CN109134944A - A kind of porous small ball and its application with different chemical functional groups - Google Patents
A kind of porous small ball and its application with different chemical functional groups Download PDFInfo
- Publication number
- CN109134944A CN109134944A CN201810989334.4A CN201810989334A CN109134944A CN 109134944 A CN109134944 A CN 109134944A CN 201810989334 A CN201810989334 A CN 201810989334A CN 109134944 A CN109134944 A CN 109134944A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- small ball
- porous small
- functional groups
- long filament
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
Abstract
The invention discloses a kind of cellulose with different functional groups/micrometer fibers element long filament porous small ball and its application, belong to composite functional material technical field.The present invention is high using intensity, price is low and size reinforcing material of other micrometer fibers element long filament as cellulose pellets in the micron-scale, overcome the too small difficult separation of traditional fibre element Microsphere Size, the disadvantages such as mechanical strength is low, the cellulose with the different functional groups/micrometer fibers element long filament porous small ball size and mechanical strength of preparation are controllable, it can be according to the actual needs of application, specific chemical functional group or macromolecular chain are chemically bonded to the cellulose porous small ball of micrometer fibers element long filament enhancing, its product can be widely used in food, dyestuff in drug and industrial and agricultural wastewater, antibiotic, the absorption of the substances such as heavy metal, it can also be applied to protein, enzyme, the carrier of the substances such as cell, it has broad application prospects.
Description
Technical field
The invention belongs to composite functional material technical fields, have different chemical functional groups more specifically to one kind
Cellulose/micrometer fibers element long filament porous small ball and preparation method thereof, while being related to it in the application of different field.
Background technique
Cellulose is that the natural high molecular substance most wide, yield is maximum and renewable, degradable is distributed in nature, because of it
The features such as easily disposing after source is wide, cheap, good biocompatibility, intensity are high and use, causes domestic and international researcher extensive
Concern, wherein the separation of modified cellulose class and purified material are one of current main research fields, can be reduced to fossil resources
Dependence and pollution to environment.
Cellulose is to be formed by D- dehydration glucopyranose acid anhydride (AGU) unit by β-Isosorbide-5-Nitrae-glucosides key connection, each AGU
Unit all contains 3 hydroxyl groups, can be functionalized to it using hydroxyl.If cellulose is prepared into porous small ball,
And its surface is functionalized accordingly, the objects such as dyestuff, antibiotic, heavy metal in food, drug and industrial and agricultural wastewater
The adsorbent of matter, the fields such as carrier of the substances such as protein, enzyme, cell, has broad application prospects.
Derived product of the cellulose microsphere as cellulose has large specific surface area, transparent performance and hydraulic performance good
The advantages that, it is widely used in fields such as biology, medicine, materials.But cellulose microsphere due to size it is smaller (≤
1mm), complex manufacturing process is not readily separated disposition after use, and unmodified cellulose microsphere is only capable of through hydroxyl effect pair
Molecule carries out non-specific adsorption, and mechanical strength is also extremely difficult to requirement, therefore limits its application.
Through retrieving, in the prior art there is also relevant technical solution, Chinese Patent Application No. CN201010283198.0,
Publication date is that the application case of 2010.12.22 discloses the preparation method of cellulose microsphere, and preparation method includes following step
It is rapid: 1) using alkali/aqueous solution of urea or/and alkali/thiourea solution as solvent, to be cooled to -5 DEG C~-12 DEG C of low temperature in advance, be then added fine
High-speed stirred dissolves dimension element at low temperature, and last low-speed centrifugal deaeration, which removes impurity, can be obtained cellulose solution；2) in high pressure
Under electric field action, electrostatic spraying is carried out, regenerated cellulose microsphere is ultimately formed.
Chinese Patent Application No. CN200810047314.1, publication date are that the application case of 2008.08.27 discloses one kind
Cellulose microsphere and its preparation method and application disperses cellulose solution in the organic solvent containing emulsifier or compound emulsifying agent
In, 1~10hr of normal temperature cure forming after stirring to droplet distribution uniformly, diluted acid, which is then added, makes cellulose regenerated formation microballoon,
Stratification filters to obtain cellulose grain, obtains cellulose microsphere after decantate.
It has been reported using ionic liquid as solvent and prepares Cellulose/Chitosan composite pellets, the bead is to Chinese herbal medicine water
In pigment have good adsorption effect.Chinese Patent Application No. CN201110341904.7, publication date be
2012.06.20 application case discloses a kind of Regenerated cellulose microspheres and preparation method thereof, and preparation method is first to be dissolved in cellulose
Cellulose solution is prepared in ionic liquid, then cellulose solution is added in oily phase, is made by anti-phase suspension and program cooling
Cellulose solution condenses into drop, and curing agent, which is then added, makes cellulose solution drop be formed by curing cellulose microsphere, finally uses
Distillation water washing and impregnating cellulose microsphere fully enters ionic liquid in soak to get to milky regenerated cellulose
Microballoon.It is well known that up to the present, the price of ionic liquid or very expensive can not carry out large-scale industrial application.
