CN108997596A - A method of from preparing reuse ionic liquid in cellulose nano-fibrous waste liquid - Google Patents
A method of from preparing reuse ionic liquid in cellulose nano-fibrous waste liquid Download PDFInfo
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- CN108997596A CN108997596A CN201810750193.0A CN201810750193A CN108997596A CN 108997596 A CN108997596 A CN 108997596A CN 201810750193 A CN201810750193 A CN 201810750193A CN 108997596 A CN108997596 A CN 108997596A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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Abstract
The invention discloses a kind of from the method for preparing reuse ionic liquid in cellulose nano-fibrous waste liquid, including using solvent pairs to carry out extraction and separation to cellulose nano-fibrous waste liquid is prepared；Extraction phase reduced pressure at room temperature is distilled, rotation extraction raffinate is collected and is dried in vacuo；Solvent is added to desciccate, acid anhydrides is precipitated, centrifuge separation is evaporated under reduced pressure supernatant, the ionic liquid recycled.In the present invention, recycle ionic liquid method is easy to operate, mild condition and does not introduce secondary pollution, with the potentiality for being applied to industrialized production, the rate of recovery of ionic liquid is higher, it may be implemented to recycle, the extractant and solvent of addition involved in removal process simultaneously can be achieved high efficiente callback and recycle, and realize greenization production.
Description
Technical field
The invention belongs to the fields of chemical waste fluid processing, more particularly, to a kind of from preparing cellulose nano-fibrous waste liquid
The method of middle recycling quaternary ammonium salt ionic liquid.
Background technique
Cellulose is the natural organic matter of rich reserves in nature, has renewable, degradable, biological close friend etc. excellent
Point is widely used in fields such as pulping and paper-making, weaving, pharmacy and high molecular materials.However, as a kind of reproducible biomass
Resource there are a large amount of intramoleculars and intermolecular hydrogen bonding and has higher crystallinity in cellulose, causes it insoluble in mostly often
It advises in solvent, it is difficult to be used directly, therefore its application is hindered.The development and application of cellulose are always to close in world wide
The hot spot of note, wherein the solvent for studying dissolved cellulose has very important significance.Ionic liquid is molten as a kind of green
Agent has many advantages, such as non-volatile, difficult oxidation, broad potential window, high extracting power, thermal stability and favorable solubility, answers extensively
For fields such as organic synthesis, electrochemistry, substance separation, biocatalysis.Ionic liquid is to the high polymer including cellulose
With very strong solvability, the tight structure of cellulose can be destroyed, and reduces internal crystallization degree.
Mixed solution made of ionic liquid and non-proton organic cosolvent has excellent solute effect to cellulose, adds
The modification to cellulose may be implemented in acid adding acid anhydride.But since the ionic liquid being related to is very expensive, and dissolve cellulose
If mixed solution is expelled directly out can biggish pollution to water body, therefore how research separates cosolvent and recycling ionic liquid pair
The waste liquid of cellulose nano-fibrous preparation application be very it is necessary to.In industrialized production, ionic liquid must be carried out
Effectively recycling, and guarantee that its rate of recovery is higher, the waste liquid of the cellulose nano-fibrous preparation just has practice significance.
Currently, what is used recycles the main of ionic liquid according to architectural characteristic and the physicochemical properties of ionic liquid
Method includes conventional vacuum distillation, molecular distillation, UF membrane, saltout, adsorb, aqueous two-phase separation and liquid-liquid extraction etc., is removed
The method of impurity mainly has solvent deposition method, microwave assisting method, fused junction crystallization etc..Due to considering the recycling ionic liquid
Method be applied to industrialized production circulation in, the recovery process of selection needs to have easy to operate, energy conservation, separating medium can
Regeneration does not introduce secondary pollution, damages the advantages that minimum, the rate of recovery is high to instrument, to guarantee the repeatable circulation of recovery system
Property.From the point of view of the recovery method of current ionic liquid, there are no the methods for being able to satisfy this requirement.
Summary of the invention
Goal of the invention: the object of the present invention is to provide a kind of from preparing high efficiente callback season in cellulose nano-fibrous waste liquid
The method of Ammonium Salt Ionic Liquid, to realize the separation of ionic liquid and reuse and avoid ionic liquid secondary pollution.
