CN106350064B - The method for preparing water soluble fluorescence carbon material using microwave heating method hydro-thermal charing black liquid - Google Patents
The method for preparing water soluble fluorescence carbon material using microwave heating method hydro-thermal charing black liquid Download PDFInfo
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- CN106350064B CN106350064B CN201610761060.4A CN201610761060A CN106350064B CN 106350064 B CN106350064 B CN 106350064B CN 201610761060 A CN201610761060 A CN 201610761060A CN 106350064 B CN106350064 B CN 106350064B
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Abstract
The invention discloses a kind of methods for preparing water soluble fluorescence carbon material using microwave heating method hydro-thermal charing black liquid, carbon material is prepared as the processing method of the environmentally protective macromolecule organic matter occurred in recent years using hydro-thermal charing, it is low in cost, reaction condition is relatively mild, and surface, which can be obtained, the new carbon of good aqueous solubility of abundant functional group.The present invention is using black liquid as raw material, in microwave high pressure reaction kettle, by microwave heating, hydro-thermal carbonization reaction is carried out in 180~250 DEG C of reaction temperature, 1~6h of reaction time, product is filtered using the funnel that aperture is 1.5-2.5 μm after the reaction was completed, obtains dark brown solution.This dark brown solution is then poured into molecular cut off it is at least 3500 bag filter and dialyse, water-soluble fluorescence carbon material has been obtained in bag filter.This carbon dots solution at 225nm other than having precipitous absorption peak, and there are also relatively weak ultraviolet characteristic absorption peaks at 350nm.After water soluble fluorescence carbon material resulting in bag filter freeze-drying, the yellow solid carbon material powder of particle diameter about 10nm or so is obtained.
Description
Technical field
The present invention relates to a kind of methods for preparing water soluble fluorescence carbon material, utilize black liquid system more particularly to a kind of
The method of standby water soluble fluorescence carbon material, is applied to sewage treatment and changing rejected material to useful resource technical field.
Background technique
In recent years, the paper waste produced pollution is only second to metallurgy, petrochemical industry occupies third, and discharge amount accounts for about whole industry
The 1/6 of wastewater discharge, wherein 90% of the total paper waste of black liquor Zhan caused by pulping process, if direct without handling
Discharge will seriously destroy ecological environment.
Main component contained in black liquid is lignin and its catabolite.Lignin is by guaiacyl, purple fourth
Perfume base and p-hydroxyphenyl structural unit form high-molecular compound.Due to its complicated structure, its industrialized utilization is limited.Have
The hydro-thermal charing of machine matter prepares carbon material, and reaction condition is mild, less energy intensive, and it is to carry out in aqueous solution, without to original
Material carries out the drying process of early period, avoids organic solvent bring problem of environmental pollution, is a kind of friendly process process.But by
In the temperature that hydro-thermal carbonizes mostly at 350 DEG C hereinafter, comparing relatively straightforward high temperature pyrolysis process at least 600 DEG C or more high temperature, temperature
Very low, charing efficiency is relatively low.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The method for preparing water soluble fluorescence carbon material using microwave heating method hydro-thermal charing black liquid, is carbonized using microwave heating hydro-thermal
Method, convert the water-soluble fluorescent carbon of high added value for the organic pollutant that main component in black liquid is lignin
Material eliminates paper-making black liquor, realizes environment and economical effects.The present invention is made by the charing of microwave heating Direct Hydrothermal
Paper black liquor, does not need catalyst, can prepare water-soluble fluorescence carbon material, and simple process has efficient, environmental protection, green
The features such as.
Purpose is created to reach foregoing invention, the present invention uses following inventive concepts:
Improved the practical application for being undoubtedly conducive to hydro-thermal charring by the effect in outfield, microwave is that frequency about exists
Electromagnetic wave within the scope of 300MHz~300GHz, compared to traditional heating method, microwave technology is promoting chemical reaction course
There is unique advantage with reaction speed and the selectivity of product aspect etc..It is micro- other than fuel factor under this heating condition
The variation of wave field frequency will lead to reactant molecule and reach dynamic balance state by moving or rotating generation torque, and molecule is caused to transport
Move has certain orientation on microcosmic, improves effective collision probability, to accelerate chemical reaction rate, improve reaction yield and selection
Property.Therefore, hydro-thermal carbonization process can be strengthened using microwave heating, is conducive to prepare water soluble fluorescence using charing black liquid
The realization of carbon material technique.
