compound, resin are compared, γ-
AlOOH prepares simple, cheap, acquisition conveniently, is the catalyst that more ideal HMF is produced.
Reaction dissolvent selection is to influence cellulose to produce another key factor of HMF.Since cellulose is closely pushed
High-molecular compound is insoluble in common organic solvents and water.Therefore, how effectively to dissolve cellulose, promote cellulose and it is non-
Phase catalyst effectively contacts, and is to improve one of cellulose degradation efficiency key factor.(ethyl alcohol, third compared with other common solvents
Ketone), ionic liquid has stronger cellulolytic capabilities, can effectively be dissolved in ionic liquid in 120 DEG C or more celluloses.
Although current ionic liquid price is higher, ionic liquid stability is strong, can be real by simple distillation, ion exchange, extraction
Existing ionic liquid is recycled, or reduces its use ratio by the way that other common agents are added, to reduce cost.Therefore, from
Sub- liquid is still one of ideal response solvent of current degraded cellulose.
Therefore, the invention discloses the methods that a kind of boehmite (γ-AlOOH) efficient catalytic cellulose produces HMF.
Summary of the invention
With glucose, fructose, xylose etc. is edible, and the higher monosaccharide of price is compared, and cellulose has non-consumption, comes
Source is extensive, lower-price characteristic, is the more ideal raw material for preparing HMF.But since cellulose is by glucose unit
The closelypacked high-molecular compound being chained up by β-Isosorbide-5-Nitrae glycosidic bond and intermolecular hydrogen bonding has high-crystallinity, low molten
Xie Du (water and common organic solvents) and it is difficult to degrade the features such as, therefore at present efficient degradation cellulose produce the difficult of HMF,
There are many technical problems, have larger challenge.Present invention aim to address common oxidized Al catalysts hydrothermal stabilities
Not strong and other complicated close of heterogeneous catalysis preparation are not suitable for the problem of producing HMF on a large scale, and it is high to provide a kind of boehmite
The method that effect catalytic cellulose prepares HMF, the catalyst boehmite property that this method uses are stablized, and raw material is cheap and easy to get, urges
Change high-efficient.
In order to achieve the above-mentioned object of the invention, the invention adopts the following technical scheme:
A kind of method that boehmite efficient catalytic cellulose prepares 5 hydroxymethyl furfural: boehmite and cellulose are added to
It in the mixed system of ionic liquid, dimethyl sulfoxide and water, is transferred in reactor after mixing evenly, under the conditions of 120 ~ 210 DEG C
It is stirred to react, deionized water is added into reaction solution after reaction and is quenched, is centrifuged, collects supernatant liquid, obtains
Degradation solution comprising 5 hydroxymethyl furfural.
Further, the method for 5 hydroxymethyl furfural is prepared are as follows: ionic liquid and dimethyl sulfoxide is first added in cellulose
Mixed solution in, stir to cellulose dissolution, add boehmite and deionized water, proceed to reactor after mixing evenly
In, it is stirred to react under the conditions of 120 ~ 210 DEG C, deionized water is added into reaction solution after reaction and is quenched, from
The heart collects supernatant liquid, obtains the degradation solution comprising 5 hydroxymethyl furfural.
Further, the mass ratio of boehmite and cellulose is 0.05:1 ~ 5:1, preferably 1:1.
Further, the mass ratio of cellulose and mixed system (ionic liquid, dimethyl sulfoxide and water) is 1:10 ~ 1:
100, preferably 1:60.
Further, the mass ratio of mixed system intermediate ion liquid and dimethyl sulfoxide is 6:0 ~ 2:4, preferably 4:2.
Further, the mass ratio of mixed system intermediate ion liquid and water is 4:2 ~ 4:0.5, preferably 4:1.
Further, the ionic liquid is 1- butyl -4- methylimidazolium chloride.
Further, the reaction time is the h of 0.5 h ~ 6, preferably 2 h.
Further, the reaction vessel is Conventional glass reactor.
