CN106179249B - A kind of preparation method of concave convex rod cellulose composite adsorption microballoon - Google Patents
A kind of preparation method of concave convex rod cellulose composite adsorption microballoon Download PDFInfo
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- CN106179249B CN106179249B CN201610701749.8A CN201610701749A CN106179249B CN 106179249 B CN106179249 B CN 106179249B CN 201610701749 A CN201610701749 A CN 201610701749A CN 106179249 B CN106179249 B CN 106179249B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
Abstract
The invention discloses a kind of preparation method of concave convex rod cellulose composite adsorption microballoon, this method includes following three steps：The pretreatment of concave convex rod and surface are modified；It is prepared by ionic liquid cellulose solution；The preparation of concave convex rod cellulose composite adsorption microballoon.Preparation process is simple and convenient, the ion liquid solvent used is safe and non-toxic, and the concave convex rod cellulose microsphere of preparation is porous, and dispersibility, biocompatibility and thermal stability are good, have many advantages, such as that adsorption capacity is strong, adsorption capacity is big, removal efficiency is high, property is stablized to water pollutant, is easily recycled；Solve concave convex rod adsorption energy force difference, recycling hardly possible; the problems such as cellulose adsorbent mechanical strength is weak, thermal stability is low; raw material sources are extensive simultaneously; it is cheap; secondary pollution is not generated, makes full use of cellulose, concave convex rod regenerated resources, practical value high; the advanced treating that can be used for water pollutant, solves energy crisis and problem of environmental pollution.
Description
Technical field：
The present invention relates to sewage treatment fields, and in particular to a kind of preparation side of concave convex rod cellulose composite adsorption microballoon
Method.
Background technology：
With the high speed development of modern society, environmental pollution caused by industrial wastewater and sanitary sewage etc. makes ecological environment meet with
It is destroyed to serious.How dirty water pollutant is economically and efficiently administered, oneself becomes environmental protection and the extremely urgent task of chemical industry
One of.
Concave convex rod has unique layer chain crystal structure and nano level fibrous crystal form, and inner duct is flourishing, than
Surface area is larger, these impart the stronger absorption property of concave convex rod and ion-exchange performance.Its to the heavy metal in waste water from
Organic pollution in son and water, such as benzene-like compounds, phenolic compound, Crude Oil ＆ Petroleum Products are made with very strong absorption
With.In addition concave convex rod itself is nontoxic, storage capacity is high, of low cost in harmless, nature, the technological operation letter in water treatment procedure
Just the advantages that, adsorption efficiency is high, nonstaining property and secondary pollution are few, makes concave convex rod in the processing table of trade effluent and sanitary sewage
Reveal excellent application potential.However concave convex rod is as a kind of natural clay, and when concave convex rod is applied in waste water, water and organic
When concave convex rod apparent competitive adsorbs, hydrone is preferentially adsorbed pollutant, is occupied the active site of concave convex rod channel surfaces, is made
It is low to organic pollutant removal rate to obtain it, limits its application in adsorbing domain.Additionally due to its surface energy is high so that concave-convex
Stick is easily assembled agglomerating, and the concave convex rod specific surface area after aggregation is reduced, to limit its adsorption capacity, and its powder
There is also certain difficulty in the recycling problem of shape form after use.
Cellulose is that nature contains most abundant renewable resource, is a kind of natural polysaccharide molecule, nontoxic, can biology
Degradation, water-resistance is strong, hydrophily, good biocompatibility, suitable porous structure with height, extremely low non-specific suction
Attached performance contains numerous amino and hydroxyl on macromolecular chain, has absorption, flocculation to metal ion, polar organic compound
Effect, is a kind of good adsorbent base material.The adsorbent prepared with cellulose is widely used in the richness of each metal ion species
Collection separation, protein isolate and purify and the removing etc. of Wastewater Dyes；But due to the intermolecular strong hydrogen of native cellulose
Key acts on, and forms very fine and close structure, the difficulty for causing cellulosic material to process, and there are mechanical strengths for cellulose adsorbent
Weak, the problems such as thermal stability is low.
Invention content：
The object of the present invention is to provide a kind of preparation method of concave convex rod cellulose composite adsorption microballoon, preparation process is simple
Convenient, the ion liquid solvent used is safe and non-toxic, and the concave convex rod cellulose microsphere of preparation is porous, dispersibility, biocompatibility
It is good with thermal stability, to water pollutant have adsorption capacity is strong, adsorption capacity is big, removal efficiency is high, property stablize, be easy to back
The advantages that receipts；It is difficult to solve concave convex rod adsorption energy force difference, recycling, cellulose adsorbent mechanical strength is weak, thermal stability is low etc. asks
Topic, while raw material sources are extensive, it is cheap, secondary pollution is not generated, cellulose, concave convex rod regenerated resources are made full use of, it is real
It is high with value, it can be used for the advanced treating of water pollutant, solve energy crisis and problem of environmental pollution.