Chinese Patent Application No. CN201710089429.6, publication date are that the application case of 2017.06.13 discloses one kind
The modified preparation method of cellulose microsphere, alkali and urea freezing are added after cellulose and cyclodextrin stirring and dissolving be scattered in just oneself
Stirring forming, heating in alkane, petroleum ether, this Pan's series emulsifier and the solution of twain series emulsifier mixing, addition glutaraldehyde,
Ethylene glycol diglycidylether and epichlorohydrin reaction 12h, dilute acid for adjusting pH, which is added, keeps cellulose composite material regeneration micro-
Ball stands and takes upper layer isolate, arrives cellulose composite microsphere after filtration drying；Obtained cellulose composite microsphere is used
Alcohol rinse purification, obtains cellulose modified composite particles after drying.
Chinese Patent Application No. CN201210070945.1, publication date are that the application case of 2012.07.11 discloses one kind
Cellulose composite microsphere and its preparation method and application, the cellulose composite microsphere is using cellulose as substrate, with macromolecule material
It is molten to prepare the mixing of cellulose/composite material using alkali/urea or alkali/thiocarbamide aqueous solution as solvent for composite material for material
Then liquid is prepared by collosol and gel phase transition and cross-linking agents.The composite material is cyclodextrin, chitosan or sea
Mosanom；The crosslinking agent is glutaraldehyde, ethylene glycol diglycidylether or epoxychloropropane.Gained cellulose composite microsphere is protected
While the advantages of having deposited cellulose family microballoon, the microsphere surface that is incorporated as of composite material increases new functional group, favorably
Further in microballoon modifies and is modified.
Summary of the invention
1. to solve the problems, such as
It is limited for non-chemically-modified cellulose/micrometer fibers element long filament porous small ball absorption property or be lack of pertinence
Or the problems such as selective absorption, it is more that the present invention provides a kind of cellulose with different chemical functional groups/micrometer fibers element long filament
Hole bead and its application are mixed together again come composite pellets processed after cellulose dissolution with micrometer fibers element long filament, can be according to application
Specific chemical functional group or macromolecular chain are chemically bonded to the fiber of micrometer fibers element long filament enhancing by the actual needs of occasion
Plain porous small ball, product can be widely used in food, dyestuff, antibiotic, heavy metal in drug and industrial and agricultural wastewater
The absorption of equal substances, can also be applied to the carrier of the substances such as protein, enzyme, cell.
2. technical solution
Invention is directed to problem of the prior art, invents a kind of using the material fiber element of fully biodegradable as fiber
The substrate of plain bead is dissolved in alkali/urea solvent, and micrometer fibers element long filament is added and pore-foaming agent instills dropwise after mixing
In dilute acid soln, stirring obtains gel state bead after a certain period of time, then is crosslinked from different chemical modifiers or macromolecular chain
And modification, the cellulose with different chemical functional groups/micrometer fibers element long filament porous small ball is prepared, traditional fibre is overcome
The too small difficult separation of plain Microsphere Size, the disadvantage that intensity is low and application range is narrow；It obtains a kind of high-fall with different chemical functional groups
Cellulose/micrometer fibers element long filament porous small ball preparation method.
To achieve the above object, technical solution provided by the invention is as follows:
A kind of porous small ball with different chemical functional groups, the porous small ball is by cellulose and micrometer fibers element long filament
Under pore-foaming agent effect, in dilute acid soln (diluted acid is one of hydrochloric acid, sulfuric acid, nitric acid, and concentration is 0.01~1mol/L)
Gel state bead (action time is 1~4h) is made, then gel state bead is crosslinked with modifying agent and modification obtains.
Further, the diameter of porous small ball is 1~3mm, and specific surface area is 0.1~12.0m2/ g, Kong Rongwei 1.5 ×
10-2~3.0 × 10-2cm3/g。
Further, the cellulose is one of wood-fibred, cotton fiber or sugarcane fiber.
Further, the cellulose be first dissolved in low-temperature alkaline/urea solvent again with micrometer fibers element long filament and cause
Hole agent mixing, then drips and stirs to get gel state bead in diluted acid.
Further, the pore-foaming agent is nanometer or micron order calcium carbonate, calcium bicarbonate, sodium carbonate, sodium bicarbonate
One of.
Further, in the low-temperature alkaline/urea solvent, the alkali is sodium hydroxide, potassium hydroxide and hydroxide
One of lithium, the mass concentration of the alkali are 3~8%, and the mass concentration of the urea is 10~14%, the low temperature is-
12~-6 DEG C；The mass concentration that cellulose is dissolved in cellulose obtained in low-temperature alkaline/urea solvent is 2~10%.