Further, the boehmite is prepared by the following method to obtain: silicon source, slow hydrolysing agent are added to
In deionized water, after mixing evenly, precipitating reagent is added dropwise, adjusts solution ph to 9, solution is then transferred to liner polytetrafluoroethyl-ne
In the reaction kettle of alkene, reaction kettle is reacted into 5 ~ 60 h at 100 ~ 300 DEG C, reaction kettle is taken out, naturally cools to room temperature, pass through
The solid after reaction is collected in centrifugation, washing, by solid at 60 ~ 180 DEG C dry 8 ~ 48 h, i.e. the acquisition thin water of solid catalyst
Aluminium stone.
Source of aluminium is inorganic aluminate and/or aluminium isopropoxide, and slow hydrolysing agent is ammonium hydrogen carbonate, and precipitating reagent is that ammonium hydroxide is molten
Liquid.
Further, source of aluminium and the molar ratio of slow hydrolysing agent are 1:2.
Further, the inorganic aluminate is selected from AlCl3、Al(NO3)3、Al2(SO4)3、AlCl3·6H2O、Al(NO3)3·
9H2O、Al2(SO4)3·16H2One or more of O, wherein Al (NO3)3、Al(NO3)3·9H2O effect is best.
Further, from the method for the degradation solution purification by liquid extraction 5 hydroxymethyl furfural comprising 5 hydroxymethyl furfural are as follows: wrapping
Ether is added in degradation solution containing 5 hydroxymethyl furfural and carries out extraction and separation for the first time, after stratification, is added and goes in upper liquid
Ionized water adds ether and carries out extraction and separation again after mixing evenly, after carrying out 2-3 extraction and separation again with this, obtains 5-
Extract liquor is evaporated under reduced pressure by hydroxymethylfurfural-ether extraction liquid under the conditions of ice-water bath, is separated ether, is obtained high concentration
5 hydroxymethyl furfural.
Beneficial effect
Compared with prior art, the present invention has the advantage that
(1) there is heterogeneous catalysis γ-AlOOH disclosed by the invention low in raw material price to be easy to get, preparation method is simple, catalysis
The stable feature of agent property has good industrial applications prospect.
(2) when producing HMF using method catalytic cellulose of the invention, there is efficient catalytic (HMF yield and selectivity
It is high), catalyst it is easily separated it is reusable, easy to operate and cost is relatively low, and (equipment is simple, catalyst and the recyclable benefit of reaction
With) the features such as, it can avoid a large amount of side reactions and generate, improve selectivity of product, reduce product separation costs, have high using valence
Value.
(3) present invention extracts HMF from ionic liquid (IL), DMSO and water mixed solution using direct one-step method, reduces
Operating procedure avoided multioperation and will lead to HMF and decomposed, and improved HMF extraction efficiency；And utilize ionic liquid, DMSO
The polar difference between HMF makes full use of the polarity of water, reduces between DMSO and ionic liquid and HMF by the way that water is first added
Active force；The high extracting power of HMF can guaranteed by HMF stability simultaneously, improve HMF extraction efficiency by ether again；It realizes
The task of step extraction HMF, can effectively solve current HMF high boiling in higher boiling intensive polar solvent DMSO and ionic liquid
Problem is purified in point-polarity solvent and ionic liquid hybrid solution.
Detailed description of the invention
Fig. 1 is the flow diagram of preparation method of the invention；
Fig. 2 is the XRD diagram of γ-AlOOH obtained by embodiment 1；
Fig. 3 is influence diagram of the volume fraction to effect of extracting of ether in extractant in embodiment 7；
Fig. 4 is extraction times in embodiment 8 to the influence diagram of effect of extracting；
Fig. 5 is solvent in embodiment 9 to the influence diagram of catalytic effect；
Fig. 6 is the reaction time in embodiment 10 to the influence diagram of catalytic effect；
Fig. 7 is reaction temperature in embodiment 11 to the influence diagram of catalytic effect；
Fig. 8 is catalyst amount in embodiment 12 to the influence diagram of catalytic effect；
Fig. 9 is water additive amount in embodiment 13 to the influence diagram of catalytic effect；
Figure 10 is catalyst circulation access times in embodiment 17 to the influence diagram of catalytic effect.