Technical solution: in order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention are as follows:
A method of from reuse ionic liquid in cellulose nano-fibrous waste liquid is prepared, steps are as follows:
1) it is extracted using methylene chloride-water double solvent extraction system to cellulose nano-fibrous waste liquid is prepared, it is quiet
It postpones ionic liquid and dimethyl sulfoxide respectively enters methylene chloride phase and water phase；
2) collect methylene chloride extraction phase, rotary evaporation remove solvent, obtain rotation extraction raffinate juxtaposition in a vacuum drying oven into
Row drying；
3) it is uniform that stirring solvent is added into thick substance to dry, supernatant is repeatedly collected after centrifugation, in room temperature
Lower vacuum distillation obtains ionic liquid regenerant, is back to cellulose dissolution.
In step 1), the waste liquid contains quaternary ammonium salt ionic liquid, dimethyl sulfoxide and anhydride component, wherein quaternary ammonium
Mass percent concentration of the ionic liquid in waste liquid is 1% or more.
In step 1), the waste liquid of cellulose nano-fibrous preparation is in methylene chloride-water used in the extraction process
Mass percent concentration is 5%~25% in extraction system.
In step 1), the mass concentration ratio of methylene chloride/water is 1~10: 1 in the extraction process.
In step 1), the number of the extraction is 1 time or more, and extraction time of repose is not less than 5min.
In step 2), the vacuum drying uses the vacuum freeze drying that temperature is -50 DEG C, vacuum degree is 20Pa
Machine, drying time are not less than 6h.
In step 3), the solvent includes one of methylene chloride, chloroform, n-butanol and water.
In step 3), the additional amount of the solvent is 5~20 times for being dried in vacuo product quality, and mixing time is
10min。
In step 3), the centrifugation is centrifuged in the centrifuge high speed that centrifugal rotational speed is 12500rpm, centrifugation time
For 10min.
The utility model has the advantages that compared with prior art, the present invention its remarkable advantage is:
1) quaternary ammonium salt ionic liquid recovery method of the invention has easy to operate, mild condition and does not introduce secondary dirt
The advantages that dye, can be applied to industrialized production.
2) it recycles to obtain in substance using this method, the ionic liquid rate of recovery can achieve 98.62%, and purity is much higher than institute
The requirement for needing ionic liquid homogeneous reaction realizes effective recycling of ionic liquid.
3) recycling substance can reconstitute with cosolvent prepares cellulose nano-fibrous solution, realizes recovery product again
It utilizes.
4) high efficiente callback recycling can be achieved in the extractant and organic solvent of addition involved in method.
Detailed description of the invention
Fig. 1 is mixture after embodiment 1 recycles13CNMR spectrogram；
Fig. 2 is mixture after embodiment 1 recycles1HNMR spectrogram；
Fig. 3 be embodiment 2 recycle after ionic liquid/dimethyl sulfoxide mixed liquor to cellulose dissolution 1min, 3h and 12h
Electron micrograph figure.
Specific embodiment
The present invention will now be described in detail with reference to examples.Cellulose nanometer is prepared used in following embodiment
The waste liquid of fiber, main component are as follows: quaternary ammonium salt ionic liquid (mass percent is greater than 1%), dimethyl sulfoxide and acid anhydrides,
The mass percent concentration of middle quaternary ammonium salt ionic liquid refers both to mass percent concentration of the ionic liquid in waste liquid.
Embodiment 1
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 1 time, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 15% of system gross mass, and the mass concentration ratio of methylene chloride/water is 10: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) methylene chloride of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed on magnetic stirring apparatus
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged at 12500rpm using desk centrifuge
10min is repeatedly centrifugated out acid anhydrides, collects supernatant, and reduced pressure at room temperature distills collection of ions liquids recovery object.
As shown in Figure 1 and Figure 2, the material composition in regenerant and chemical structure are measured by nuclear magnetic spectrogram,13In CNMR spectrogram
A, peak corresponding to b, c, d, e, f and1In HNMR spectrogram peak corresponding to A, B, C, D, E prove removal process obtained in from
Sub- liquid is identical as the quaternary ammonium salt ionic liquid initially used, and structure does not change.
