CN107175136A - A kind of weak-base anion-exchange resin and the method that levulic acid is purified using it - Google Patents
A kind of weak-base anion-exchange resin and the method that levulic acid is purified using it Download PDFInfo
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- CN107175136A CN107175136A CN201710560631.2A CN201710560631A CN107175136A CN 107175136 A CN107175136 A CN 107175136A CN 201710560631 A CN201710560631 A CN 201710560631A CN 107175136 A CN107175136 A CN 107175136A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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Abstract
The application belongs to levulic acid preparing technical field, and in particular to a kind of weak-base anion-exchange resin and the levulic acid purification process using the resin.The resin is used to isolate and purify the levulic acid in hydrolysising original liquid, and the hydrolysising original liquid is that biological material coproduction prepares furfural and hydrolysising original liquid in levulic acid technique；Preparing raw material has resin matrix, the first porous load graphene, the second porous load CNT, initiator, organic solvent, reagent and additive in polymerization.When purifying the dilute aqueous solution containing levulic acid using weak-base anion-exchange resin provided herein, it is not necessary to the thick purification technique of vacuum distillation, energy consumption cost can be greatly reduced.On the other hand, resin provided herein can live again, it can recycle, have the advantages that total exchange capacity height, exchange velocity are fast, there is preferably practical value and popularization and application meaning for reducing the purifying cost of levulic acid, the production efficiency of raising levulic acid.
Description
Technical field
The application belongs to levulic acid preparing technical field, and in particular to a kind of weak-base anion-exchange resin and utilization
The levulic acid purification process of the resin.
Background technology
Levulic acid is a kind of while the polyfunctional compound containing carbonyl, α-hydrogen and carboxyl, is the various light industries of synthesis
The base stock of product, in organic synthesis and industrial or agricultural, pharmaceuticals industry, with extensive use value.For example：Levulic acid
Hydrogenation product gamma-valerolactone be a kind of senior solvent and can be as producing synthetic rubber, cold resistant plasticizer and surfactant
Intermediate product；Acetyl chloride propionic acid can as industrial circulating water bacteriostatic agent；The amine salt of acetyl chloride propionic acid agriculturally may be used
It is used as herbicide and defoliant；Pharmaceutically, its calcium salt can be made into the products such as intravenous injection and indocin.
In general, levulic acid is made by raw materials such as starch, glucose, celluloses through depth hydrolysis.Actual production
In, levulic acid is obtained as coproduction product purification in furfural production technology.Its main production process is：By agricultural crop straw
Sour water solution is prepared after furfural co-production levulic acid, contains levulic acid and furfural product in obtained hydrolysising original liquid simultaneously；It is right
Hydrolysising original liquid first passes through high temperature membrane pressure filtering technique, and the furfural in hydrolysising original liquid is separated, and is left dilute water containing levulic acid
Solution is purified again.
In traditional levulic acid method of purification：It is different with the boiling point of water using levulic acid, slightly carried using vacuum distillation
Pure technology, is the thick solution of levulic acid containing a small amount of water by the dilute aqueous solution purification containing levulic acid, then passes through secondary fine again
Technology is evaporated, the thick solution is further purified, the pure solution of levulic acid that purity reaches 99% is obtained.But this method is deposited
In the higher defect of obvious energy consumption, main cause is：After hydrolysising original liquid separation furfural, second in the dilute aqueous solution containing levulic acid
The content of acyl propionic acid is in below 2wt%, and concentration is relatively low, wherein surpasses 80%, it is necessary to remove in purification technique thick using vacuum distillation
Moisture, this consumption to heat is very big, it is necessary to which wasting substantial amounts of fuel produces thermal source, thus causes the production of levulic acid
Cost remains high, and whole traditional purifying process production cycle is longer, limits the lifting of levulic acid production efficiency.Cause
And it is necessary further improvement for levulic acid purification technique pole.
The content of the invention
Present invention aims at a kind of weak-base anion-exchange resin that application is purified for levulic acid is provided, utilize
The resin can realize lower cost and the more quick purification to levulic acid, so as to improve the preparation effect of levulic acid
Rate.
Details are as follows for the technical scheme that the application is taken.