Specific embodiment
The present invention is further explained below with reference to embodiment.Percentage composition in following embodiments is such as without special theory
Bright is mass percentage.Production firm is not specified in agents useful for same or instrument and equipment, is accordingly to be regarded as to purchase by market
The conventional products bought.
Embodiment 1
Under 800 revs/min of magnetic agitation, by the NH of 0.75 mol/L of 40 mL4HCO3Solution is slowly added into 10
mL 1.5 mol/L Al(NO3)3In solution.After it becomes clear transparent solutions, it is slowly dropped into 25% concentrated ammonia solution, is adjusted
Save pH to 9.After it becomes uniform mixed liquor, it is transferred into the reaction kettle of 100 mL inner liner polytetrafluoroethylenes,
12 h are reacted at 150 DEG C.When reaching the time of setting between when reacted, reaction kettle is taken out.After naturally cooling to room temperature, open
Reaction kettle carries out the separation and washing work of catalyst, obtains solid product.Finally, this solid product is done at 150 DEG C
Dry 12 h, that is, the solid catalyst γ-AlOOH obtained.This solid catalyst is subjected to XRD analysis.As shown in Fig. 2, from Fig. 2
As can be seen that all diffraction maximums of sample are consistent with orthogonal γ-AlOOH(JCPDS 021-1307) marker diffraction maximum, simultaneously
The diffraction maximum of other materials is not observed, illustrates that the sample of synthesis is the γ-AlOOH of high-purity.
Under 800 revs/min of magnetic agitation, 0.1 g cellulose is added to 4.0 g ionic liquid 1- butyl -4-
In the mixed solution of methylimidazolium chloride (BmimCl) and 2.0 g dimethyl sulfoxides (DMSO), stirring is until cellulose is completely molten
Solution, forms uniform reaction solution.0.1 g catalyst γ-AlOOH and 1.0 g deionized waters are added in this reaction solution again, to
Above-mentioned reaction system is transferred in 160 DEG C of oil bath crucibles by it after mixing evenly, reacts 2 h under 800 revs/min of magnetic agitations.
After reaction, the cold deionized water of 20 mL is added to reaction solution immediately to be quenched.Again with centrifuge with 10000
Rev/min speed separate 5 min, collect supernatant liquid, obtain include HMF degradation solution.This little degradation solution is taken out, is spent
After ionized water dilutes 200 times, high performance liquid chromatography is recycled to analyze the product in degradation solution, this reaction is calculated
HMF yield is 58.4% and HMF is selectively 60%, and the conversion ratio of cellulose is 97%.
In the degradation solution obtained after to above-mentioned centrifuge separation, 20 mL ether are added and carry out extraction and separation.Stand 10 min
Afterwards, supernatant liquid is taken out.20 mL deionized waters are added into this upper liquid again, after mixing evenly, are added into this uniform liquid
10 mL ether carry out extraction and separation.After standing 10 min, upper solution is taken out.With this, this process is repeated twice, in taking-up
Layer liquid, obtains final ether-HMF extraction solution.Meanwhile lower liquid all in the above process is collected, it is carried out at 80 DEG C
Rotary distillation recycles ionic liquid and DMSO.And then, by this ether-HMF extraction solution, in ice-water bath, decompression steaming is carried out
Processing is evaporated, recycles diethyl ether solution (making extractant next time), obtains the HMF of high concentration.Take this little HMF, with 20 mL go from
After sub- water dilution, using efficient liquid phase chromatographic analysis HMF content, it is 94% that HMF purity, which is calculated, extraction yield 59%.
Embodiment 2
γ-AlOOH preparation method and embodiment 1 are identical.Cellulose degradation produces HMF experimentation also as embodiment 1 is identical.