Further, the mass ratio of the cellulose and the micrometer fibers element long filament and the pore-foaming agent is 10:(1
~5): (2~10).
Further, the chemical modifier is maleic anhydride, epoxychloropropane, ethylenediamine, carbon disulfide, quaternary ammonium salt
The mass ratio of at least one of cation high molecular and anion pp acid, gel state bead and the modifying agent is 10:
(0.1~10), reaction time are 0.5~6h.
A kind of adsorbent, be the above-mentioned porous small ball with different chemical functional groups, be used for food, medicine field and
The absorption of the substances such as dyestuff, antibiotic, heavy metal in industrial and agricultural wastewater.
A kind of carrier is the above-mentioned porous small ball with different chemical functional groups, is used as protein, enzyme, cell etc.
The carrier of substance.
The detailed preparation method packet of the above-mentioned cellulose with different chemical functional groups/micrometer fibers element long filament porous small ball
Include following steps:
Cellulose is added in low-temperature alkaline/urea solvent, strong stirring obtains certain mass concentration to after being completely dissolved
Micrometer fibers element long filament and pore-foaming agent are added thereto by cellulose solution, are instilled mixture dropwise after being dispersed with stirring uniformly dilute
In acid solution, stirring obtains gel state bead after a certain period of time, washs removal with distilled water immersion after gel state bead is taken out
Pore-foaming agent reacts the water soluble compound generated with diluted acid, places into acetone and impregnates, obtains cellulose/micrometer fibers element long filament
Porous small ball finally hands over obtained cellulose/micrometer fibers element long filament porous small ball from different modifying agent or macromolecule
Join and modified, prepares the cellulose with different chemical functional groups/micrometer fibers element long filament porous small ball.
The present invention also provides the cellulose with different chemical functional groups/micrometer fibers element long filament porous small ball use
On the way, can be used as food, in drug and industrial and agricultural wastewater the substances such as heavy metal, dyestuff, antibiotic adsorbent, or can be used as egg
The carrier of the substances such as white matter, enzyme, cell.
Micrometer fibers element long filament is the cellulose-derived products just to grow up recently, Young's modulus with higher and drawing
Breaking strength is stretched, compared to similar product nanofibrils cellulose, Cellulose nanocrystal palpus and Cellulose nanocrystal body, there is intensity
The high, advantages such as price is low, are the novel composite reinforcements for being suitble to industrially scalable application.The present invention is directed to the prior art
The problem of, invention dissolves cellulose using alkali cheap and easy to get/urea solvent, then using micrometer fibers element long filament as strengthening material
Material, while pore-foaming agent is added to prepare cellulose/micrometer fibers element long filament porous small ball, finally by the different types of official of introducing
It can roll into a ball and obtain being suitble to different application, the single-minded cellulose with different chemical functional groups/micrometer fibers element long filament more
Hole bead, method particularly includes: by not chemically modified cellulose/micrometer fibers element long filament porous small ball respectively with maleic acid
The reaction of the modifying agent such as acid anhydride, epoxychloropropane, ethylenediamine, carbon disulfide, quaternary ammonium salt cationic macromolecule and anion pp acid
Or crosslinking, so that bead surface is introduced chemical groups, these functional groups such as carboxylic acid group, amido, quaternary ammonium group can be improved the absorption of bead
Capacity.The raw material that the invention uses is renewable, degradable cellulose, and preparation process is simple and easy, for developing greenization
Learn, promote energy-saving and emission-reduction and realize that Community health, stable sustainable development have great strategic significance.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) cellulose prepared by the present invention with different chemical functional groups/micrometer fibers element long filament porous small ball uses
Intensity is high, price is low and size reinforcing material of other micrometer fibers element long filament as cellulose pellets in the micron-scale, overcomes biography
The disadvantages such as the undersized hardly possible of cellulose microsphere of uniting separates, mechanical strength is low, cellulose/micron with different functional groups of preparation
The size and mechanical strength of cellulosic filaments porous small ball are controllable, can be according to the additive amount of micrometer fibers element long filament to the ruler of bead
Very little and mechanical strength is regulated and controled, to adapt to different application.
(2) cellulose prepared by the present invention with different chemical functional groups/micrometer fibers element long filament porous small ball is being made
Pore-foaming agent is added to during standby, aperture, density etc. are controllable, can be according to needs are applied, by changing pore-foaming agent type and adding
Ratio is added to regulate and control the aperture of cellulose pellets, density, to obtain the cellulose pellets for being suitble to different applications to need.