A kind of weak-base anion-exchange resin, the resin is used to isolate and purify the levulic acid in hydrolysising original liquid, described
Hydrolysising original liquid is that biological material coproduction prepares furfural and hydrolysising original liquid in levulic acid technique；
During being easy to use, in terms of specification, the weak-base anion-exchange resin diametrically 0.74 ~ 0.9mm or so resin
Ball particle；
By percentage to the quality, its preparing raw material has：
60 ~ 80wt% of resin matrix；The resin matrix is acrylic acid, methyl acrylate, methyl methacrylate, metering system
One or more of arbitrary proportion mixtures in acid butyl ester, styrene；
First porous 0.1 ~ 5wt% of load；The first porous load be graphene, the graphene be single-layer graphene,
One or more of arbitrary proportion mixtures in multi-layer graphene, graphene oxide；
Second porous 1 ~ 7wt% of load；The second porous load position CNT, the CNT is armchair shape
One or more of arbitrary proportion mixtures in nanotube, zigzag nanotubes, chiral nanotubes；
0.5 ~ 7wt% of initiator；The initiator is benzoyl peroxide, azodiisobutyronitrile, hydroperoxidation to Meng's alkane, peroxide
Change one or more of arbitrary proportion mixtures in two diisopropyl carbonates；
3 ~ 12wt% of organic solvent；The organic solvent is ethyl acetate, tetrahydrofuran, chloroform, Isosorbide-5-Nitrae-dioxane, N, N- bis-
One or more of arbitrary proportion mixtures in methyl nitrosourea；
2 ~ 9wt% of reagent and additive in polymerization；The reagent and additive in polymerization is Nano-meter SiO_22。
The preparation method of the weak-base anion-exchange resin, specifically includes following steps：
（1）Dry resin matrix is scattered in organic solvent, 24 ~ 48h is swelled at a temperature of 40 ~ 60 DEG C, is preferably stirred when being swelled
It is swelled under the conditions of mixing, speed of agitator may be designed as：100~150r/min；
（2）In step（1）Be swelled in system add reagent and additive in polymerization ensure to stir, be warming up to 70 ~ 90 DEG C insulation 2 ~ 5h；For
Ensure to be uniformly mixed, rotating speed may be designed as during stirring：100~150r/min；
After insulation terminates, initiator is added, continuing 1 ~ 2h of insulation ensures that reaction is complete；After addition initiator in insulating process, it is
Ensure that reaction is abundant, preferably last for being incubated under stirring condition, now speed of agitator may be designed as：80~120r/min；
（3）By step（2）Reaction system be transferred in vacuum plant, be slowly added to the first porous carrier and second it is porous carry
Body, starts to vacuumize, and vacuum is 0.06 ~ 0.08MPa, while being heated to 60 ~ 80 DEG C of 20 ~ 24h of insulation；In insulating process, it is
Ensure that reaction is abundant, preferably last for stirring reaction system, speed of agitator may be designed as：200~300r/min；
Reaction is to load the weak-base anion-exchange resin after modification after terminating；
For ease of using, preferably by react terminate anion exchange resin crushed through forming machine, be prepared into diameter 0.74 ~
0.9mm or so resin ball particle.
To ensure that resin balls preserve using effect（It is easy to preserve and follow-up using effect）, can be by resin ball particle by as follows
Step carries out preservation pretreatment：
First, by resin ball particle organic solvent（It is ethyl acetate, tetrahydrofuran, chloroform, 1 with dissolving organic solvent,
One or more of arbitrary proportion mixtures in 4- dioxane, N, N- dimethylformamides）Washed, and dried；Specific washing
And mode of operation refers to following steps：
By resin ball particle, 150r/min stirs 10min in organic solvent, then filters, and repeats this step and is no less than three times；
Then in 80 DEG C of temperature, N21h is dried under protective atmosphere；
Secondly, it is miscellaneous with remove that resin balls contain by above-mentioned cleaning and resin ball particle 4%NaOH solution soaks 3 ~ 5h after drying
Matter；Immersion is filtered after terminating, then is washed to deionized water pH≤8, and vacuumizing filtration；
Finally, with 2 ~ 5h of soaked in absolute ethyl alcohol, drying process is vacuumized.