During preparing 5 hydroxymethyl furfural, reaction dissolvent intermediate ion liquid and DMSO constant rate are kept, it will be anti-
It answers solvent (ionic liquid and DMSO) to increase to 9.0 g, investigates influence of the reactant concentration to catalytic effect.Detailed process is such as
Under: under 800 revs/min of magnetic agitation, 0.1 g cellulose is added to 6.0 g ionic liquid 1- butyl -4- methyl chlorides
In the mixed solution for changing imidazoles (BmimCl) and 3.0 g dimethyl sulfoxides (DMSO), stirring is completely dissolved up to cellulose, is formed
Uniform reaction solution.0.1 g catalyst γ-AlOOH and 1.0 g deionized waters are added in this reaction solution again.To its stirring
After uniformly, above-mentioned reaction system is transferred in 160 DEG C of oil bath crucibles, reacts 2 h under 800 revs/min of magnetic agitations.Reaction knot
Shu Hou is added the cold deionized water of 20 mL to reaction solution immediately and is quenched.Again with centrifuge with 10000 revs/min
Speed separate 5 min, collect supernatant liquid, obtain include HMF degradation solution.This little degradation solution is taken out, deionized water is used
After 200 times of dilution, high performance liquid chromatography is recycled to analyze the product in degradation solution, the HMF that this reaction is calculated is produced
Rate is 60.3% and HMF is selectively 61.4%, and the conversion ratio of cellulose is 98%.
Embodiment 3
During preparing 5 hydroxymethyl furfural, reaction dissolvent intermediate ion liquid and DMSO constant rate are kept, will be reacted molten
Agent (ionic liquid and DMSO) is reduced to 3.0 g, investigates influence of the reactant concentration to catalytic effect.Detailed process is as follows:
Under 800 revs/min of magnetic agitation, 0.1 g cellulose is added to 2.0 g ionic liquid 1- butyl -4- methylimidazolium chlorides
(BmimCl) and in the mixed solution of 1.0 g dimethyl sulfoxides (DMSO), stirring is completely dissolved up to cellulose, is formed uniform
Reaction solution.0.1 g catalyst γ-AlOOH and 1.0 g deionized waters are added in this reaction solution again.After mixing evenly to it,
Above-mentioned reaction system is transferred in 160 DEG C of oil bath crucibles, reacts 2 h under 800 revs/min of magnetic agitations.After reaction, it stands
The cold deionized water of 20 mL is added to reaction solution to be quenched.Again with centrifuge with 10000 revs/min of speed point
From 5min, supernatant liquid is collected, obtains the degradation solution comprising HMF.This little degradation solution is taken out, dilutes 200 times with deionized water
Afterwards, high performance liquid chromatography is recycled to analyze the product in degradation solution, the HMF yield that this reaction is calculated is 50.3%
It is selectively 54.1% with HMF, the conversion ratio of cellulose is 93%.
It can be seen that in the mixed reaction solvent content of ionic liquid and DMSO from embodiment 1-3 not less than 6.0 g, i.e., it is fine
When tieing up cellulose content not higher than 1.7%, reaction dissolvent content influences HMF yield and selectivity little.Once but reaction solution contains
Amount is lower than 6.0 g, i.e., when glucose content is higher than 1.7%, reaction dissolvent content has a significant impact to HMF yield and selectivity.Instead
Answer the amount of solvent lower, HMF yield and selectivity are lower, this may be related in ion liquid dissolving degree with cellulose, react molten
The content of agent is lower, and ionic liquid content is fewer, and the content for dissolving cellulose is fewer, cellulose and catalyst contact probability
It decreases, catalytic effect is poorer.