Conceived according to foregoing invention, the present invention adopts the following technical solutions:
A method of water soluble fluorescence carbon material being prepared using microwave heating method hydro-thermal charing black liquid, including as follows
Step:
A. hydro-thermal charring process: black liquid is added in microwave reaction kettle, is carried out at being 180-250 DEG C in temperature
Hydro-thermal carbonization reaction is carried out in the reaction time of 1-6h；As currently preferred technical solution, in the case where temperature is 220-240 DEG C
It carries out carrying out hydro-thermal carbonization reaction in the reaction time of 3-4h；
B. the separation of water soluble fluorescence carbon material: after hydro-thermal carbonization reaction in the step a, to reaction kettle
After cooled to room temperature, then product after reaction taken out from reaction kettle, then using aperture be 1.5-2.5 μm funnel into
Row filters, and obtains dark brown solution, then by this dark brown solution pour into molecular cut off be at least 3500 bag filter carry out it is saturating
Analysis, the solution finally obtained in bag filter, as with the water-soluble carbon dots solution of fluorescent characteristic；It is preferable to use the leakages of G5 sand core
Bucket filters product；
C. water soluble fluorescence carbon material is collected: by the resulting water solubility carbon dots solution in bag filter in the step b
After freeze-drying, yellow solid carbon material powder, as water soluble fluorescence carbon material are obtained.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. main component in black liquid is wooden by the method that the present invention enhances hydro-thermal charing using microwave heating
The organic pollutant of plain class, is converted into the water soluble fluorescence carbon material of high added value, solves paper-making black liquor, realize environment with
Economical effects；
2. hydro-thermal charing of the present invention prepares place of the carbon material as the environmentally protective macromolecule organic matter occurred in recent years
Reason method, low in cost, reaction condition is relatively mild, and surface, which can be obtained, the novel carbon materials of good aqueous solubility of abundant functional group
Material.
Detailed description of the invention
Fig. 1 is the UV-visible spectrum of water-soluble carbon dots solution prepared by the embodiment of the present invention one.
Fig. 2 is transmission electron microscope (TEM) image of water soluble fluorescence carbon material prepared by the embodiment of the present invention one.
Specific embodiment
Details are as follows for the preferred embodiment of the present invention:
Embodiment one:
In the present embodiment, referring to Fig. 1 and Fig. 2, a kind of utilization microwave heating method hydro-thermal charing black liquid is prepared water-soluble
The method of property fluorescence carbon material, includes the following steps:
A. the 300ml black liquid black liquid containing lignin 30% hydro-thermal charring process: is added to microwave reaction kettle
In, setting temperature is 240 DEG C, carries out the hydro-thermal carbonization reaction of 3h at this temperature；
B. the separation of water soluble fluorescence carbon material: after hydro-thermal carbonization reaction in the step a, to reaction kettle
After cooled to room temperature, then product after reaction taken out from reaction kettle, the G5 sand core for the use of aperture being then 1.5-2.5 μm
Funnel is filtered, and dark brown solution is obtained, this dark brown solution is then poured into the bag filter that molecular cut off is 3500 and is carried out
Dialysis, the solution finally obtained in bag filter, as with the water-soluble carbon dots solution of fluorescent characteristic；
C. water soluble fluorescence carbon material is collected: by the resulting water solubility carbon dots solution in bag filter in the step b
After freeze-drying, yellow solid carbon material powder, as water soluble fluorescence carbon material are obtained.
Experimental test and analysis:
The water soluble fluorescence carbon material point of water-soluble carbon dots solution and step c preparation to the step b preparation of the present embodiment
It carry out not experimental test and analysis.Fig. 1 be step b preparation water-soluble carbon dots solution UV-visible spectrum, in addition to
Have outside precipitous absorption peak at 225nm, there are also relatively weak ultraviolet characteristic absorption peaks at 350nm.Fig. 2 is to be by molecular weight
After 3500 bag filter dialysis, transmission electron microscope (TEM) image of gained yellow solid carbon dots powder after solution is lyophilized in bag filter,
That is the water-soluble fluorescent carbon material transmission sem image of step c preparation.Its particle diameter is close to 10nm as seen from Figure 2.This implementation
The aqueous solution of the water soluble fluorescence carbon material of example preparation is placed 1 week at room temperature, without any apparent sedimentation, is shown
Steady in a long-term is homogeneous.The aqueous solution of water soluble fluorescence carbon material manufactured in the present embodiment Continuous irradiation under 365nm exciting light
30min, fluorescence intensity is almost unchanged, shows it with excellent anti-light Bleachability, be conducive to carbon dots cell-targeting tracer, at
The application of picture etc..In addition, sodium chloride of the aqueous solution of water soluble fluorescence carbon material manufactured in the present embodiment in 0-2.0M is dense
It spends in range, fluorescence intensity is also basicly stable constant, illustrates there is good saline-alkaline tolerance, is conducive to it in biochemical analysis and detection
The application of aspect.
