CN108212212A - A kind of temperature sensitive acidic ionic liquid and preparation method thereof and the purposes in catalysis microcrystalline cellulose hydrolysis - Google Patents
A kind of temperature sensitive acidic ionic liquid and preparation method thereof and the purposes in catalysis microcrystalline cellulose hydrolysis Download PDFInfo
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- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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Abstract
Purposes the present invention relates to a kind of temperature sensitive acidic ionic liquid and preparation method thereof and in catalysis microcrystalline cellulose hydrolysis.The temperature sensitive acidic ionic liquid is the acidic ion liquid by a kind of quaternary ammonium salt in choline, choline chloride, glycine betaine and empgen BB and a kind of fluorine-containing acid molecule synthesis in tetrafluoro boric acid, trifluoromethanesulfonic acid and double trifluoromethanesulfonic acid acid imides.The ionic liquid not strong acid groups such as sulfur acid, reduce the corrosion to consersion unit, and be easily isolated and recycled, largely enhance liquid acid catalyst and repeat utility.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of temperature sensitive acidic ionic liquid, which can
To be used to be catalyzed the preparation method of microcrystalline cellulose hydrolysis and the ionic liquid and its micro- as Two Liquid Phases catalyst system
Application in crystalline cellulose hydrolytic process.
Background technology
Cellulose is the most important component part of biomass resource, is mainly bonded by glucose by β-Isosorbide-5-Nitrae glucosides
It closes.But due to cellulose hydroxyl group rich content, thus cellulose has complicated intramolecular and intermolecular hydrogen bonding network knot
Structure so that cellulose has higher crystallinity, and is insoluble in the common solvent such as water.Cellulose is hydrolyzed into glucose, then
Continue catalyzed conversion generation bio-fuel, chemical intermediate and chemicals, Ke Yiji through biological and chemical method by glucose again
Alleviate dependence of the China to fossil energy in big degree.
It is also a most important step that cellulose, which is hydrolyzed into the first step that glucose is biomass energy catalyzed conversion, thus each
State scientific research personnel conducts extensive research cellulose hydrolysis.Cellulase is the ideal catalyst of hydrocellulose, China
A kind of method that patent 201580037593.1 discloses enzymatic hydrolysis ligno-cellulosic materials and sugar fermentation, first with acid
And/or then alkali carries out water with cellulase again then with polyalcohol (particularly glycerine) sequential processes ligno-cellulosic materials
Solution reaction, can effectively realize the hydrolysis or liquefaction of ligno-cellulosic materials.Chinese patent 201710655858.5 discloses
A kind of process of the efficient enzyme hydrolysis lignocellulosic of multistage.But although cellulose hydrolyzation method reaction condition is mild,
But reaction time long efficiency is low, technique and its complexity and cellulase is expensive, it is difficult to carry out large-scale commercial production.
Chinese patent 201610624249.9,201610623755.6,201410275761.8,201410199751.0 discloses one kind
The preparation method of sulfonation carbon solid acid although solid acid catalyst is small to equipment corrosion, can recycle, and preparing should
Class catalyst is typically that carbon skeleton is generated after high temperature cabonization with the biomass-based carbon material such as glucose, fructose, cellulose, then
After the concentrated sulfuric acid or oleum sulfonation, catalyst surface is supported on using sulfonic acid group as acidic-group.These methods are not
It is evitable there are acidic active sites density is small, catalyst hydrothermal stability is poor, the disadvantages such as preparation process complexity.In addition it is most heavy
What is wanted is that complicated crystal structure is not soluble in water, and solid acid catalyst has contacted in water with cellulose since cellulose has
Limit, largely limit the efficiency in catalytic reaction process, this be also solid acid catalyst be difficult to it is hydrolyzed in cellulose
In journey the main reason for industrialization.In order to improve cellulose hydrolysis efficiency, homogeneous acids such as sulfuric acid, hydrochloric acid, maleic acid, formic acid at present
It is the most common acidic catalyst of industrial hydrocellulose.Chinese patent 201410845046.3 discloses a kind of sulfonate functional
Change the method that ionic liquid meets catalyst system and catalyzing catalyzing hydrolysis cellulose.Chinese patent 201410156496.1 discloses a kind of weak
The method that polarity acid Two Liquid Phases catalyzing hydrolysis cellulose prepares glucose.Chinese patent 201610091292.3 discloses a kind of pole
The method that the non-proton system catalyzing hydrolysis cellulose of property prepares reducing sugar.But still used in the above method sulfuric acid or its
As acidic catalyst, liquid acid catalysis is serious to equipment corrosion for his organic acid, and acid waste liquid needs neutralisation treatment after reacting
After could discharge, increase processing cost and environmental pressure.However the most important problem of aforesaid liquid acid or acidic catalyst
Difficult separation and recovery in water, it is not strong to repeat usability.The thus liquid acid catalyst of reasonable design is ensureing its catalytic performance
Under the premise of, without using being applicable in the strong acid such as sulfuric acid to reduce the extent of corrosion to consersion unit, and it is recyclable to improve catalyst
Performance is and its necessary.