The ionic liquid rate of recovery is 94.02%.The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, in room temperature
It is lower that the dissolution for realizing cellulose is uniformly mixed with 1wt% pulpboard.
Embodiment 2
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 1 time, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 15% of system gross mass, and the mass concentration ratio of methylene chloride/water is 5: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) methylene chloride of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed on magnetic stirring apparatus
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged at 12500rpm using desk centrifuge
10min is repeatedly centrifugated out acid anhydrides, collects supernatant, and reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid rate of recovery is 85.09%.The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, in room temperature
It is lower that the dissolution for realizing cellulose is uniformly mixed with 1wt% pulpboard.
As shown in figure 3, adding dimethyl sulfoxide into regenerant forms mixed liquor, re-apply in the molten of cellulose
Solution.When dissolving 1min at room temperature, cellulose is very thin backbone in the visual field；When dissolving 3h, cellulose long-chain part
It is broken or is dissolved as short fragment；When dissolving 12h, the visual field is entirely dark, shows that cellulose is completely dissolved.Therefore ion after the recovery
Liquid can re-apply the dissolution in cellulose.
Embodiment 3
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 1 time, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 15% of system gross mass, and the mass concentration ratio of methylene chloride/water is 1: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) methylene chloride of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed on magnetic stirring apparatus
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged at 12500rpm using desk centrifuge
10min is repeatedly centrifugated out acid anhydrides, collects supernatant, and reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid rate of recovery is 43.32%.The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, in room temperature
It is lower that the dissolution for realizing cellulose is uniformly mixed with 1wt% pulpboard.
Embodiment 4
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 1 time, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 5% of system gross mass, and the mass concentration ratio of methylene chloride/water is 5: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) methylene chloride of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed on magnetic stirring apparatus
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged at 12500rpm using desk centrifuge
10min is repeatedly centrifugated out acid anhydrides, collects supernatant, and reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid rate of recovery is 79.06%.The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, in room temperature
It is lower that the dissolution for realizing cellulose is uniformly mixed with 1wt% pulpboard.
Embodiment 5
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 1 time, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 25% of system gross mass, and the mass concentration ratio of methylene chloride/water is 5: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) methylene chloride of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed on magnetic stirring apparatus
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged at 12500rpm using desk centrifuge
10min is repeatedly centrifugated out acid anhydrides, collects supernatant, and reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid rate of recovery is 81.26%.The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, in room temperature
It is lower that the dissolution for realizing cellulose is uniformly mixed with 1wt% pulpboard.
Embodiment 6
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 2 times, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 15% of system gross mass, and the mass concentration ratio of methylene chloride/water is 5: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) methylene chloride of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed on magnetic stirring apparatus
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged at 12500rpm using desk centrifuge
10min is repeatedly centrifugated out acid anhydrides, collects supernatant, and reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid rate of recovery is 88.72%.The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, in room temperature
It is lower that the dissolution for realizing cellulose is uniformly mixed with 1wt% pulpboard.
Embodiment 7
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 3 times, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 15% of system gross mass, and the mass concentration ratio of methylene chloride/water is 5: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) methylene chloride of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed on magnetic stirring apparatus
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged at 12500rpm using desk centrifuge
10min is repeatedly centrifugated out acid anhydrides, collects supernatant, and reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid rate of recovery is 95.43%.The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, in room temperature
It is lower that the dissolution for realizing cellulose is uniformly mixed with 1wt% pulpboard.
Embodiment 8
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 1 time, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 15% of system gross mass, and the mass concentration ratio of methylene chloride/water is 5: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) chloroform of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed on magnetic stirring apparatus
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged at 12500rpm using desk centrifuge
10min is repeatedly centrifugated out acid anhydrides, collects supernatant, and reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid rate of recovery is 83.44%.The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, in room temperature
It is lower that the dissolution for realizing cellulose is uniformly mixed with 1wt% pulpboard.
Embodiment 9
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 1 time, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 15% of system gross mass, and the mass concentration ratio of methylene chloride/water is 5: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) n-butanol of its 5 times of quality is added into vacuum drying product, is existed on magnetic stirring apparatus with 500rpm revolving speed
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged 10min at 12500rpm using desk centrifuge,
It is repeatedly centrifugated out acid anhydrides, collects supernatant, reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid rate of recovery is 85.10%.The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, in room temperature
It is lower that the dissolution for realizing cellulose is uniformly mixed with 1wt% pulpboard.