(3) cellulose prepared by the present invention with different functional groups/micrometer fibers element long filament porous small ball be pass through by
Cellulose/micrometer fibers element long filament porous small ball be crosslinked and be modified from different modifying agent introducing different chemical functional groups or height
Strand and be prepared, introduce functional group or macromolecular chain it is controllable, can according to apply needs, pass through change modifying agent
Type and dosage regulate and control the functional group's type and grafting amount of cellulose pellets, are suitble to different applications needs to obtain
Cellulose pellets.
(4) cellulose with different chemical functional groups of the invention/micrometer fibers element long filament porous small ball preparation process
It is simple and environmentally-friendly, without ionic liquid as solvent, it is suitble to industrialized production, is greatly broadened the application range of cellulose pellets,
And porous small ball can use in packed tower, separation is easy.
(5) preparation method whole preparation process of the invention is cheap, simple and easy and environmentally friendly, lower to equipment requirement, peace
Atoxic；Cellulose prepared by the present invention with different functional groups/micrometer fibers element long filament porous small ball has preferable machine
Tool performance, thermal stability, acidproof alkali ability, recycling and separation property, can be widely used in food, drug and workers and peasants
The absorption of the substances such as industry Wastewater Dyes, antibiotic, heavy metal can also be applied to the load of the substances such as protein, enzyme, cell
Body has broad application prospects.
Detailed description of the invention
Fig. 1 is the Electron microscope figure and chemical structure schematic diagram of the porous small ball product in the present invention；
Fig. 2 is to have different or macromolecular chain functional group cellulose/micrometer fibers element long filament porous small ball in the present invention
Product pictorial diagram；
Fig. 3 is the TGA curve graph of CMFCs and MCMFCs；
Fig. 4 is the DTG curve graph of CMFCs and MCMFCs；
Fig. 5 is the reusability result figure that MCMFCs adsorbs MB.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
4g bleaching bagasse cellulose is added in -10 DEG C 96g sodium hydroxide (7wt%)/urea (12wt%) solvent, by force
The cellulose solution that power stirring (800 revs/min are selected in the present embodiment) obtains 4wt% to after being completely dissolved, by 1.2g microns
Cellulosic filaments (commercial product is about 300-600 microns, the long filament that diameter is 2-10 microns) and 4g nanometers or micron order carbonic acid
Calcium is added thereto, and is instilled mixture dropwise in the dilute hydrochloric acid solution of 0.1mol/L after being dispersed with stirring uniformly, is obtained after stirring 2h
Gel state bead washs removal calcium carbonate with distilled water immersion after taking out gel state bead and reacts the water solubility generated with hydrochloric acid
Calcium chloride is placed into acetone and is impregnated, and obtains cellulose/micrometer fibers element long filament porous small ball, then by the maleic acid of itself and 2g
Acid anhydride carries out cross-linking reaction, prepares the cellulose with carboxylic acid group and hydroxy functional group/micrometer fibers element long filament porous small ball, such as
Shown in Fig. 2, the Electron microscope and chemical structure schematic diagram of bead are as shown in Figure 1.
Utilize full-automatic multistation specific surface, micropore and mesoporous pore analysis instrument (BELSORP-max_MicrotracBEL, day
This) cellulose/micrometer fibers element long filament porous small ball specific surface area made from the present embodiment is tested as 11.93m2/ g, Kong Rong
It is 3.02 × 10-2cm3/g。
In order to disclose cellulose/fibrillation cellulose pellets (being denoted as: CMFCs) and maleic anhydride modified CMFCs (note
Are as follows: MCMFCs) hot property, TGA and DTG curve is as shown in Figure 3 and Figure 4.For CMFCs and MCMFCs, in 25 DEG C and 700 DEG C
Between within the temperature range of total mass loss be respectively 92.7% and 93.3% (see Fig. 3).CMFCs and MCMFCs at 25 DEG C and
Initial weight loss between 100 DEG C is 8%, this is because combining the evaporation of water in sample.Compared with CMFCs, MCMFCs's
Decompose and occur in three phases: first time weight loss is 8%, since 50 DEG C of TGA curve, due to releasing from MCMFC
The combination water put；Second of decomposition occurs at 160 DEG C or so, it may be possible to due to the initial stage of thermal degradation；Third time weight damage
It loses and occurs be higher than 290 DEG C of temperature, corresponding to the main thermal cracking of cellulose and microfibrillated cellulose, the maximum of CMFCs
The thermal decomposition peak value of weight loss is 349 DEG C, than 11 DEG C of MCMFCs high (as shown in Figure 4).Illustrate that CMFCs and MCMFCs all have
Preferable heat resistance, and CMFCs sphere is shown than by the higher heat resistance of maleic anhydride modified sphere.
Cellulose/micron made from the present embodiment is tested using BT-2900LD wet-dry change image granularity particle shape analysis system
The partial size of cellulosic filaments porous small ball is 1.12mm.