Therefore, in order to improve microcrystalline cellulose hydrolysis rate, it is still desirable to design novel recyclable homogeneous acid catalyst.
Invention content
According to an aspect of the present invention, it is an object of the present invention to provide a kind of temperature sensitive acidic ionic liquid, institutes
It is the acidic ion liquid with quaternary ammonium salt cheap and easy to get and fluorine-containing acid molecule synthesis to state ionic liquid.The ionic liquid is free of
The strong acid groups such as sulfuric acid reduce the corrosion to consersion unit, and are easily isolated and recycled, and largely enhance liquid acid
Catalyst repeats utility.
Preferably, the quaternary ammonium salt in the ionic liquid is selected from choline, choline chloride, glycine betaine and empgen BB
In one kind.
Preferably, the quaternary ammonium salt is preferably glycine betaine or empgen BB.
Preferably, the fluorine-containing acidic molecular in the ionic liquid is selected from tetrafluoro boric acid, trifluoromethanesulfonic acid and double fluoroforms
At least one of sulfonic acid acid imide.
Preferably, the ionic liquid puts at normal temperatures in solid-state and restores liquid phase state in water.
Preferably, the ionic liquid water solubility change with temperature, under room temperature ionic liquid it is not soluble in water and with water shape
Liquid-phase system in pairs, as temperature gradually rises, ionic liquid solubility gradually increase and gradually formation miscible with water in water
Homogeneous system.Ionic liquid is completely soluble in water after temperature is higher than 60 DEG C, and homogeneous catalysis system is formed with water.Work as temperature
When being gradually reduced as below room temperature, ion liquid dissolving degree reduces and is gradually precipitated from water, restores biliquid phase system again.
The term " room temperature " refers to the temperature range less than 30 DEG C and higher than 10 DEG C.
According to another aspect of the present invention, it is a further object to provide the temperature sensitive acidic ionic liquids
Preparation method, the preparation method includes the following steps：
(1) it is 1 according to molar ratio by quaternary ammonium salt and fluorine-containing acidic molecular:1 adds in input water, at a temperature of 30~80 DEG C
It is stirred to react 0.5~4h；
(2) reaction system is down to after room temperature removes water by rotary evaporation in vacuo and can obtain cured temperature sensitive type acidity
Ionic liquid.
Preferably, quaternary ammonium salt described in step (1) is in choline, choline chloride, glycine betaine and empgen BB
One kind.
Preferably, the quaternary ammonium salt is glycine betaine or empgen BB.
Preferably, fluorine-containing acidic molecular described in step (1) is selected from tetrafluoro boric acid, trifluoromethanesulfonic acid and double trifluoromethanesulfonic acids
One kind in acid imide.
Preferably, temperature sensitive acidic ionic liquid synthesis temperature described in step (1) is 50~70 DEG C, generated time 1
~2h.
Preferably, the synthesis of temperature sensitive acidic ionic liquid described in step (2) terminates after being cooled to room temperature, and temperature sensitive type is acid
Ionic-liquid catalyst is separated from the water to form biliquid phase structure.Then water is hanged be evaporated off rear temperature sensitive acidic ionic liquid by
Gradually cure, then by cured temperature sensitive acidic ionic liquid, dry 12h, taking-up can obtain temperature sensitive under 40 DEG C of vacuum conditions
Type acidic ionic liquid catalysts.
According to another aspect of the present invention, it is a further object to provide the temperature sensitive acidic ionic liquids
Purposes of the catalyst in catalyzing hydrolysis microcrystalline cellulose.