Using the levulic acid purification process of the weak-base anion-exchange resin, comprise the following steps：
（1）The pretreatment of hydrolysising original liquid：High temperature membrane is carried out to furfural in hydrolysising original liquid prepared by biological material acid hydrolysis process
After press filtration separation, due to the remaining dilute aqueous solution containing levulic acid（Trapped fluid）In containing certain acid, it is necessary to be adjusted to weak
Alkalescence, adjusts pH=8 ~ 9；During regulation, specifically it is adjusted for example with the sodium hydrate aqueous solution of 0.3% mass fraction；
（2）The pretreatment of exchanger resin：
With reference to《The ion exchange resin preprocess methods of GB/T5476-1996》Method is pre-processed to resin, specifically：
Alternately washed with deionized water, 1 mol/L hydrochloric acid, 1 mol/L sodium hydroxide solution respectively, then tree is rinsed with pure water
Fat, it is then to 60 DEG C of exchanger resin vacuum drying, 2 more than h in vacuum drying chamber, i.e., complete until pH=9 or so of flushing water
Into the pretreatment of weak-base anion-exchange resin；
Further, the weak-base anion-exchange resin after the completion of pretreatment can be carried out to upper prop to use, with resin balls
Exemplified by, upper prop is carried out with reference to following ratio, in internal diameter 3.0cm, length are 50cm, resin layers of balls filling height is 40cm；
（3）Absorption is swapped to levulic acid：With step（2）Weak-base anion-exchange resin is used as absorption after middle pretreatment
Agent, to step（1）The dilute aqueous solution containing levulic acid carries out saturation absorption after middle pretreatment；
During adsorption operations, levulinic acid content is preferably 1.0 ~ 2.0% in trapped fluid, and most preferably 1.5% or so；Trapped fluid temperature
Preferably remain in 60 ~ 100 DEG C or so, most preferably 80 DEG C or so；Adsorption time should not be less than 120min, be preferably not less than
180min, but long adsorption time also lacks necessity, can be no more than 210min；
After the completion of absorption, weak-base anion-exchange resin is carried out to elute attached, the levulic acid solution slightly purified, enters one
Walk rectifying separation, you can obtain the pure solution of levulic acid；
Specifically washing desorption processing method refers to following processing mode：
The resin balls for being adsorbed with levulic acid are immersed in ethyl acetate solution, 15min or so is stirred under room temperature condition, are utilized
Ethyl acetate parses levulic acid from resin balls, you can obtain the ethyl acetate solution containing levulic acid, then profit
It is different with ethyl acetate boiling point with levulic acid, further rectifying separation, you can obtain the pure solution of levulic acid；And solve desorption
Exchanger resin afterwards（Resin ball particle）It is renewable recycling after pretreatment.
In general, purified using weak-base anion-exchange resin provided herein dilute water-soluble containing levulic acid
During liquid, due to not needing the thick purification technique of vacuum distillation, thus energy consumption cost can be greatly reduced, meanwhile, levulic acid is tentatively dense
The contracting time also can significantly shorten.On the other hand, because weak-base anion-exchange resin provided herein can live again, and can
Recycle, while have the advantages that total exchange capacity is high, exchange velocity is fast, thus for reduce the purifying of levulic acid into
Originally, improving the production efficiency of levulic acid has preferably practical value and popularization and application meaning.
Brief description of the drawings
Fig. 1 is influence of the levulic acid concentration to levulic acid adsorption effect；
Fig. 2 is impact effect of the trapped fluid temperature to adsorption rate；
Fig. 3 is impact effect of the swap time to adsorption rate.
Embodiment
Explanation is further explained to the application with reference to embodiment, before specific embodiment is introduced, with regard to following realities
Part Experimental Background situation briefly introduction in example is applied to be described as follows.
Hydrolysising original liquid：
Standard biologic matter raw material is prepared in furfural technique, and biomass by hydrolyzation mainly using two grades of hydrolysis tandem process, passes through control
Different hydrolysising conditions improves the selectivity of stalk hydrolysate；
By taking raw material of the maize straw briquetting as reaction as an example, it carries out under 170 ~ 180 DEG C and 0.8 ~ 1.0MPa pressure
One-stage hydrolysis, prepares furfural；Then supercharging is started to warm up, is carried out under 210 ~ 230 DEG C and the effect of 0.2 ~ 0.25MPa pressure
The second level is hydrolyzed, and prepares levulic acid, and last gained mixed solution is hydrolysising original liquid, is entered for certain batch hydrolysising original liquid
Row constituent content detects that pH=5.5 ~ 6 of hydrolysising original liquid, its composition detection result is as shown in the table：
From upper table data can be seen that the hydrolysising original liquid come out from second order reaction device, main component is furfural and levulinic
Acid, simultaneously containing a small amount of biomass suspended powder.
It is for the technical process that hydrolysising original liquid carries out furfural separation：Filtering is first passed through, suspension therein is removed
Grain impurity；Remove the hydrolysising original liquid temperature after impurity and maintain 80 DEG C or so, be then introduced directly into press filtration membrane separation device, open
Air pump, keeps the pressure difference in press filtration membrane separation device to maintain 1.2MPa or so, proceeds by press filtration UF membrane furfural；Separation
Main component is levulic acid in trapped fluid after furfural, then using weak-base anion-exchange resin prepared in the application
Levulic acid product in trapped fluid is purified.