Absorption property experiment:
Take 1g the present embodiment cellulose/micrometer fibers element long filament obtained with carboxylic acid group and hydroxy functional group porous small
Ball is added in 1000mL 500mg/L methyl blue (MB) solution, under the conditions of 298K, pH=7, carries out the adsorption kinetic data,
Solution is taken out every 10min, using MB concentration in ultraviolet-uisible spectrophotometer test solution, and is drawn made from the present embodiment
Cellulose with carboxylic acid group and hydroxy functional group/curve of adsorption kinetics of the micrometer fibers element long filament porous small ball to MB, root
According to quasi- analysis second stage model, cellulose/micrometer fibers element long filament porous small ball absorption with carboxylic acid group and hydroxy functional group
Speed is fast, adsorption capacity is high, and 90min can reach adsorption equilibrium, and maximum adsorption capacity is up to 436.5mg/g, carboxylic acid group and hydroxyl
Base can carry out complex reaction with many heavy metal ion, dyestuff, and carboxylic acid group is anionic group, especially to positively charged weight
Metal ion, dyestuff, antibiotic have excellent adsorption capacity.Non-modified cellulose/micrometer fibers element long filament is porous small
Ball needs 12h to can be only achieved adsorption equilibrium, maximum adsorption capacity 58.3mg/g.
It is regenerated within 60 minutes by immersing the adsorbent for being loaded with dyestuff in hydrochloric acid (1mol/L) solution.Once regenerating extensive
After multiple, MCMFCs will be reused for MB removal in following five periods (see Fig. 5).The recycling of adsorbent for application be to
Close important, desorption efficiency is presented with different circulation time.It can be seen from the figure that with the increase of circulation time, MB
Desorption efficiency and removal rate gradually decrease, but the 5th circulation when be kept at 87.1% and 85.1%.Therefore, as a result table
Bright MCMFCs is a kind of effectively and with cost-benefit adsorbent, has very big regeneration potential.
Embodiment 2
10g gossypin is added in -12 DEG C 90g potassium hydroxide (8wt%)/urea (10wt%) solvent, is strongly stirred
It mixes to after being completely dissolved and obtains the cellulose solution of 10wt%, 5g micrometer fibers element long filament and 2g sodium carbonate are added thereto, stirred
It mixes and instills mixture dropwise after being uniformly dispersed in the dilute nitric acid solution of 0.01mol/L, obtain gel state bead after stirring 4h, it will
Gel state bead washs the water-soluble sodium nitrate of removal sodium carbonate and nitric acid reaction generation with distilled water immersion after taking out, place into
It is impregnated in acetone, obtains cellulose/micrometer fibers element long filament porous small ball, then by itself and the epoxychloropropane of 2g and the second two of 2g
Amine carries out cross-linking reaction, prepares the cellulose with amino and hydroxy functional group/micrometer fibers element long filament porous small ball.
Cellulose made from the present embodiment/micrometer fibers element long filament porous small ball specific surface area is 0.15m2/ g, Kong Rong
It is 1.56 × 10-2cm3/ g, partial size 2.98mm.
Embodiment 3
2g Eucalyptus Fibers element is added in -6 DEG C 98g lithium hydroxide (3wt%)/urea (14wt%) solvent, is strongly stirred
It mixes to after being completely dissolved and obtains the cellulose solution of 2wt%, 0.2g micrometer fibers element long filament and 2g sodium bicarbonate are added thereto,
Mixture is instilled in the dilution heat of sulfuric acid of 1mol/L after being dispersed with stirring uniformly dropwise, obtains gel state bead after stirring 1h, it will
Gel state bead washs the water-soluble sodium sulphate of removal sodium bicarbonate and sulfuric acid reaction generation with distilled water immersion after taking out, then puts
Enter in acetone and impregnate, obtain cellulose/micrometer fibers element long filament porous small ball, then by its epoxychloropropane with 0.4g, 0.3g
Ethylenediamine and 0.3g carbon disulfide reacted, it is fine to prepare the cellulose with amino, hydroxyl and mercapto functional group/micron
Tie up plain long filament porous small ball.
Cellulose made from the present embodiment/micrometer fibers element long filament porous small ball specific surface area is 10.12m2/ g, Kong Rong
It is 2.53 × 10-2cm3/ g, partial size 1.78mm.
Embodiment 4
3g bagasse cellulose is added in -8 DEG C 97g sodium hydroxide (6wt%)/urea (11wt%) solvent, is strongly stirred
It mixes to after being completely dissolved and obtains the cellulose solution of 3wt%, it is added in 0.6g micrometer fibers element long filament and 1.5g calcium bicarbonate
In, mixture is instilled dropwise in the dilute hydrochloric acid solution of 0.5mol/L after being dispersed with stirring uniformly, it is small to obtain gel state after stirring 1h
Ball washs removal calcium bicarbonate with distilled water immersion after taking out gel state bead and reacts the water-soluble chlorination generated with hydrochloric acid
Calcium is placed into acetone and is impregnated, and obtains cellulose/micrometer fibers element long filament porous small ball, then by the quaternary ammonium salt list of itself and 0.5g
Body carries out graft polymerization reaction, and it is porous small to prepare cellulose/micrometer fibers element long filament with the grafting of cation high molecular chain
Ball.