According to another aspect of the present invention, it is a further object to provide a kind of acid using the temperature sensitive type
The method of ionic liquid-catalyzed hydrolyzing microcrystalline cellulose, the described method comprises the following steps：
1) it is 0.5 by mass ratio:1 to 8:1 temperature sensitive acidic ionic liquid is put into water jointly with microcrystalline cellulose, water
Mass ratio with microcrystalline cellulose is 20:1 to 40:1, in the reactor at a temperature of 130~200 DEG C, reaction 3~for 24 hours；
2) reaction kettle cooled to room temperature after reaction, is detached remaining cellulose residue filter using filter paper,
Ionic liquid phase liquid is separated by dispenser, obtains the hydrolysis production of ionic liquid phase and water phase, wherein microcrystalline cellulose
Object is primarily present in water phase, and a small amount of hydrolysate is present in ionic liquid phase；
3) it adds in a small amount of fresh deionized water into ionic liquid phase, continues lock out operation with dispenser after fully shaking,
Repeatedly the hydrolysate washes clean in ionic liquid, the ionic liquid of recycling can be repeated to make after washing separation
With；
4) cleaning solution in step 3) with the water phase in step 2) is merged, quantitative analysis is carried out to product in the water phase.
Preferably, ionic-liquid catalyst described in step 1) and microcrystalline cellulose mass ratio are preferably 2:1 to 6:1, more
Preferably 1:1 to 6:1, more preferably 1:1.
Preferably, reaction temperature described in step 1) is preferably 150~170 DEG C, and the reaction time is preferably 6~12h.
Preferably, dispenser described in step 2) can be separatory funnel.
Preferably, the method for the catalyzing hydrolysis microcrystalline cellulose does not use other inorganic acids or organic acid, does not use it
Its catalyst.
Advantageous effect
(1) acidic functionality of the Thermo-sensitive ion is-COOH and-OH, and acidity is weaker than traditional liquid acid, such as sulfuric acid, salt
Acid, nitric acid etc. greatly reduce the corrosivity to reactor.
(2) acidic ion liquid can play the role of destroying cellulose hydrogen bond network structure, therefore containing only in itself
Still there is excellent hydrolysing activity when having weak acid group as acidic functionality.
(3) acidic ion liquid is in aqueous phase reactions, and solubility is increased with reaction temperature and increased, when more than stagnation temperature
Ionic-liquid catalyst dissolves each other to form homogeneous acid catalytic systems completely with water phase after degree.
(4) acidic ion liquid is after reaction was completed, and solubility declines with reaction temperature and reduced, when being cooled to room temperature
Ionic-liquid catalyst is separated to form biliquid phase structure from water phase afterwards, detaches and returns convenient for acidic ionic liquid catalysts
It receives.
(5) the temperature sensitive type Two Liquid Phases catalyst system, passes through modulation acidic ion liquid and the mass ratio of microcrystalline cellulose
Example can regulate and control the selectivity of microcrystalline cellulose conversion ratio and glucose and levulic acid.
(6) recycling of such acidic ionic liquid catalysts is convenient, and it is anti-that used catalyst can be directly thrown into lower part
Ying Zhong.When activity is substantially reduced, by the catalyst of recycling in hydrogen peroxide oxidation processes (40 DEG C, for 24 hours), you can by ionic liquid
Body surface area carbon removes, catalyst activity recovery again.
(7) critical-temperature of the solubility of such acidic ionic liquid catalysts in water and formation homogeneous system can lead to
The solubility of quaternary ammonium salt molecular side chain length and pendant hydrophilic group in water is crossed to adjust.
(8) low in raw material price needed for such acidic ionic liquid catalysts, it is simple and easy to get.And catalyst preparation conditions
Mildly, preparation process is simple, meets present social desirability, has extensive industrialization prospect.