Main production raw material：
Graphene（Model：TNIRGO）, CNT（Model：TNIM8）, it is the limited public affairs of Chinese Academy of Sciences's Chengdu organic chemistry
Take charge of product；
Nano-meter SiO_22（Model：HDK N20）, it is Shanghai Kai Yin Chemical Co., Ltd.s product；
Main production equipments：
Vacuum plant is used when preparing anion exchange resin, is the model of Yu Hua Instrument Ltd. of Henan Province production：
SHZ-D（Ⅲ）Product.
Embodiment 1
The present embodiment provides weak-base anion-exchange resin, by percentage to the quality, and its preparing raw material has：
Resin matrix 66wt%；Specifically have：20wt% acrylic acid, 24 wt% methyl acrylates, 22 wt% methyl methacrylates；
First porous load 5wt%；Specifically have：1.5wt% single-layer graphenes, 3.5wt% multi-layer graphenes；
Second porous load 7wt%；Specially：Armchair nanotubes；
Initiator 7wt%；Specially：2wt% benzoyl peroxides, 5wt% azodiisobutyronitriles；
The wt% of organic solvent 6；Specially：2wt% ethyl acetate, 1wt% tetrahydrofurans, 0.5wt% chloroforms, 2.5wt% 1,4- dioxies
Six rings；
Reagent and additive in polymerization 9wt%；The reagent and additive in polymerization is Nano-meter SiO_22。
Its preparation process is specially：
（1）Dry resin matrix is scattered in organic solvent, 24h is swelled at a temperature of 40 DEG C, is entered when being swelled under stirring condition
Row is swelled, and speed of agitator is designed as：150r/min；
（2）In step（1）Be swelled in system and add reagent and additive in polymerization, 150r/min continues to stir 2h to ensure to be well mixed, together
When be warming up to 70 DEG C；
Then initiator is added, 80r/min persistently stirs 1 hour to ensure that reaction is abundant；
（3）By step（2）Reaction system be transferred in vacuum plant, be slowly added to the first porous carrier and second it is porous carry
Body, continues heating stirring 20h, speed of agitator is 300r/min；
After reaction terminates, the anion exchange resin for reacting end is crushed through forming machine, 0.74 ~ 0.9mm of diameter is prepared into left
Right resin ball particle.
To ensure resin balls preservation effect, resin ball particle is pre-processed as follows：
First, by resin ball particle organic solvent（It is identical with aforementioned organic solvents）Washed, and dried；
Secondly, above-mentioned resin ball particle is soaked into 3h with 4%NaOH solution, to remove the impurity that resin balls contain；Mistake after immersion terminates
Filter, then it is washed to deionized water pH≤8, and vacuumizing filtration；
Finally, soaked in absolute ethyl alcohol 5h is used, drying process is vacuumized.
Embodiment 2
The weak-base anion-exchange resin that the present embodiment is provided, by percentage to the quality, its preparing raw material have：
Resin matrix 80wt%；Specifically have：25wt% styrene, 30 wt% butyl methacrylates, 25 wt% methyl methacrylates
Ester；
First porous load 5wt%；Specifically have：1wt% multi-layer graphenes, 4wt% graphene oxides；
Second porous load 6.5wt%；Specially：3wt% zigzag nanotubes, 3.5wt% chiral nanotubes；
Initiator 3.5wt%；Specially：1wt% azodiisobutyronitriles, 1wt% hydroperoxidations are to Meng's alkane, the carbon of 1.5wt% peroxidating two
Sour diisopropyl ester；
The wt% of organic solvent 3；Specially：1wt% 1,4- dioxane, 0.5wt% tetrahydrofurans, 0.5wt% chloroforms, 1wt%N,
N- dimethylformamides；
Reagent and additive in polymerization 2wt%；The reagent and additive in polymerization is Nano-meter SiO_22。
Preparation process be the same as Example 1, only adjustment member parameter is as follows；
Step（1）In, 48h is swelled at a temperature of 50 DEG C, speed of agitator is designed as when being swelled：120r/min；
Step（2）In, add after reagent and additive in polymerization, 100r/min continues to stir 4h, is warming up to 90 DEG C, adds after initiator, 100r/
Min continues to stir 2h；
Step（3）In, continue heating stirring 24h, rotating speed 200r/min；
Equally it is prepared into 0.74 ~ 0.9mm of diameter or so resin ball particle.