Cellulose made from the present embodiment/micrometer fibers element long filament porous small ball specific surface area is 4.31m2/ g, Kong Rong
It is 1.96 × 10-2cm3/ g, partial size 2.14mm.
Embodiment 5
7g gossypin is added in -6 DEG C 93g lithium hydroxide (5wt%)/urea (13wt%) solvent, strong stirring
2.8g micrometer fibers element long filament and 5g calcium carbonate are added thereto by the cellulose solution that 7wt% is obtained to after being completely dissolved, stirring
Mixture is instilled after being uniformly dispersed in the dilute hydrochloric acid solution of 0.2mol/L dropwise, obtains gel state bead after stirring 3h, will coagulate
Colloidal state bead washs removal calcium carbonate with distilled water immersion after taking out and reacts the water-soluble calcium chloride generated with hydrochloric acid, places into third
It is impregnated in ketone, obtains cellulose/micrometer fibers element long filament porous small ball, then the acrylic acid of itself and 2g are subjected to in-situ grafting polymerization
Cellulose/micrometer fibers element long filament porous small ball with the grafting of poly- third carboxylic acid chain is prepared in reaction.
Cellulose made from the present embodiment/micrometer fibers element long filament porous small ball specific surface area is 4.52m2/ g, Kong Rong
It is 2.47 × 10-2cm3/ g, partial size 2.1mm.
Comparative example 1
4g bleaching bagasse cellulose is added in -10 DEG C 96g sodium hydroxide (7wt%)/urea (12wt%) solvent, by force
Power, which is stirred to after being completely dissolved, obtains the cellulose solution of 4wt%, and 4g calcium carbonate is added thereto, and will mix after being dispersed with stirring uniformly
It closes object to instill dropwise in the dilute hydrochloric acid solution of 0.1mol/L, obtains gel state bead after stirring 2h, after gel state bead is taken out
Removal calcium carbonate is washed with distilled water immersion and reacts the water-soluble calcium chloride generated with hydrochloric acid, is placed into acetone and is impregnated, obtains
Cellulose/micrometer fibers element long filament porous small ball, then the maleic anhydride of itself and 2g are subjected to cross-linking reaction, it prepares with carboxylic acid
The cellulose porous small ball of base and hydroxy functional group.
The specific surface area of cellulose porous small ball made from this comparative example is 0.91m2/ g, Kong Rongwei 0.82 × 10- 2cm3/ g, partial size 1.76mm.
The aforementioned description to specific exemplary embodiment of the invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining specific principle of the invention and its actually answering
With so that those skilled in the art can be realized and utilize a variety of different exemplary implementation schemes of the invention and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of porous small ball with different chemical functional groups, which is characterized in that the porous small ball is by cellulose and micron
Under pore-foaming agent effect gel state bead is made, then with modifying agent to gel state bead in cellulosic filaments in dilute acid soln
Crosslinking and modification obtain.
2. a kind of porous small ball with different chemical functional groups according to claim 1, which is characterized in that porous small ball
Diameter be 1~3mm, specific surface area be 0.1~12.0m2/ g, Kong Rongwei 1.5 × 10-2~3.0 × 10-2cm3/g。
3. a kind of porous small ball with different chemical functional groups according to claim 1 or 2, which is characterized in that described
Cellulose be one of wood-fibred, cotton fiber or sugarcane fiber.
4. a kind of porous small ball with different chemical functional groups according to claim 3, which is characterized in that the fibre
Dimension element is first dissolved in low-temperature alkaline/urea solvent to be mixed with micrometer fibers element long filament and pore-foaming agent again, is then dripped and is stirred in diluted acid
Obtain gel state bead.
5. a kind of porous small ball with different chemical functional groups according to claim 4, which is characterized in that the cause
Hole agent is one of nanometer or micron order calcium carbonate, calcium bicarbonate, sodium carbonate, sodium bicarbonate.
6. a kind of porous small ball with different chemical functional groups according to claim 4 or 5, which is characterized in that described
Low-temperature alkaline/urea solvent in, the alkali is one of sodium hydroxide, potassium hydroxide and lithium hydroxide, the quality of the alkali
Concentration is 3~8%, and the mass concentration of the urea is 10~14%, and the low temperature is -12~-6 DEG C.
7. a kind of porous small ball with different chemical functional groups according to claim 6, which is characterized in that the fiber
The mass ratio of the plain and micrometer fibers element long filament and the pore-foaming agent is 10:(1~5): (2~10).