Description of the drawings
Fig. 1 is to prepare the acidic ionic liquid catalysts obtained in embodiment 1 to dissolve photo in high-temperature water, when temperature liter
During to 60 DEG C, ionic-liquid catalyst is dissolving each other completely with water, forms homogeneous catalyst system；
Fig. 2 is to prepare the acidic ionic liquid catalysts obtained in embodiment 1 photo is precipitated in room temperature water, when temperature drops
During to room temperature, ionic-liquid catalyst is precipitated from water phase, forms Two Liquid Phases catalyst system；
Fig. 3 is to prepare the acidic ionic liquid catalysts obtained in embodiment 1 during catalyzing hydrolysis microcrystalline cellulose,
Catalyst rate of charge and cellulose conversion ratio and the relation schematic diagram (reaction condition of glucose and levulic acid：Microcrystalline cellulose
Element：0.5g, reaction temperature：170 DEG C, the reaction time：12h)；
Fig. 4 is to prepare the acidic ionic liquid catalysts obtained in embodiment 4 to dissolve photo in high-temperature water, when temperature liter
During to 70 DEG C, ionic-liquid catalyst is dissolving each other completely with water, forms homogeneous catalyst system；
Fig. 5 is to prepare the acidic ionic liquid catalysts obtained in embodiment 4 photo is precipitated in room temperature water, when temperature drops
During to room temperature, ionic-liquid catalyst is precipitated from water phase, forms Two Liquid Phases catalyst system；
Fig. 6 is to prepare the acidic ionic liquid catalysts obtained in embodiment 5 to dissolve photo in high-temperature water, when temperature liter
During to 120 DEG C, ionic-liquid catalyst dissolves each other with water section, forms part homogeneous catalyst system；
Fig. 7 is to prepare the acidic ionic liquid catalysts obtained in embodiment 5 photo is precipitated in room temperature water, when temperature drops
During to room temperature, ionic-liquid catalyst is precipitated from water phase, forms Two Liquid Phases catalyst system.
Specific embodiment
Hereinafter, it will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims in the term that uses should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of appropriate definition term is to carry out the principle of best interpretations, according to meaning corresponding with the technical aspect of the present invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
In the preparation method of temperature sensitive acidic ionic liquid according to the present invention after evaporative removal water, without further
Purifying, because the reaction is in strict accordance with stoichiometric ratio 1:1 reaction, almost without the residual of other molecules and ion, so as to effectively
Ground simplifies treatment process.
The fluorine-containing temperature-sensitive to ionic liquid has an impact in temperature sensitive acidic ionic liquid according to the present invention, because
It is hydrophobic group for the fluorine in ionic liquid, can regulates and controls ion to a certain extent by using the different molecule of fluorinated volume
The solubility of liquid in water.If being changed to chlorine plasma, such as conventional imidazolitm chloride plasma liquid is then dissolved at room temperature
Biliquid phase system can not be formed in water.
Temperature-sensitive is faced in the selection of the reactant quaternary ammonium salt of temperature sensitive acidic ionic liquid according to the present invention
Boundary's temperature and catalytic activity also have an impact, with the growth of alkyl chain in quaternary ammonium salt or the change of oxygen-containing group, ionic liquid with
The critical-temperature that water dissolves each other completely can also increase, and during for example, by using empgen BB as quaternary ammonium salt, which can
To be increased to 70 DEG C.When using choline as quaternary ammonium salt, when temperature rises to 120 DEG C, ionic-liquid catalyst and water section
It dissolves each other.
Preferably, temperature sensitive acidic ionic described in the step of preparation method of the temperature sensitive acidic ionic liquid (2)
Liquid synthesis terminates after being cooled to room temperature, and temperature sensitive acidic ionic liquid catalyst is separated from the water to form biliquid phase structure.So
After moisture therein is removed by rotary evaporation in vacuo afterwards, dry 12h, takes out and is cooled to room temperature i.e. under 40 DEG C of vacuum conditions
It can obtain cured temperature sensitive acidic ionic liquid catalyst.
At normal temperatures, if temperature sensitive acidic ionic liquid prepared in accordance with the present invention be kept completely separate with moisture after can be in
Solid-state, but as long as liquid phase state can be restored even if at normal temperatures, therefore above-mentioned outstanding steaming and vacuum drying operation are all by touching water
Be in order to which water therein is removed, ionic liquid is cured, convenient for weighing ionic liquid in subsequent reaction, otherwise ionic liquid
Body in water when, it is difficult to quantitatively be fed intake.
Temperature sensitive acidic ionic liquid according to the present invention has the water-soluble property changed with temperature, under room temperature from
Sub- liquid is not soluble in water and forms biliquid phase system with water, and as temperature gradually rises, solubility is gradual in water for ionic liquid
Increase and gradually formation homogeneous system miscible with water.Ionic liquid is completely soluble in water after temperature is higher than 60 DEG C, with water
Form homogeneous catalysis system.When temperature is gradually reduced as below room temperature, ion liquid dissolving degree reduces and is gradually analysed from water
Go out, restore biliquid phase system again.
The term " room temperature " refers to the temperature range less than 30 DEG C and higher than 10 DEG C.