When preserve processing to resin ball particle, processing method be the same as Example 1 only adjusts following parameter setting：
When being rinsed to resin ball particle with organic solvent, with organic solvent formula in the present embodiment（That is, 1wt% Isosorbide-5-Nitraes-dioxy six
Ring, 0.5wt% tetrahydrofurans, 0.5wt% chloroforms, 1wt%N, N- dimethylformamides）；
5h is soaked with 4%NaOH solution to exchanger resin；
Finally use soaked in absolute ethyl alcohol 2.5h.
Embodiment 3
The weak-base anion-exchange resin that the present embodiment is provided, by percentage to the quality, its preparing raw material have：
Resin matrix 70wt%；Specifically have：25wt% acrylic acid, 15wt% methyl methacrylates, 30wt% styrene；
First porous load 3wt%；Specifically have：1wt% multi-layer graphenes, 2wt% graphene oxides；
The second porous wt% of load 3；Specially：0.5wt% armchair nanotubes, 1wt% zigzag nanotubes, 1.5wt% hands
Property nanotube；
Initiator 5wt%；Specially：2wt% benzoyl peroxides, 1wt% azodiisobutyronitriles, 2wt% hydroperoxidations are to Meng's alkane；
Organic solvent 10wt%；Specially：2wt% ethyl acetate, 1wt% chloroforms, 3.5wt% Isosorbide-5-Nitraes-dioxane, 3.5wt% N,
N- dimethylformamides；
Reagent and additive in polymerization 9wt%；The reagent and additive in polymerization is Nano-meter SiO_22。
Preparation process be the same as Example 1, only adjustment member parameter is as follows；
Step（1）In, 40h is swelled at a temperature of 40 DEG C, speed of agitator is designed as when being swelled：100r/min；
Step（2）In, add after reagent and additive in polymerization, 150r/min continues to stir 5h, is warming up to 80 DEG C, adds after initiator, 100r/
Min continues to stir 1h；
Step（3）In, continue heating stirring 36h, rotating speed 200r/min；
Equally it is prepared into 0.74 ~ 0.9mm of diameter or so resin ball particle.
When preserve processing to resin ball particle, processing method be the same as Example 1 only adjusts following parameter setting：
When being rinsed to resin ball particle with organic solvent, with organic solvent formula in the present embodiment（That is, 2wt% ethyl acetate,
1wt% chloroforms, 3.5wt% Isosorbide-5-Nitraes-dioxane, 3.5wt% N, N- dimethylformamides）；
4h is soaked with 4%NaOH solution to exchanger resin；
Finally use soaked in absolute ethyl alcohol 3h.
Embodiment 4
The weak-base anion-exchange resin that the present embodiment is provided, by percentage to the quality, its preparing raw material have：
Resin matrix 77wt%；Specifically have：20wt% acrylic acid, 12wt% methyl methacrylates, 15wt% butyl methacrylates,
30wt% styrene；
First porous load 3wt%；Specifically have：1wt% single-layer graphenes, 2wt% graphene oxides；
Second porous load 4wt%；Specially：2wt% armchair nanotubes, 2wt% zigzag nanotubes；
Initiator 4wt%；Specially：2wt% benzoyl peroxides, 2wt% di-isopropyl peroxydicarbonates；
Organic solvent 5wt%；Specially：1wt% ethyl acetate, 1wt% tetrahydrofurans, 1.5wt% chloroforms, 1.5wt%1,4- dioxies six
Ring；
Reagent and additive in polymerization 7wt%；The reagent and additive in polymerization is Nano-meter SiO_22。
Preparation process be the same as Example 1, only adjustment member parameter is as follows；
Step（1）In, 24h is swelled at a temperature of 50 DEG C, speed of agitator is designed as when being swelled：120r/min；
Step（2）In, add after reagent and additive in polymerization, 120r/min continues to stir 3h, is warming up to 80 DEG C, adds after initiator, 100r/
Min continues to stir 2h；
Step（3）In, continue heating stirring 20h, rotating speed 300r/min；
Equally it is prepared into 0.74 ~ 0.9mm of diameter or so resin ball particle.
When preserve processing to resin ball particle, processing method be the same as Example 1 only adjusts following parameter setting：
When being rinsed to resin ball particle with organic solvent, with organic solvent formula in the present embodiment（That is, 1wt% ethyl acetate,
1wt% tetrahydrofurans, 1.5wt% chloroforms, 1.5wt%1,4- dioxane）；
5h is soaked with 4%NaOH solution to exchanger resin；
Finally use soaked in absolute ethyl alcohol 3h.