Embodiment 4
The experimentation and raw material additional amount that γ-AlOOH preparation method and preparation condition, cellulose degradation produce HMF are completely such as
Embodiment 1 is identical.Only change HMF extracting process, investigation is added without influence of the water to extraction results.Detailed process is as follows: to
It is obtained after centrifuge separation in the degradation solution of upper layer, 20 mL ether is added and carry out extraction and separation.After standing 10 min, upper liquid is taken out
Body.20 mL ether are directly added into this upper liquid again and carry out extraction and separation.After standing 10 min, upper solution is taken out.With this
It is repeating this process 2 times, is taking out upper solution, obtain the extract liquor of ether-HMF.Then, by the extract liquor of this ether-HMF,
In ice-water bath, vacuum distillation processing is carried out, recycles diethyl ether solution (making next extractant), obtains the HMF of high concentration.It takes a small amount of
This HMF, after the dilution of 20 mL deionized waters, using efficient liquid phase chromatographic analysis HMF content, it is 19% that HMF purity, which is calculated,
Extraction yield is 42%.This description of test, be added water have a significant impact to extraction results, be added without water be difficult separate reaction dissolvent (from
Sub- liquid and DMSO mixed solution) and HMF, it is difficult to achieve the purpose that separating-purifying.
Embodiment 5
The experimentation and raw material additional amount that γ-AlOOH preparation method and preparation condition, cellulose degradation produce HMF are completely such as
Embodiment 1 is identical.Only change HMF extracting process, carries out two step separating and extracting methods.Detailed process is as follows: will collect upper layer
Liquid is evaporated under reduced pressure at 150 DEG C, separating ionic liquid first, obtains the degradation solution of DMSO- water-HMF.By this collect degradation solution into
The ether of 10 mL is added in row water-ether extraction and separation to this degradation solution first, after being sufficiently mixed, after standing 10 min, takes out
Supernatant liquid.20 mL deionized waters are added into this upper liquid again, after mixing evenly, 10 mL second are being added into this uniform liquid
Ether carries out extraction and separation.After standing 10 min, upper solution is taken out.It repeats this process 2 times, takes out supernatant liquid, obtain most
Whole ether-HMF extract liquor.Then, by this ether-HMF extract liquor, in ice-water bath, vacuum distillation processing is carried out, recycles ether
Solution (makees extractant next time), obtains the HMF of high concentration.This little HMF is taken, after the dilution of 20 mL deionized waters, is utilized
Efficient liquid phase chromatographic analysis HMF content, it is 98% that HMF purity, which is calculated, extraction yield 45%.
Comparative example 1, it can be seen that although two extraction HMF purity are higher, extraction yield is decreased obviously, overall effect
Not as good as a step extraction and separation.
Embodiment 6
The experimentation and raw material additional amount that γ-AlOOH preparation method and preparation condition, cellulose degradation produce HMF are completely such as
As embodiment 1.Influence of the type of HMF extractant to extraction results is investigated, respectively with toluene, acetone (Acetone), acetic acid
Ethyl ester, methyl isopropyl ketone, tetrahydrofuran (THF) and petroleum ether are extractant, and extraction process is as in Example 1.It extracts knot
Shown in fruit table 1, ether is best as extractant effect of extracting as can be drawn from Table 1.
Influence of the different extractants of table 1 to HMF extraction results
| Toluene | Acetone | Ethyl acetate | Methyl isopropyl ketone | Tetrahydrofuran | Petroleum ether | Ether | |
| HMF purity (%) | 32 | 58 | 65 | 85 | 86 | 76 | 94 |
| HMF extraction yield (%) | 5 | 18 | 6 | 35 | 20 | 8 | 59 |
Embodiment 7
The experimentation and raw material additional amount that γ-AlOOH preparation method and preparation condition, cellulose degradation produce HMF are completely such as
As embodiment 1.Under the premise of keeping first time extractant ether additional amount constant, i.e., into the supernatant liquid after centrifuge separation
It is added under the conditions of 10 mL ether, investigates since influence of the percentage by volume of ether to extraction results in extractant second,
Keeping ether and water total volume is 30 mL, is investigated when ether volume fraction is respectively 17%, 20%, 33%, 50%, 67% and 80% pair
The influence of extraction results, experimentation are gone as embodiment 1, and extraction results are as shown in Figure 3.As can be seen from Figure 3, in ether body
Fraction is 33%, i.e., when ether/water volume ratio is 1:2, effect of extracting is best.