The temperature-sensitive is remarkably contributing to the liquid phase separation after catalysis microcrystalline cellulose hydrolysis.It is adopted according to the present invention
With in the method for the temperature sensitive acidic ionic liquid catalyzing hydrolysis microcrystalline cellulose due to being biliquid phase system, i.e., it is described temperature sensitive
Type acidic ionic liquid catalysts are also liquid-phase catalyst, therefore can effectively realize the hydrolysis to cellulose.Temperature-sensitive
It is difficult mainly to solve liquid acid catalyst recycling, common liq acid such as sulfuric acid, hydrochloric acid, nitric acid etc., after reaction at room temperature still
It is soluble in water, it can not be separated from the water, therefore the catalyst such as common inorganic acid can not by simply outstanding steaming operation
Realize recycling, and will after the reaction plus the substance of soda lime etc neutralize after discharge, if not neutralizing direct blowdown i.e. pair
Environment pollutes.
The temperature sensitive acidic ionic liquid of preparation according to the present invention is by regulating and controlling catalyst temperature-sensitive, it is possible to
The recycling of liquid acid catalyst is realized, from larger improvement after catalyst recycling or environmental problem all meetings.With temperature
While the ionic-liquid catalyst of quick property has hydrolysis effect, solves the problems, such as the recycling of acidic catalyst.It is commercialized
Ionic liquid is generally dissolved in water and does not have acidic-group, also needs to couple other acidic catalysts and be reacted, also very big journey
Application of the ionic liquid during hydrocellulose is limited on degree.
It can largely be destroyed additionally, due to the temperature sensitive acidic ionic liquid inherently acidic catalyst of the present invention
Cellulose crystals structure accelerates reaction rate, other acidic catalysts need not be added compared to other biliquid phase systems.
The step of method according to the present invention using the temperature sensitive acidic ionic liquid catalyzing hydrolysis microcrystalline cellulose
1) mass ratio of temperature sensitive acidic ionic liquid and microcrystalline cellulose is 0.5 in:1 to 8:1, preferably 2:1 to 6:1, more preferably
It is 1:1 to 6:1, more preferably 1:1.When the mass ratio of temperature sensitive acidic ionic liquid and microcrystalline cellulose is less than 0.5:When 1, i.e.,
Temperature sensitive acidic ionic liquid dosage is insufficient, then the hydrolysis of microcrystalline cellulose is not enough；When temperature sensitive acidic ionic liquid with
The mass ratio of microcrystalline cellulose is more than 8:When 1, i.e., temperature sensitive acidic ionic liquid is excessive, then later stage separation is needed using more
Water is washed, and not economical enough.
The step of method according to the present invention using the temperature sensitive acidic ionic liquid catalyzing hydrolysis microcrystalline cellulose
1) mass ratio of water and microcrystalline cellulose is 20 in:1 to 40:1.The limitation of amount of water be primarily due to add in water it is moderate,
To ensure that cellulose can be sufficiently stirred and reacted with catalyst in water.The very little cellulose of water stirs insufficient influence
Catalyst mass transfer in water, thus influence hydrolysis efficiency.Then catalyst is diluted water by water transition too much, catalyst unit concentration
Reduction also influences hydrolysis efficiency, thus certain control need to be carried out to water.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not form any limit to the present invention
System, it will be appreciated by those skilled in the art that each falling within the present invention without departing from the modification in the range of the essence of the present invention and design
Protection domain.Unless stated otherwise, the reagent and instrument used in following embodiment is commercially available product.
Prepare embodiment 1
After glycine betaine (0.03mol) stirs evenly in water with double trifluoromethanesulfonic acid acid imides (0.03mol), in 60 DEG C of oil
Heating reaction 1h under the conditions of bath.Reaction terminates after being cooled to room temperature, using outstanding steaming by moisture removal in flask, the solid that will be obtained
The dry 12h under 40 DEG C of vacuum conditions, obtained solid is cured acidic ionic liquid catalysts.
Fig. 1 is that the acidic ionic liquid catalysts obtained in embodiment 1 dissolve photo in high-temperature water, when temperature rises to 60
DEG C when, ionic-liquid catalyst is dissolving each other completely with water, formed homogeneous catalyst system.
Fig. 2 is that photo is precipitated in the acidic ionic liquid catalysts obtained in embodiment 1 in room temperature water, when temperature is down to room
Wen Shi, ionic-liquid catalyst are precipitated from water phase, form Two Liquid Phases catalyst system.