The present invention is achieved by the following technical programs：
A kind of preparation method of concave convex rod cellulose composite adsorption microballoon, this method include following three steps：
A, the pretreatment of concave convex rod and surface are modified：Powder concave convex rod impregnates 8- with the dilute hydrochloric acid that mass fraction is 5-10%
To neutrality, it is 9 to be distributed to ethyl alcohol and water volume ratio for washing after 12h:In 1 mixed solution, silane coupling agent is added, in 40-50
It is adsorbed after ultrasound 50min at DEG C, adsorbed product is dried to obtain silane-modified attapulgite after isolating and purifying at 110 DEG C, grinding
It is spare；The mass ratio of the powder concave convex rod and silane coupling agent is 4: 1~6: 1；
B, the preparation of ionic liquid cellulose solution：The fibre of 2~6 parts by weight is added in the ionic liquid of 100 parts by weight
Dimension element, 90~110 DEG C are stirred to cellulose and are completely dissolved, and obtain ionic liquid cellulose solution；
C, the preparation of concave convex rod cellulose composite adsorption microballoon：It is added in the ionic liquid cellulose solution that step b is obtained
The silane-modified attapulgite obtained in step a, silane-modified attapulgite quality are ionic liquid cellulose solution quality
0.2-0.4 times, 90~100 DEG C, after stirring 20~30 minutes under 80~200rpm rotating speeds, oil phase and surfactant, oil is added
The mass ratio of the volume ratio 4: 1~6: 1 of phase and ionic liquid cellulose solution, surfactant and oil phase is 1: 40~1: 100,
Stirring 15~20 minutes forms inverse suspension system, is cooled to 30~50 DEG C by program, curing agent, the body of curing agent is added
Product is 2~3 times of ionic liquid cellulose solution volume, is kept stirring 20 minutes, and it is micro- to form concave convex rod cellulose composite adsorption
Ball；It is washed with deionized and impregnates, hygrometric state screening obtains concave convex rod cellulose composite adsorption microballoon.
Described program cooling refers to the rate of every 5 DEG C of 10min coolings.
The preparation method of the concave convex rod cellulose composite adsorption microballoon, specifically includes following steps：
A, concave convex rod obtains the powder that granularity is 200 mesh through extruding, shearing, crushing, is the dilute of 5-10% with mass fraction
Salt acid soak 8-12h is washed with deionized again be precipitated to neutrality after to be distributed to ethyl alcohol and water volume ratio be 9:1 mixed solution
In, silane coupling agent is added in stirring, the ultrasound 50min at 40-50 DEG C, 50 DEG C of stirring and adsorbing 4h, adsorbed product are divided through filtering
It is washed successively with toluene, absolute ethyl alcohol and deionized water from after and removes extra silane coupling agent, it is dry at 110 DEG C, it obtains
Silane-modified attapulgite, grinding are spare；The mass ratio of the powder concave convex rod and silane coupling agent is 4: 1~6: 1；
B, the preparation of ionic liquid cellulose solution：The fibre of 2~6 parts by weight is added in the ionic liquid of 100 parts by weight
Dimension element, 90~110 DEG C are stirred to cellulose and are completely dissolved, and speed of agitator is 80~200rpm, obtains ionic liquid fiber
Plain solution；
C, the preparation of concave convex rod cellulose composite adsorption microballoon：It is added in the ionic liquid cellulose solution that step b is obtained
The silane-modified attapulgite obtained in step a, silane-modified attapulgite quality are ionic liquid cellulose solution quality
0.2-0.4 times, 90~100 DEG C, after stirring 20~30 minutes under 80~200rpm rotating speeds, oil phase and surfactant, oil is added
The mass ratio of the volume ratio 4: 1~6: 1 of phase and ionic liquid cellulose solution, surfactant and oil phase is 1: 40~1: 100,
It is stirred 15~20 minutes under 300~500rpm rotating speeds, forms inverse suspension system, cooled down with 5 DEG C of rate of every 10min coolings
To 30~50 DEG C, cellulose solution condenses balling-up；Curing agent is added, the volume of curing agent is ionic liquid cellulose solution volume
2~3 times；Rotating speed is reduced to 200rpm after five minutes, is kept stirring 20 minutes, and cellulose solution cures rapidly, and it is fine to form concave convex rod
Concave convex rod cellulose composite adsorption microballoon is filtered out from reaction solution, is spent by the plain composite adsorption microballoon of dimension, room temperature to be down to
Then ion water washing impregnates microballoon 48 hours in deionized water；Hygrometric state sieves, and obtains concave convex rod cellulose composite adsorption
Microballoon.