Embodiment 5
The weak-base anion-exchange resin that the present embodiment is provided, by percentage to the quality, its preparing raw material have：
Resin matrix 70wt%；Specifically have：30wt% acrylic acid, 20wt% methyl methacrylates, 20wt% styrene；
First porous load 5wt%；Specifically have：1wt% multi-layer graphenes, 4wt% graphene oxides；
Second porous load 5wt%；Specially：2wt% chiral nanotubes, 3wt% zigzag nanotubes；
Initiator 6wt%；Specially：1wt% benzoyl peroxides, 3wt% azodiisobutyronitriles, 2wt% dicetyl peroxydicarbonates two are different
Propyl ester；
Organic solvent 6wt%；Specially：3wt% ethyl acetate, 2wt% tetrahydrofurans, 1wt% chloroforms；
Reagent and additive in polymerization 8wt%；The reagent and additive in polymerization is Nano-meter SiO_22。
Preparation process be the same as Example 1, only adjustment member parameter is as follows；
Step（1）In, 36h is swelled at a temperature of 60 DEG C, speed of agitator is designed as when being swelled：120r/min；
Step（2）In, add after reagent and additive in polymerization, 120r/min continues to stir 4h, is warming up to 90 DEG C, adds after initiator, 120r/
Min continues to stir 3h；
Step（3）In, continue heating stirring 24h, rotating speed 250r/min；
Equally it is prepared into 0.74 ~ 0.9mm of diameter or so resin ball particle.
When preserve processing to resin ball particle, processing method be the same as Example 1 only adjusts following parameter setting：
When being rinsed to resin ball particle with organic solvent, with organic solvent formula in the present embodiment（That is, 3wt% ethyl acetate,
2wt% tetrahydrofurans, 1wt% chloroforms）；
4h is soaked with 4%NaOH solution to exchanger resin；
Finally use soaked in absolute ethyl alcohol 3h.
Embodiment 6
The weak-base anion-exchange resin that the present embodiment is provided, by percentage to the quality, its preparing raw material have：
Resin matrix 75wt%；Specifically have：20wt% acrylic acid, 25wt% butyl methacrylates, 30wt% methyl acrylates；
First porous load 4wt%；Specifically have：3wt% single-layer graphenes, 1wt% multi-layer graphenes；
Second porous load 5wt%；Specially：2wt% armchair nanotubes, 1wt% zigzag nanotubes, 2wt% chiralitys are received
Mitron；
Initiator 3wt%；Specially：1wt% benzoyl peroxides, 0.5wt% azodiisobutyronitriles, 0.5wt% hydroperoxidations are to Meng
Alkane, 1wt% di-isopropyl peroxydicarbonates；
Organic solvent 8wt%；Specially：2wt% ethyl acetate, 4wt% tetrahydrofurans, 1wt%N, N- dimethylformamides, 1wt% 1,
4- dioxane；
Reagent and additive in polymerization 5wt%；The reagent and additive in polymerization is Nano-meter SiO_22。
Preparation process be the same as Example 1, only adjustment member parameter is as follows；
Step（1）In, 48h is swelled at a temperature of 40 DEG C, speed of agitator is designed as when being swelled：100r/min；
Step（2）In, add after reagent and additive in polymerization, 100r/min continues to stir 5h, is warming up to 70 DEG C, adds after initiator, 80r/
Min continues to stir 1h；
Step（3）In, continue heating stirring 20h, rotating speed 200r/min；
Equally it is prepared into 0.74 ~ 0.9mm of diameter or so resin ball particle.
When preserve processing to resin ball particle, processing method be the same as Example 1 only adjusts following parameter setting：
When being rinsed to resin ball particle with organic solvent, with organic solvent formula in the present embodiment（That is, 1wt% ethyl acetate,
2wt% tetrahydrofurans, 0.5wt%N, N- dimethylformamides, 0.5wt%1,4- dioxane）；
3h is soaked with 4%NaOH solution to exchanger resin；
Finally use soaked in absolute ethyl alcohol 2h.
Embodiment 7
By taking the resin ball particle prepared by embodiment 4 as an example, to different levulic acid concentration bars in dilute aqueous solution containing levulic acid
Levulic acid adsorption effect under part, under condition of different temperatures, under the conditions of different adsorption times is determined, related experiment letter
It is described below.