Prepare embodiment 2
After glycine betaine (0.03mol) stirs evenly in water with tetrafluoro boric acid (0.03mol), add under the conditions of 60 DEG C of oil baths
Thermal response 1h.Reaction terminates after being cooled to room temperature, and is steamed using outstanding by moisture removal in flask, by obtained solid in 40 DEG C of vacuum
Under the conditions of dry 12h, obtained solid is cured acidic ionic liquid catalysts.
Prepare embodiment 3
After glycine betaine (0.03mol) stirs evenly in water with trifluoromethanesulfonic acid (0.03mol), under the conditions of 60 DEG C of oil baths
Heating reaction 1h.Reaction terminates after being cooled to room temperature, and is steamed using outstanding by moisture removal in flask, and obtained solid is true at 40 DEG C
Dry 12h under empty condition, obtained solid is cured acidic ionic liquid catalysts.
Prepare embodiment 4
After empgen BB (0.03mol) stirs evenly in water with tetrafluoro boric acid (0.03mol), in 60 DEG C of oil baths
Under the conditions of heating reaction 1h.Reaction terminates after being cooled to room temperature, and is steamed using outstanding by moisture removal in flask, obtained solid is existed
Dry 12h under 40 DEG C of vacuum conditions, obtained solid is cured acidic ionic liquid catalysts.
Fig. 4 is to prepare the acidic ionic liquid catalysts obtained in embodiment 4 to dissolve photo in high-temperature water, when temperature liter
During to 70 DEG C, ionic-liquid catalyst is dissolving each other completely with water, forms homogeneous catalyst system；Fig. 5 is obtained to prepare in embodiment 4
To acidic ionic liquid catalysts photo is precipitated in room temperature water, when temperature is down to room temperature, ionic-liquid catalyst is from water
It is precipitated in phase, forms Two Liquid Phases catalyst system.
Prepare embodiment 5
After choline (0.03mol) stirs evenly in water with double trifluoromethanesulfonic acid acid imides (0.03mol), in 120 DEG C of oil
Heating reaction 1h under the conditions of bath.Reaction terminates after being cooled to room temperature, using outstanding steaming by moisture removal in flask, the solid that will be obtained
The dry 12h under 40 DEG C of vacuum conditions, obtained solid is cured acidic ionic liquid catalysts.
Fig. 6 is to prepare the acidic ionic liquid catalysts obtained in embodiment 5 to dissolve photo in high-temperature water, when temperature liter
During to 120 DEG C, ionic-liquid catalyst dissolves each other with water section, forms part homogeneous catalyst system；Fig. 7 is prepares embodiment
Photo is precipitated in the acidic ionic liquid catalysts obtained in 5 in room temperature water, when temperature is down to room temperature, ionic-liquid catalyst
It is precipitated from water phase, forms Two Liquid Phases catalyst system.
EXPERIMENTAL EXAMPLE 1
The ionic-liquid catalyst being prepared in preparation embodiment 1 to 5 is subjected to microcrystalline cellulose in accordance with the following methods
Hydrolysising experiment.
1) 0.5g ionic-liquid catalysts, 0.5g microcrystalline celluloses and 20mL deionized waters are added to 40mL polytetrafluoroethyl-nes
In the reaction kettle of alkene liner, 12h is reacted at 170 DEG C；
2) it and then by reaction kettle is cooled to room temperature, remaining cellulose residue filter is detached using filter paper, passes through liquid separation
Device separates ionic liquid phase liquid, obtains ionic liquid phase and water phase, and the hydrolysate of wherein microcrystalline cellulose is mainly deposited
It is in water phase, a small amount of hydrolysate is present in ionic liquid phase；
3) it adds in a small amount of fresh deionized water into ionic liquid phase, continues lock out operation with dispenser after fully shaking,
The hydrolysate washes clean in ionic liquid, the ionic liquid of recycling can repeatedly be may be reused after washing separation；
4) cleaning solution in step 3) with the water phase in step 2) is merged, quantitative analysis is carried out to product in the water phase,
The results are shown in Table 1.
Table 1：
Fig. 3 is to prepare the acidic ionic liquid catalysts obtained in embodiment 1 during catalyzing hydrolysis microcrystalline cellulose,
Catalyst rate of charge and cellulose conversion ratio and the relation schematic diagram (reaction condition of glucose and levulic acid：Microcrystalline cellulose
Element：0.5g, reaction temperature：170 DEG C, the reaction time：12h).