Embodiment 8
γ-AlOOH preparation method and preparation condition and cellulose degradation produce HMF experimentation and raw material additional amount it is complete
As in Example 1.The influence of extraction times (1,2,3,4,5,6 and 7 time) to effect of extracting is investigated, experimentation goes to implement
As example 1, extraction results are as shown in Figure 4.4 it can know from figure, at extraction times 4 times, effect of extracting is best.
Embodiment 9
γ-AlOOH preparation method and preparation condition are as in Example 1.Cellulose degradation produces HMF experimentation also as implemented
Example 1 is identical, changes reaction dissolvent, and the variation for investigating reaction dissolvent influences catalytic effect.Experimental result is as shown in figure 5, IL is
Ionic liquid；DMSO is dimethyl sulfoxide；DMF is N ' dinethylformamide；THF is tetrahydrofuran；Acetone is acetone；
XILRefer to ionic liquid in the mass fraction of in the mixed solvent.As can be drawn from Figure 5 using ionic liquid and DMSO mixed liquor as
When solvent and the two mass ratio are 4:2, catalytic effect is best.
Embodiment 10
γ-AlOOH preparation method and preparation condition are as in Example 1.Cellulose degradation produces HMF experimentation also as implemented
Example 1 is identical, and the reaction time of only adjustment catalysis reaction, (0.5 h to 6 h) investigated influence of the reaction time to catalytic effect.
Experimental result is as shown in Figure 6.As can be seen from Figure 6 the catalysis reaction time is 2 h, and catalytic effect is best.
Embodiment 11
γ-AlOOH preparation method and preparation condition are as in Example 1.Cellulose degradation produces HMF experimentation also as implemented
Example 1 is identical, only the reaction temperature (120 DEG C to 210 DEG C) of modulation catalysis reaction, investigates reaction temperature to the shadow of catalytic effect
It rings.Experimental result is as shown in Figure 7.As can be seen from Figure 7 reaction temperature is 160 DEG C, and catalytic effect is best.
Embodiment 12
γ-AlOOH preparation method and preparation condition are as in Example 1.Cellulose degradation produces HMF experimentation also as implemented
Example 1 is identical, and only (0.05 g to 0.2 g), investigates influence of the dosage to catalytic effect of catalyst to regulating catalyst dosage.It is real
It is as shown in Figure 8 to test result.As can be seen from Figure 8 when catalyst amount is 0.1 g, catalytic effect is best.
Embodiment 13
γ-AlOOH preparation method and preparation condition are as in Example 1.Cellulose degradation produces HMF experimentation also as implemented
Example 1 is identical, and only the additive amount (0 to 4 mL) of modulation water, investigates influence of the additive amount to catalytic effect of water.Experimental result is such as
Shown in Fig. 9.As can be seen from Figure 9 when the additive amount of water is 1.0 mL, catalytic effect is best.
Embodiment 14
γ-AlOOH preparation method and preparation process are as in Example 1, and modulation silicon source prepares different γ-AlOOH, use respectively
Al2(SO4)3、AlCl3With Al (i-OPr)3Instead of original Al (NO3)3γ-AlOOH is prepared, and is made with the γ-AlOOH that this is prepared
HMF is produced for the hydrolysis of catalyst cellulose, it is identical that cellulose degradation prepares HMF process such as embodiment 1.Specific experiment knot
Fruit is as shown in table 2.
HMF is produced in the γ-AlOOH catalytic cellulose degradation of the different silicon source preparations of table 2
| Silicon source | Al2(SO4)3 | AlCl3 | Al(i-OPr)3 | Al(NO3)3 |
| HMF(%) | 35.6 | 48.6 | 20 | 58.4 |
| HMF selectivity (%) | 45 | 54 | 34 | 60 |
| Cellulose conversion ratio (%) | 79 | 89 | 59 | 97 |
From table 2 it can be seen that γ-AlOOH the ratio prepared by raw material of inorganic silicon source is by silicon source of organic silicon source as raw material system
Standby γ-AlOOH has more preferable catalytic effect.And in inorganic silicon source, with Al (NO3)3γ-as silicon source preparation
The catalytic effect of AlOOH is best.