Before experiment, the part physical and chemical index of the resin ball particle prepared by embodiment 4 is detected, it is as a result as follows：
。
Using the levulic acid purification process of the weak-base anion-exchange resin, comprise the following steps：
（1）The pretreatment of hydrolysising original liquid：High temperature membrane is carried out to furfural in hydrolysising original liquid prepared by biological material acid hydrolysis process
After press filtration separation, due to the remaining dilute aqueous solution containing levulic acid（Hereinafter referred to as trapped fluid）In containing certain acid, it is necessary to
Alkalescent is adjusted to, pH=8 are adjusted（In the acid levulic acid aqueous solution, stirring adds the sodium hydrate aqueous solution of alkalescence,
PH is adjusted to alkalescent）；During regulation, it is adjusted using the sodium hydrate aqueous solution of 0.3% mass fraction；
（2）The pretreatment of activation before exchanger resin use：
With reference to《The ion exchange resin preprocess methods of GB/T5476-1996》Method is pre-processed to resin, specifically：
Alternately washed with deionized water, 1 mol/L hydrochloric acid, 1 mol/L sodium hydroxide solution respectively, then tree is rinsed with pure water
Fat, it is then to 60 DEG C of exchanger resin vacuum drying, 2 more than h in vacuum drying chamber, i.e., complete until pH=9 or so of flushing water
Into the activating pretreatment of weak-base anion-exchange resin；
When swapping absorption to levulic acid in trapped fluid, carried out using upper prop absorption exchanged form, when above-mentioned, in internal diameter
3.0cm, length is in 50cm, resin layers of balls filling height are 40cm；
（3）Absorption is swapped to levulic acid：With step（2）Weak-base anion-exchange resin is used as absorption after middle pretreatment
Agent, to step（1）The dilute aqueous solution containing levulic acid carries out saturation absorption after middle pretreatment；
After the completion of absorption, weak-base anion-exchange resin is carried out to elute attached, the levulic acid solution slightly purified, enters one
Walk rectifying separation, you can obtain the pure solution of levulic acid.
It should be noted that in following experiments, levulinic acid content is detected using gas chromatography analysis in trapped fluid, root
The rate of recovery of levulic acid is calculated according to levulinic acid content before and after being adsorbed in trapped fluid.
Levulic acid concentration influences on levulic acid adsorption effect in trapped fluid
Trapped fluid temperature remains 80 DEG C, and resin balls retain adsorption time to trapped fluid and are set as 210min, to various concentrations second
The trapped fluid of acyl propionic acid is adsorbed, as a result as shown in Figure 1.Analysis shows：
Influence of the levulic acid trapped fluid of various concentrations to adsorption rate increases with the increase of concentration before this, in levulic acid
When concentration reaches 1.5%, adsorption rate is 90.63%, and adsorption rate has reached peak value, with the increasing of levulic acid concentration in trapped fluid
Plus, adsorption rate is begun to decline.Trend is found out from figure, and peak value occurs in adsorption rate, illustrates that weak base formula anion exchange resin exists
Balance has been reached to the levulic acid absorption of 1.5% concentration in the 210min of research, the levulic acid trapped fluid of the concentration has been rung
Highest should be worth.
Influence of the trapped fluid temperature to levulic acid adsorption effect
Resin balls retain trapped fluid adsorption time and are set as in 180min, trapped fluid that levulinic acid content is 1.54%, to difference
Trapped fluid temperature has carried out levulic acid absorption, as a result as shown in Figure 2.Analysis shows：
When trapped fluid temperature is from when dropping to 80 DEG C for 100 DEG C, with the reduction of temperature, adsorption rate is being stepped up, and works as trapped fluid
Temperature from when being reduced to 20 DEG C for 80 DEG C, adsorption rate does not increase anti-drop, starts to gradually reduce.
Adsorb influence of the swap time to levulic acid adsorption effect
Levulic acid concentration is 1.54% in trapped fluid, and trapped fluid temperature is 80 DEG C, and adsorption rate in the case of different adsorption times is entered
Row is determined and calculated, as a result as shown in Figure 3.Analysis shows：
In preceding 210min, with the increase of absorption swap time, absorption of the weak base formula anion exchange resin to levulic acid
Rate is gradually increasing, but after 210min, with the increase of exchange adsorption time, the adsorption rate of levulic acid is kept substantially
It is constant, slightly decline a little, but weak base formula anion exchange resin still can reach 90% to levulic acid adsorption rate.
Weak base formula anion exchange resin reuses effect
If to eluting attached alkalescence anion-exchange resin, carrying out the reuse of different number of times, and calculate returning for levulic acid
Yield, to examine exchanger resin to reuse effect.The rate of recovery to levulic acid after different numbers of repetition is counted, as a result
It is as shown in the table：
。
As can be seen from the above table, after multiplicating, still there is exchanger resin preferably absorption to exchange effect, thus
With preferable recycling value.