As shown in figure 3, cellulose conversion ratio and glucose and levulic acid can selectively increase with catalyst inventory
Add and change, be embodied in cellulose conversion ratio and increase, glucose selective reduces and levulic acid selectively increases.
Claims (10)
1. a kind of temperature sensitive acidic ionic liquid, the ionic liquid is quaternary ammonium salt and the acid ion of fluorine-containing acid molecule synthesis
Liquid.
2. temperature sensitive acidic ionic liquid according to claim 1, which is characterized in that the quaternary ammonium salt in the ionic liquid
One kind in choline, choline chloride, glycine betaine and empgen BB, preferably glycine betaine or dodecyl beet
Alkali.
3. temperature sensitive acidic ionic liquid according to claim 1, which is characterized in that the fluoric-containing acid in the ionic liquid
Property molecule be selected from least one of tetrafluoro boric acid, trifluoromethanesulfonic acid and double trifluoromethanesulfonic acid acid imides.
4. temperature sensitive acidic ionic liquid according to claim 1, which is characterized in that the ionic liquid is at normal temperatures
Solid-state puts into and restores liquid phase state in water；Ionic liquid is completely soluble in water after temperature is higher than 60 DEG C, is formed with water
Homogeneous catalysis system, when temperature is gradually reduced as below room temperature, ion liquid dissolving degree reduces and is gradually precipitated from water, weight
It is new to restore biliquid phase system.
5. the preparation method of temperature sensitive acidic ionic liquid as claimed in any of claims 1 to 4, the preparation side
Method includes the following steps：
(1) it is 1 according to molar ratio by quaternary ammonium salt and fluorine-containing acidic molecular:1 adds in input water, is stirred at a temperature of 30~80 DEG C
React 0.5~4h；
(2) reaction system is down to after room temperature removes water by rotary evaporation in vacuo and can obtain cured temperature sensitive acidic ionic
Liquid；
Preferably, quaternary ammonium salt described in step (1) in choline, choline chloride, glycine betaine and empgen BB one
Kind, more preferably glycine betaine or empgen BB；
Preferably, it is sub- to be selected from tetrafluoro boric acid, trifluoromethanesulfonic acid and double trifluoromethanesulfonic acid acyls for fluorine-containing acidic molecular described in step (1)
One kind in amine.
6. the preparation method of temperature sensitive acidic ionic liquid according to claim 5, which is characterized in that institute in step (1)
It is 50~70 DEG C to state temperature sensitive acidic ionic liquid synthesis temperature, and generated time is 1~2h；
Preferably, the synthesis of temperature sensitive acidic ionic liquid described in step (2) terminates after being cooled to room temperature, temperature sensitive acidic ionic
Liquid catalyst is separated from the water to form biliquid phase structure, then hangs water and rear temperature sensitive acidic ionic liquid is evaporated off gradually admittedly
Change, then by cured temperature sensitive acidic ionic liquid, dry 12h, taking-up can obtain temperature sensitive type acid under 40 DEG C of vacuum conditions
Property ionic-liquid catalyst.
7. temperature sensitive acidic ionic liquid as claimed in any of claims 1 to 4 is in catalyzing hydrolysis microcrystalline cellulose
In purposes.
8. a kind of use temperature sensitive acidic ionic liquid catalyzing hydrolysis crystallite as claimed in any of claims 1 to 4
The method of cellulose, the described method comprises the following steps：
1) it is 0.5 by mass ratio:1 to 8:1 temperature sensitive acidic ionic liquid is put into water jointly with microcrystalline cellulose, water with it is micro-
The mass ratio of crystalline cellulose is 20:1 to 40:1, in the reactor at a temperature of 130~200 DEG C, reaction 3~for 24 hours；
2) reaction kettle cooled to room temperature after reaction, remaining cellulose residue filter is detached, pass through using filter paper
Dispenser separates ionic liquid phase liquid, obtains the hydrolysate master of ionic liquid phase and water phase, wherein microcrystalline cellulose
It is present in water phase, a small amount of hydrolysate is present in ionic liquid phase；
3) it adds in a small amount of fresh deionized water into ionic liquid phase, continues lock out operation with dispenser after fully shaking, repeatedly
The hydrolysate washes clean in ionic liquid, the ionic liquid of recycling can be may be reused after washing separation；
4) cleaning solution in step 3) with the water phase in step 2) is merged, quantitative analysis is carried out to product in the water phase.