Embodiment 10
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 1 time, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 15% of system gross mass, and the mass concentration ratio of methylene chloride/water is 5: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) water of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed in room temperature on magnetic stirring apparatus
Under be stirred.Substance after stirring is transferred in centrifuge tube, is centrifuged 10min at 12500rpm using desk centrifuge, repeatedly
It is centrifugated out acid anhydrides, collects supernatant, reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid rate of recovery is 67.29%.The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, in room temperature
It is lower that the dissolution for realizing cellulose is uniformly mixed with 1wt% pulpboard.
Embodiment 11
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 1 time, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 15% of system gross mass, and the mass concentration ratio of methylene chloride/water is 5: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) methylene chloride of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed on magnetic stirring apparatus
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged at 12500rpm using desk centrifuge
10min is repeatedly centrifugated out acid anhydrides, collects supernatant, and reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, is uniformly mixed at room temperature with 1wt% pulpboard real
The dissolution of existing cellulose is centrifuged and carries out washing to cellulose and collect supernatant, carries out the recycling of ionic liquid again.Ionic liquid
Body recovered frequency is 2 times, the rate of recovery 83.95%.
Embodiment 12
A method of quaternary ammonium salt ionic liquid being recycled in cellulose nano-fibrous waste liquid from preparing, steps are as follows:
1) fetch from prepare cellulose nano-fibrous waste liquid 3g (containing mass percent concentration for 5% quaternary ammonium salt from
Sub- liquid), sequentially add methylene chloride, water is uniformly mixed, and stands 10min, extraction times are 1 time, keep most of dimethyl sub-
Sulfone enters water phase.Wherein, waste liquid quality accounts for the 15% of system gross mass, and the mass concentration ratio of methylene chloride/water is 5: 1.
2) lower layer's methylene chloride extraction phase is collected, at room temperature rotary evaporation 20min, extremely there is no liquid to distillate for observation,
Rotation extraction raffinate is collected, the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, vacuum dried sample 12h are used.
3) methylene chloride of its 5 times of quality is added into vacuum drying product, with 500rpm revolving speed on magnetic stirring apparatus
It is stirred at room temperature.Substance after stirring is transferred in centrifuge tube, is centrifuged at 12500rpm using desk centrifuge
10min is repeatedly centrifugated out acid anhydrides, collects supernatant, and reduced pressure at room temperature distills collection of ions liquids recovery object.
The ionic liquid obtained after recycling rejoins dimethyl sulfoxide, is uniformly mixed at room temperature with 1wt% pulpboard real
The dissolution of existing cellulose is centrifuged and carries out washing to cellulose and collect supernatant, carries out the recycling of ionic liquid again.Ionic liquid
Body recovered frequency is 3 times, the rate of recovery 74.33%.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (9)
1. a kind of from the method for preparing reuse ionic liquid in cellulose nano-fibrous waste liquid, which is characterized in that steps are as follows:
1) it is extracted using methylene chloride-water double solvent extraction system to cellulose nano-fibrous waste liquid is prepared, after standing
Ionic liquid and dimethyl sulfoxide respectively enter methylene chloride phase and water phase；
2) methylene chloride extraction phase is collected, rotary evaporation removes solvent, obtains rotation extraction raffinate juxtaposition and is done in a vacuum drying oven
It is dry；
3) it is uniform that stirring solvent is added into thick substance to dry, supernatant is repeatedly collected after centrifugation, subtracts at room temperature
Pressure distillation obtains ionic liquid regenerant, is back to cellulose dissolution.
2. it is according to claim 1 from the method for preparing reuse ionic liquid in cellulose nano-fibrous waste liquid, it is special
Sign is, in step 1), the waste liquid contains quaternary ammonium salt ionic liquid, dimethyl sulfoxide and anhydride component, wherein quaternary ammonium salt
Mass percent concentration of the ionic liquid in waste liquid is 1% or more.