Since lignin is the main component of black liquid, direct emission will cause very big destruction to environment.This implementation
Example hydro-thermal charing prepares processing method of the carbon material as the environmentally protective macromolecule organic matter occurred in recent years, at low cost
Honest and clean, reaction condition is relatively mild, and surface, which can be obtained, the new carbon of good aqueous solubility of abundant functional group.This patent is to make
Paper black liquor is raw material, in microwave high pressure reaction kettle, by microwave heating, carries out hydro-thermal carbonization reaction, after the reaction was completed product
It is filtered using G5 sand core funnel, obtains dark brown solution.It is 3500 that this dark brown solution, which is then poured into molecular cut off,
Bag filter is dialysed, and water-soluble fluorescence carbon material has been obtained in bag filter.This carbon dots solution is precipitous in addition to having at 225nm
Absorption peak outside, there are also relatively weak ultraviolet characteristic absorption peak at 350nm.By water soluble fluorescence carbon materials resulting in bag filter
After material freeze-drying, the yellow solid carbon material powder of particle diameter about 10nm or so is obtained.Condition of the present embodiment in microwave heating
Under, organic matter lignin main in black liquor is carbonized, water-soluble fluorescence carbon material is obtained, by main component in black liquid
For the organic pollutant of lignin, it is converted into the water soluble fluorescence carbon material of high added value, solves paper-making black liquor, is realized
Environment and economical effects.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a kind of to prepare water soluble fluorescence carbon material using microwave heating method hydro-thermal charing black liquid
Method includes the following steps:
A. the 300ml black liquid black liquid containing lignin 30% hydro-thermal charring process: is added to microwave reaction kettle
In, setting temperature is 220 DEG C, carries out the hydro-thermal carbonization reaction of 4h at this temperature；
B. this step is the same as example 1；
C. this step is the same as example 1.
Experimental test and analysis:
Experimental test and analysis is carried out to water soluble fluorescence carbon material manufactured in the present embodiment.Water solubility manufactured in the present embodiment
The aqueous solution of fluorescence carbon material is placed 1 week at room temperature, without any apparent sedimentation, is shown steady in a long-term equal
Phase.The aqueous solution of water soluble fluorescence carbon material manufactured in the present embodiment Continuous irradiation 30min, fluorescence under 365nm exciting light is strong
Spend almost unchanged, show it with excellent anti-light Bleachability, be conducive to carbon dots cell-targeting tracer, in terms of answer
With.In addition, the aqueous solution of water soluble fluorescence carbon material manufactured in the present embodiment is within the scope of the sodium chloride concentration of 0-2.0M, fluorescence
Intensity is also basicly stable constant, illustrates there is good saline-alkaline tolerance, is conducive to its application in terms of biochemical analysis and detection.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of to prepare water soluble fluorescence carbon material using microwave heating method hydro-thermal charing black liquid
Method includes the following steps:
A. the 300ml black liquid black liquid containing lignin 30% hydro-thermal charring process: is added to microwave reaction kettle
In, setting temperature is 180 DEG C, carries out the hydro-thermal carbonization reaction of 6h at this temperature；
B. this step is the same as example 1；
C. this step is the same as example 1.
The efficiency of water soluble fluorescence carbon material manufactured in the present embodiment is low some compared to embodiment, but due to the present embodiment
Using the method that assisted microwave synthesis heats, still higher than traditional direct high temperature pyrolysis process carries out the preparation of hydro-thermal carbonization reaction
The efficiency of fluorescence carbon material, so the present embodiment still realizes the purpose of the present invention.
Example IV:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of to prepare water soluble fluorescence carbon material using microwave heating method hydro-thermal charing black liquid
Method includes the following steps:
A. the 300ml black liquid black liquid containing lignin 30% hydro-thermal charring process: is added to microwave reaction kettle
In, setting temperature is 250 DEG C, carries out the hydro-thermal carbonization reaction of 1h at this temperature；
B. this step is the same as example 1；
C. this step is the same as example 1.
The efficiency of water soluble fluorescence carbon material manufactured in the present embodiment is low some compared to embodiment, but due to the present embodiment
Using the method that assisted microwave synthesis heats, still higher than traditional direct high temperature pyrolysis process carries out the preparation of hydro-thermal carbonization reaction
The efficiency of fluorescence carbon material, so the present embodiment still realizes the purpose of the present invention.
The embodiment of the present invention is illustrated above in conjunction with attached drawing, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
The skill of the method for water soluble fluorescence carbon material is prepared using microwave heating method hydro-thermal charing black liquid without departing from the present invention
Art principle and inventive concept, belong to protection scope of the present invention.
Claims (3)
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