9. the method for hydrolyzing microcrystalline cellulose according to claim 8, which is characterized in that preferably, described in step 1)
Ionic-liquid catalyst and microcrystalline cellulose mass ratio are preferably 2:1 to 6:1, more preferably 1:1 to 6:1, more preferably 1:1；
Preferably, reaction temperature described in step 1) is preferably 150~170 DEG C, and the reaction time is preferably 6~12h；
Preferably, dispenser described in step 2) can be separatory funnel.
10. the method for hydrolyzing microcrystalline cellulose according to claim 8, which is characterized in that the catalyzing hydrolysis crystallite is fine
The method of dimension element does not use other inorganic acids or organic acid, does not use other catalyst.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113005459A (en) * | 2021-02-23 | 2021-06-22 | 常州工学院 | Ionic liquid compound corrosion inhibitor and application thereof |
| CN116217790A (en) * | 2023-03-15 | 2023-06-06 | 普立思生物科技有限公司 | Polyion liquid for biomass pretreatment and application method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007147222A2 (en) * | 2006-06-21 | 2007-12-27 | Katholieke Universiteit Leuven | Novel ionic liquids |
| WO2008115250A3 (en) * | 2006-07-03 | 2008-12-31 | Matheson Tri Gas Inc | Fluid storage and purification method and system using ionic liquid in particular di-imidazolium cation |
| CN102989513A (en) * | 2012-11-28 | 2013-03-27 | 华中农业大学 | Acidic ionic liquid catalyst, synthesis method thereof, and method for catalyzing microcrystalline cellulose hydrolysis |
| CN104016853A (en) * | 2014-06-09 | 2014-09-03 | 大连理工大学 | Method for preparing acetylpropionic acid by catalytically converting lignocelluloses |
| CN105315164A (en) * | 2014-08-01 | 2016-02-10 | 中国科学院大连化学物理研究所 | Environment-friendly choline ionic liquid and preparation method therefor |
| CN106398742A (en) * | 2016-12-12 | 2017-02-15 | 青岛科技大学 | Method for preparing alkylation gasoline by polyether type acid ionic liquid coupling trifluoromethanesulfonic acid catalysis |
| CN106632855A (en) * | 2016-10-21 | 2017-05-10 | 天津工业大学 | Multifunctional high-strength gel and preparation method thereof |
-
2018
- 2018-01-29 CN CN201810082919.8A patent/CN108212212A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007147222A2 (en) * | 2006-06-21 | 2007-12-27 | Katholieke Universiteit Leuven | Novel ionic liquids |
| WO2008115250A3 (en) * | 2006-07-03 | 2008-12-31 | Matheson Tri Gas Inc | Fluid storage and purification method and system using ionic liquid in particular di-imidazolium cation |
| CN102989513A (en) * | 2012-11-28 | 2013-03-27 | 华中农业大学 | Acidic ionic liquid catalyst, synthesis method thereof, and method for catalyzing microcrystalline cellulose hydrolysis |
| CN104016853A (en) * | 2014-06-09 | 2014-09-03 | 大连理工大学 | Method for preparing acetylpropionic acid by catalytically converting lignocelluloses |
| CN105315164A (en) * | 2014-08-01 | 2016-02-10 | 中国科学院大连化学物理研究所 | Environment-friendly choline ionic liquid and preparation method therefor |
| CN106632855A (en) * | 2016-10-21 | 2017-05-10 | 天津工业大学 | Multifunctional high-strength gel and preparation method thereof |
| CN106398742A (en) * | 2016-12-12 | 2017-02-15 | 青岛科技大学 | Method for preparing alkylation gasoline by polyether type acid ionic liquid coupling trifluoromethanesulfonic acid catalysis |
Non-Patent Citations (1)
| Title |
|---|
| YAN WANG ET AL.: "Catalytic alcoholysis of bagasse cellulose for the total reducing sugars with temperature-sensitive phase-variable ionic liquid", 《SEPARATION SCIENCE AND TECHNOLOGY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113005459A (en) * | 2021-02-23 | 2021-06-22 | 常州工学院 | Ionic liquid compound corrosion inhibitor and application thereof |
| CN113005459B (en) * | 2021-02-23 | 2023-05-30 | 常州工学院 | Ionic liquid compound corrosion inhibitor and application thereof |
| CN116217790A (en) * | 2023-03-15 | 2023-06-06 | 普立思生物科技有限公司 | Polyion liquid for biomass pretreatment and application method thereof |
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