Embodiment 15
γ-AlOOH preparation method and preparation process are as in Example 1, only regulating catalyst γ-AlOOH preparation temperature, will
150 DEG C of original preparation temperature is adjusted in 100 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 180 DEG C or 200 DEG C
Any one, and using the γ-AlOOH that this is prepared as catalyst cellulose degradation prepare HMF.Cellulose degradation preparation
HMF process such as embodiment 1 is identical.The results are shown in Table 3 for it.From table 3, it can be deduced that when preparation temperature is 150 DEG C, preparation
γ-AlOOH catalytic effect it is best.
HMF is produced in the γ-AlOOH catalytic cellulose degradation of 3 different temperatures of table preparation
| Preparation temperature (DEG C) | 100 | 130 | 150 | 160 | 180 | 200 |
| HMF(%) | 44.3 | 52.5 | 58.4 | 55.6 | 50.2 | 46.8 |
| HMF selectivity (%) | 53 | 56 | 60 | 59 | 55 | 54 |
| Cellulose conversion ratio (%) | 83 | 93 | 97 | 95 | 92 | 87 |
Embodiment 16
γ-AlOOH preparation method and preparation process are as in Example 1, only regulating catalyst γ-AlOOH preparation time, will
Original 12 h of preparation time is adjusted to any one in 2 h, 6 h, 12 h, 18 h, 24 h, 36 h or 48 h, and is made with this
Standby γ-AlOOH prepares HMF as catalyst cellulose degradation.Cellulose degradation prepares HMF process such as 1 phase of embodiment
Together.The results are shown in Table 4 for it.From table 4, it can be deduced that when preparation time is 12 h, the catalytic effect of the γ-AlOOH of preparation
Most preferably.
HMF is produced in the γ-AlOOH catalytic cellulose degradation of 4 different time of table preparation
| Preparation time (h) | 2 | 6 | 12 | 18 | 24 | 36 | 48 |
| HMF(%) | 11.3 | 40.3 | 58.4 | 57.3 | 56.3 | 54.6 | 52.6 |
| HMF selectivity (%) | 25 | 49 | 60 | 60 | 59 | 57 | 56 |
| Cellulose conversion ratio (%) | 45 | 82 | 97 | 96 | 95 | 95 | 94 |
Embodiment 17
Catalyst circulation reuses experiment.Solid residue is dried after being centrifugated using in embodiment 1 as cellulose next time
The catalyst of HMF experiment is produced in degradation.Detailed process is as follows: being centrifugally separating to obtain in experimental example 1 for the first time using γ-AlOOH's
Residue removes surface unreacted cellulose and remaining reaction respectively after the washing of deionized water, ethyl alcohol and γ-penta lactones
Object (such as glucose, fructose, HMF) dries in 100 DEG C of vacuum ovens, obtains solid residue, as experiment next time
Catalyst carries out catalytic cycle using experiment, investigates the stability of catalyst, cellulose hydrolysis produces experimentation and crosses experimental example
1 is identical.Its catalytic result is as shown in Figure 10.As shown in Figure 10, catalyst γ-AlOOH has good catalytic stability, 5 weights
After multiple use, larger change does not occur for the catalytic efficiency of catalyst, and HMF yield and cellulose conversion ratio are respectively 47.8% He
91%。
Protection content of the invention is not limited to above embodiments.Without departing from the spirit and scope of the invention, originally
Field technical staff it is conceivable that variation and advantage be all included in the present invention, and with the attached claims be protection
Range.