8. a kind of porous small ball with different chemical functional groups according to claim 7, which is characterized in that the chemistry
Modifying agent is maleic anhydride, epoxychloropropane, ethylenediamine, carbon disulfide, quaternary ammonium salt cationic macromolecule and anion pp
The mass ratio of at least one of acid, gel state bead and the modifying agent be 10:(0.1~10), the reaction time be 0.5~
6h。
9. a kind of adsorbent, which is characterized in that have different chemical functional groups' described in any one of claim 1-8
Porous small ball, the absorption for substances such as dyestuff, antibiotic, heavy metals in food, medicine field and industrial and agricultural wastewater.
10. a kind of carrier, which is characterized in that have different chemical functional groups' described in any one of claim 1-8
Porous small ball, the carrier as substances such as protein, enzyme, cells.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810989334.4A CN109134944A (en) | 2018-08-28 | 2018-08-28 | A kind of porous small ball and its application with different chemical functional groups |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810989334.4A CN109134944A (en) | 2018-08-28 | 2018-08-28 | A kind of porous small ball and its application with different chemical functional groups |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109134944A true CN109134944A (en) | 2019-01-04 |
Family
ID=64828679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810989334.4A Pending CN109134944A (en) | 2018-08-28 | 2018-08-28 | A kind of porous small ball and its application with different chemical functional groups |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109134944A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110559956A (en) * | 2019-09-06 | 2019-12-13 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Hollow porous cellulose microsphere and preparation method and application thereof |
| CN111363738A (en) * | 2020-04-22 | 2020-07-03 | 圣清环保股份有限公司 | Microbial agent for repairing cadmium-polluted soil and preparation method and application thereof |
| CN112237904A (en) * | 2020-10-29 | 2021-01-19 | 华南师范大学 | Straw fiber adsorbing material and preparation method and application thereof |
| CN114702732A (en) * | 2022-06-07 | 2022-07-05 | 江苏集萃智能液晶科技有限公司 | Polymer particle with double-size pore channel and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101036876A (en) * | 2007-01-25 | 2007-09-19 | 天津大学 | Method for preparing super-hole fibrin microsphere protein absorbing medium |
| CN101921410A (en) * | 2010-09-16 | 2010-12-22 | 武汉工程大学 | Method for preparing cellulose microspheres |
| CN102504285A (en) * | 2011-11-03 | 2012-06-20 | 中国科技开发院广西分院 | Regenerated cellulose microspheres and preparation method thereof |
| CN102553545A (en) * | 2012-03-16 | 2012-07-11 | 川渝中烟工业有限责任公司 | Cellulose composite microsphere and preparation method thereof |
| CN103159532A (en) * | 2011-12-08 | 2013-06-19 | 东北林业大学 | Porous lignin particle composite fertilizer preparation method |
| CN103756016A (en) * | 2013-12-25 | 2014-04-30 | 武汉工程大学 | Cellulose micro-sphere with uniform size as well as preparation method and application thereof |
| CN106565983A (en) * | 2016-11-09 | 2017-04-19 | 武汉工程大学 | Micron-order phosphate radical modified cellulose microsphere and preparation method and application thereof |
| CN107522877A (en) * | 2017-07-18 | 2017-12-29 | 武汉工程大学 | Quaternized cellulose bead, preparation method and purposes |
| CN108187756A (en) * | 2018-01-03 | 2018-06-22 | 福建农林大学 | A kind of preparation method of memory-type photocatalytic fiber element microballoon |
-
2018
- 2018-08-28 CN CN201810989334.4A patent/CN109134944A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101036876A (en) * | 2007-01-25 | 2007-09-19 | 天津大学 | Method for preparing super-hole fibrin microsphere protein absorbing medium |
| CN101921410A (en) * | 2010-09-16 | 2010-12-22 | 武汉工程大学 | Method for preparing cellulose microspheres |
| CN102504285A (en) * | 2011-11-03 | 2012-06-20 | 中国科技开发院广西分院 | Regenerated cellulose microspheres and preparation method thereof |
| CN103159532A (en) * | 2011-12-08 | 2013-06-19 | 东北林业大学 | Porous lignin particle composite fertilizer preparation method |
| CN102553545A (en) * | 2012-03-16 | 2012-07-11 | 川渝中烟工业有限责任公司 | Cellulose composite microsphere and preparation method thereof |
| CN103756016A (en) * | 2013-12-25 | 2014-04-30 | 武汉工程大学 | Cellulose micro-sphere with uniform size as well as preparation method and application thereof |
| CN106565983A (en) * | 2016-11-09 | 2017-04-19 | 武汉工程大学 | Micron-order phosphate radical modified cellulose microsphere and preparation method and application thereof |