Claims (9)
1. a kind of weak-base anion-exchange resin, it is characterised in that by percentage to the quality, its preparing raw material has：
60 ~ 80wt% of resin matrix；The resin matrix is acrylic acid, methyl acrylate, methyl methacrylate, metering system
One or more of arbitrary proportion mixtures in acid butyl ester, styrene；
First porous 0.1 ~ 5wt% of load；The first porous load is graphene；
Second porous 1 ~ 7wt% of load；The second porous load position CNT；
0.5 ~ 7wt% of initiator；
3 ~ 12wt% of organic solvent；
2 ~ 9wt% of reagent and additive in polymerization；The reagent and additive in polymerization is Nano-meter SiO_22。
2. weak-base anion-exchange resin as claimed in claim 1, it is characterised in that the graphene be single-layer graphene,
One or more of arbitrary proportion mixtures in multi-layer graphene, graphene oxide；
The CNT is one or more of arbitrary proportions in armchair nanotubes, zigzag nanotubes, chiral nanotubes
Mixture；
The initiator is benzoyl peroxide, azodiisobutyronitrile, hydroperoxidation to Meng's alkane, di-isopropyl peroxydicarbonate
Middle one or more of arbitrary proportion mixtures；
The organic solvent is ethyl acetate, tetrahydrofuran, chloroform, Isosorbide-5-Nitrae-dioxane, N, it is a kind of in N- dimethylformamides or
Several arbitrary proportion mixtures.
3. weak-base anion-exchange resin as claimed in claim 1, it is characterised in that the weak-base anion-exchange resin
Diametrically 0.74 ~ 0.9mm resin ball particle.
4. the preparation method of any one of claim 1 ~ 3 weak-base anion-exchange resin, it is characterised in that specifically include
Following steps：
（1）Dry resin matrix is scattered in organic solvent, it is swelled 24 ~ 48h at a temperature of 40 ~ 60 DEG C；
（2）In step（1）Be swelled in system add reagent and additive in polymerization ensure to stir, be warming up to 70 ~ 90 DEG C insulation 2 ~ 5h；
After insulation terminates, initiator is added, continuing 1 ~ 2h of insulation ensures that reaction is complete；
（3）By step（2）Reaction system be transferred in vacuum plant, add the first porous carrier and the second porous carrier, take out
Vacuum, while being heated to 60 ~ 80 DEG C of 20 ~ 24h of insulation.
5. the preparation method of weak-base anion-exchange resin as claimed in claim 4, it is characterised in that by exchanger resin by such as
Lower step carries out preservation pretreatment：
First, exchanger resin is washed with organic solvent, and dried；
Secondly, by above-mentioned cleaning and exchanger resin NaOH solution soaks 3 ~ 5h after drying, to remove the impurity that resin balls contain；Leaching
Bubble is filtered after terminating, then is washed to deionized water pH≤8, and vacuumizing filtration；
Finally, with 2 ~ 5h of soaked in absolute ethyl alcohol, drying process is vacuumized.
6. using any one of claim 1 ~ 3 weak-base anion-exchange resin in constructed levulic acid purifying side
Method, its spy is, comprises the following steps：
（1）The pretreatment of hydrolysising original liquid：After being separated to furfural in hydrolysising original liquid prepared by biological material acid hydrolysis process,
Adjust pH=8 ~ 9；
（2）The pretreatment of exchanger resin：
With reference to《The ion exchange resin preprocess methods of GB/T5476-1996》Method is pre-processed to exchanger resin；
（3）Absorption is swapped to levulic acid：With step（2）Weak-base anion-exchange resin is used as absorption after middle pretreatment
Agent, to step（1）The dilute aqueous solution containing levulic acid carries out saturation absorption after middle pretreatment；
After the completion of absorption, weak-base anion-exchange resin is carried out to elute attached, the levulic acid solution slightly purified, enters one
Walk rectifying separation, you can obtain the pure solution of levulic acid.
7. levulic acid purification process as claimed in claim 6, its spy is, step（1）In, during regulation, specifically using 0.3%
The sodium hydrate aqueous solution of mass fraction is adjusted.
8. levulic acid purification process as claimed in claim 6, its spy is, specifically washes desorption processing method and be：
The exchanger resin for being adsorbed with levulic acid is immersed in ethyl acetate solution, using ethyl acetate by levulic acid from friendship
Change in resin and parse, you can obtain the ethyl acetate solution containing levulic acid, recycle levulic acid and ethyl acetate
Boiling point is different, further rectifying separation, you can obtain the pure solution of levulic acid.
9. levulic acid purification process as claimed in claim 6, its spy is, step（3）In, levulinic acid content in trapped fluid
For 1.0 ~ 2.0%；Trapped fluid temperature is maintained at 60 ~ 100 DEG C；Adsorption time is no less than 120min.
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