Claims (10)
1. a kind of method that boehmite efficient catalytic cellulose prepares 5 hydroxymethyl furfural, which is characterized in that by boehmite
It is added to cellulose in the mixed system of ionic liquid, dimethyl sulfoxide and water, is transferred in reactor after mixing evenly,
It is stirred to react under the conditions of 120 ~ 210 DEG C, deionized water is added into reaction solution after reaction and is quenched, is centrifuged, receives
Collect supernatant liquid to get the degradation solution comprising 5 hydroxymethyl furfural.
2. the method that boehmite efficient catalytic cellulose according to claim 1 prepares 5 hydroxymethyl furfural, feature
It is, the mass ratio of the boehmite and cellulose is 0.05:1 ~ 5:1.
3. the method that boehmite efficient catalytic cellulose according to claim 1 prepares 5 hydroxymethyl furfural, feature
It is, the mass ratio of the cellulose and mixed system is 1:10 ~ 1:100.
4. the method that boehmite efficient catalytic cellulose according to claim 1 prepares 5 hydroxymethyl furfural, feature
It is, the mass ratio of the mixed system intermediate ion liquid and dimethyl sulfoxide is 6:0 ~ 2:4.
5. the method that boehmite efficient catalytic cellulose according to claim 1 prepares 5 hydroxymethyl furfural, feature
It is, the mass ratio of the mixed system intermediate ion liquid and water is 4:2 ~ 4:0.5.
6. the method that boehmite efficient catalytic cellulose according to claim 1 prepares 5 hydroxymethyl furfural, feature
It is, the reaction time is the h of 0.5 h ~ 6.
7. the method that boehmite efficient catalytic cellulose according to claim 1 prepares 5 hydroxymethyl furfural, feature
It is, the boehmite is prepared by the following method to obtain: silicon source, slow hydrolysing agent is added in deionized water,
After mixing evenly, precipitating reagent is added dropwise, adjusts solution ph to 9, then solution is transferred to the reaction kettle of inner liner polytetrafluoroethylene
In, reaction kettle is reacted into 5 ~ 60 h at 100 ~ 300 DEG C, reaction kettle is taken out, room temperature is naturally cooled to, by being centrifuged, washing receipts
Solid is dried 8 ~ 48 h by the solid after collection reaction at 60 ~ 180 DEG C, i.e. acquisition solid catalyst boehmite；
Wherein, source of aluminium is inorganic aluminate and/or aluminium isopropoxide, and slow hydrolysing agent is ammonium hydrogen carbonate, and precipitating reagent is ammonium hydroxide
Solution.
8. the method that boehmite efficient catalytic cellulose according to claim 7 prepares 5 hydroxymethyl furfural, feature
It is, the molar ratio of source of aluminium and slow hydrolysing agent is 1:2.
9. the method that boehmite efficient catalytic cellulose according to claim 7 prepares 5 hydroxymethyl furfural, feature
It is, the inorganic aluminate is selected from AlCl3、Al(NO3)3、Al2(SO4)3、AlCl3·6H2O、Al(NO3)3·9H2O、Al2
(SO4)3·16H2One or more of O.
10. the method that boehmite efficient catalytic cellulose according to claim 1 prepares 5 hydroxymethyl furfural, feature
Be, further include the steps that from the degradation solution purification by liquid extraction 5 hydroxymethyl furfural comprising 5 hydroxymethyl furfural, specifically: comprising
Ether is added in the degradation solution of 5 hydroxymethyl furfural and carries out extraction and separation for the first time, after stratification, obtains upper liquid；In upper liquid
Middle addition deionized water adds ether and carries out extraction and separation again, carry out 2-3 extraction and separation again with this after mixing evenly
Afterwards, 5 hydroxymethyl furfural-ether extraction liquid is obtained, extract liquor is evaporated under reduced pressure under the conditions of ice-water bath, separates ether, i.e.,
?.
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| SHAOHUA XIAO 等: "Efficient conversion of cellulose into biofuel precursor 5-hydroxymethylfurfural in dimethyl sulfoxide–ionic liquid mixtures", 《BIORESOURCE TECHNOLOGY》 * |
| 周理龙 等: "纤维素在离子液体中的降解转化", 《化学进展》 * |
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