| CN107522877A (en) * | 2017-07-18 | 2017-12-29 | 武汉工程大学 | Quaternized cellulose bead, preparation method and purposes |
| CN108187756A (en) * | 2018-01-03 | 2018-06-22 | 福建农林大学 | A kind of preparation method of memory-type photocatalytic fiber element microballoon |
Non-Patent Citations (6)
| Title |
|---|
| YUAN LI 等: "Absorbents based on maleic anhydride-modified cellulose fibers/diatomite for dye removal", 《JOURNAL OF MATERIALS SCIENCE》 * |
| YUAN LI 等: "Novel Composite Adsorbent Consisting of Dissolved Cellulose Fiber/Microfibrillated Cellulose for Dye Removal from Aqueous Solution", 《ACS SUSTAINABLE CHEMISTRY ENGINEERING》 * |
| 常春雨 等: "《新型纤维素、甲壳素水凝胶的构建、结构和性能》", 31 October 2015, 知识产权出版社 * |
| 张力田 等: "《碳水化合物化学》", 31 July 2013, 中国轻工业出版 * |
| 曾丹林 等: "纤维素制备微球材料的研究进", 《材料导报》 * |
| 车如心: "《界面与胶体化学》", 31 August 2012, 中国铁道出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110559956A (en) * | 2019-09-06 | 2019-12-13 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Hollow porous cellulose microsphere and preparation method and application thereof |
| CN111363738A (en) * | 2020-04-22 | 2020-07-03 | 圣清环保股份有限公司 | Microbial agent for repairing cadmium-polluted soil and preparation method and application thereof |
| CN111363738B (en) * | 2020-04-22 | 2023-11-21 | 圣清环保股份有限公司 | Microbial agent for repairing cadmium-polluted soil and preparation method and application thereof |
| CN112237904A (en) * | 2020-10-29 | 2021-01-19 | 华南师范大学 | Straw fiber adsorbing material and preparation method and application thereof |
| CN112237904B (en) * | 2020-10-29 | 2022-09-27 | 华南师范大学 | Straw fiber adsorbing material and preparation method and application thereof |
| CN114702732A (en) * | 2022-06-07 | 2022-07-05 | 江苏集萃智能液晶科技有限公司 | Polymer particle with double-size pore channel and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109134944A (en) | A kind of porous small ball and its application with different chemical functional groups | |
| KR101783951B1 (en) | Graphene-containing Viscose Fiber and Preparation Method thereof | |
| CN103866487B (en) | The preparation method of a kind of nano micro crystal cellulose/chitosan/polyvinyl alcohol composite nanometer film | |
| CN101612540B (en) | Method for preparing cellulose microsphere by taking ionic liquid as solvent | |
| JP5072846B2 (en) | Use of aqueous sodium hydroxide / thiourea solution in the manufacture of cellulose products on a pilot scale | |
| CN101921410B (en) | Method for preparing cellulose microspheres | |
| CN107556495A (en) | A kind of preparation method of functional nano cellulose composite aerogel | |
| CN102504285A (en) | Regenerated cellulose microspheres and preparation method thereof | |
| CN111793223B (en) | Method for preparing nano-grade regenerated cellulose by adopting molten salt system | |
| CN102344685A (en) | Method for preparing nano cellulose microfibril reinforced polymer composite material | |
| CN103756016A (en) | Cellulose micro-sphere with uniform size as well as preparation method and application thereof | |
| CN106450108A (en) | Preparation method of modified cellulose lithium battery diaphragm under sodium hydroxide/urea system | |
| CN109012638B (en) | Preparation method of carboxylated hierarchical porous cellulose adsorption balls | |
| CN106179244A (en) | A kind of cellulose base is composite porous and its production and use | |
| CN111253597B (en) | Chitin nanofiber/polyaniline composite gel film and preparation method thereof | |
| CN104226268A (en) | Modified cellulose/graphene oxide composite microsphere and preparation method thereof | |
| CN109232993A (en) | A kind of preparation method of cellulose/micrometer fibers element long filament porous small ball | |
| CN1699442A (en) | Solvent for dissolving cellulose and its preparation method and use | |
| CN101607178A (en) | A kind of preparation method of doughnut perforated membrane | |
| Yao et al. | Application of cellulose to chromatographic media: Cellulose dissolution, and media fabrication and derivatization | |
| CN103990439A (en) | Method for preparing cellulose acetate butyrate microsphere adsorption material | |
| CN107501615A (en) | A kind of preparation method of high strength regenerative cellulose film | |
| CN104262642A (en) | Method for dissolving cellulose in aqueous solution of NaOH/thiourea at normal temperature | |
| CN104497362B (en) | A kind of preparation method of cellulose/nanometer silicon nitride composite membrane | |
| CN105463846B (en) | A kind of water-soluble sizing agent composition for carbon fiber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190104 |
|
| RJ01 | Rejection of invention patent application after publication |