3. it is according to claim 1 from the method for preparing reuse ionic liquid in cellulose nano-fibrous waste liquid, it is special
Sign is, in step 1), in extraction process, and mass percent concentration of the waste liquid used in methylene chloride-water extraction system
It is 5%~25%.
4. it is according to claim 1 from the method for preparing reuse ionic liquid in cellulose nano-fibrous waste liquid, it is special
Sign is, in step 1), the mass concentration ratio of methylene chloride/water is 1~10: 1 in the extraction process.
5. it is according to claim 1 from the method for preparing reuse ionic liquid in cellulose nano-fibrous waste liquid, it is special
Sign is, in step 1), the number of extraction is 1 time or more, and extraction time of repose is not less than 5min.
6. it is according to claim 1 from the method for preparing reuse ionic liquid in cellulose nano-fibrous waste liquid, it is special
Sign is, in step 2), vacuum drying uses the vacuum freeze drier that temperature is -50 DEG C, vacuum degree is 20Pa, dry
Time is not less than 6h.
7. it is according to claim 1 from the method for preparing reuse ionic liquid in cellulose nano-fibrous waste liquid, it is special
Sign is, in step 3), the solvent is selected from methylene chloride, chloroform, n-butanol and water.
8. it is according to claim 1 from the method for preparing reuse ionic liquid in cellulose nano-fibrous waste liquid, it is special
Sign is, in step 3), the additional amount of the solvent is 5~20 times for being dried in vacuo product quality, and mixing time is
10min。
9. it is according to claim 1 from the method for preparing reuse ionic liquid in cellulose nano-fibrous waste liquid, it is special
Sign is, in step 3), the centrifugation is centrifuged in the centrifuge high speed that centrifugal rotational speed is 12500rpm, and centrifugation time is
10min。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880131A (en) * | 2019-01-25 | 2019-06-14 | 华中科技大学 | A kind of ionic liquid plasticized fibre element clean method for preparing |
| CN114044755A (en) * | 2021-10-25 | 2022-02-15 | 惠州市绿色能源与新材料研究院 | Efficient ionic liquid decoloring and purifying method |
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| CN102677510A (en) * | 2011-03-11 | 2012-09-19 | 中国科学院过程工程研究所 | Method for separating cellulose and lignin from plant fiber raw material by utilizing ion liquid |
| CN102797187A (en) * | 2012-09-07 | 2012-11-28 | 南开大学 | Method for extracting cellulose in biomass raw material by utilizing ionic liquid |
| WO2016005920A2 (en) * | 2014-07-09 | 2016-01-14 | Reliance Industries Limited | Method for recovery of ionic liquid and system thereof |
| CN107245766A (en) * | 2017-07-03 | 2017-10-13 | 南京林业大学 | A kind of cellulose nano-fibrous preparation method of low energy consumption |
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Patent Citations (4)
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| CN102677510A (en) * | 2011-03-11 | 2012-09-19 | 中国科学院过程工程研究所 | Method for separating cellulose and lignin from plant fiber raw material by utilizing ion liquid |
| CN102797187A (en) * | 2012-09-07 | 2012-11-28 | 南开大学 | Method for extracting cellulose in biomass raw material by utilizing ionic liquid |
| WO2016005920A2 (en) * | 2014-07-09 | 2016-01-14 | Reliance Industries Limited | Method for recovery of ionic liquid and system thereof |
| CN107245766A (en) * | 2017-07-03 | 2017-10-13 | 南京林业大学 | A kind of cellulose nano-fibrous preparation method of low energy consumption |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880131A (en) * | 2019-01-25 | 2019-06-14 | 华中科技大学 | A kind of ionic liquid plasticized fibre element clean method for preparing |
| CN109880131B (en) * | 2019-01-25 | 2020-11-17 | 华中科技大学 | Clean manufacturing method of ionic liquid plasticized cellulose |
| CN114044755A (en) * | 2021-10-25 | 2022-02-15 | 惠州市绿色能源与新材料研究院 | Efficient ionic liquid decoloring and purifying method |
| CN114044755B (en) * | 2021-10-25 | 2023-09-22 | 惠州市绿色能源与新材料研究院 | Decolorization and purification method for ionic liquid |
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| CN108997596B (en) | 2020-12-15 |
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