In step a, the silane coupling agent is selected from γ-(2,3- glycidoxy) propyl trimethoxy silicane, N-2
One kind in (aminoethyl) 3- aminopropyl trimethoxysilanes, vinyltrimethoxysilane.
In step a, granularity be 200 mesh powder concave convex rod with mass fraction be 5-10% dilute hydrochloric acid impregnate 8-12h after,
It is in fluffy similar colloidal sol form that attapulgite, which obtains activation, is carried out at the modification of surface through silane coupling agent after washing to neutrality
Reason, concave convex rod surface becomes appropriate lipophile from total hydrophilic, enhances dispersibility in organic solvent, reduce concave convex rod
Agglomeration, be conducive to organic pollution concave convex rod apparent competitive adsorb.
In step b, the ionic liquid is 1- butyl -3- methylimidazole villaumites or 1- allyl -3- methylimidazole vinegar
Hydrochlorate；The one kind of the cellulose in paper pulp, absorbent cotton, purified cotton or microcrystalline cellulose.
Native cellulose has the design feature that crystallinity is high, intermolecular and intramolecule contains a large amount of hydrogen bonds, makes its hardly possible
It is dissolved in water and common organic solvent.Ionic liquid is a kind of green solvent of novel cellulose, can effectively destroy cellulose
Crystal structure reduces its crystallinity, not only can effectively dissolve cellulose, and good reaction ring can also be provided for cellulose
Border.
In step c, the surfactant is or mixtures thereof Tween 80, Span 85；The oil phase be pump oil,
Mineral oil, paraffin oil or peanut oil；The curing agent is or mixtures thereof water, ethyl alcohol, acetone.
Beneficial effects of the present invention are as follows：
(1) present invention directly dissolves cellulose, simple for process, nontoxic, environmental pollution using solion as solvent
It is small, and can recycle again.
(2) by silane coupling agent to concave convex rod carry out surface modification, make concave convex rod surface polarity reduction, surface nature by
Total hydrophilic becomes appropriate lipophile, enhances dispersibility in organic solvent, reduces the agglomeration of concave convex rod, is conducive to
Organic pollution is adsorbed in concave convex rod apparent competitive.
(3) present invention couples modified attapulgite with two kinds of sorbing materials of cellulose of ion liquid dissolving, generates collaboration
Effect enhances concave convex rod and the intermolecular compatibility of organic cellulose, improves the binding force of molecular interface, promote fiber
Plain microballoon forming, effectively improves absorption property；In addition concave convex rod component is embedded in the reticular structure of regenerated cellulose, effectively improves
The mechanical strength and thermal stability of microballoon；Meanwhile cellulose provides good carrier function for concave convex rod, further avoids recessed
Convex stick aggregation, is conducive to the recycling of concave convex rod adsorbent.
(4) concave convex rod is nontoxic, harmless, storage capacity is high, of low cost；Cellulose is widely present in green plants, is certainly
The right most abundant renewable resource in boundary, makes full use of attapulgite, cellulose to not only conform with the requirement of " Green Chemistry ", can be with
Solve the influence that environmental pollution is brought.Compatibility is carried out by the host materials such as cellulose and attapulgite, formation has both porous knot
The sorbing material of structure and stronger pollutant adsorption capacity, so as to get adsorbent have that adsorption capacity is strong, adsorption capacity is big, removal
Efficient advantage, property are stablized, are easily recycled.
In short, preparation process of the present invention is simple and convenient, the ion liquid solvent used is safe and non-toxic, by modified attapulgite with
Two kinds of sorbing material couplings of cellulose of ion liquid dissolving, generate synergistic effect, and the concave convex rod cellulose microsphere of preparation is porous,
Dispersibility, biocompatibility and thermal stability are good, have that adsorption capacity is strong, adsorption capacity is big, removal efficiency to water pollutant
High, property is stablized, the advantages that being easily recycled；Solve concave convex rod adsorption energy force difference, recycling hardly possible, cellulose adsorbent mechanical strength
It is weak, the problems such as thermal stability is low, while raw material sources are extensive, cheap, do not generate secondary pollution, make full use of cellulose,
Concave convex rod regenerated resources, practical value is high, can be used for the advanced treating of water pollutant, solves energy crisis and environmental pollution
Problem.
Specific implementation mode：
It is the further explanation to the present invention below, rather than limiting the invention.
Embodiment 1：
By attapulgite through extruding, shearing, crushing, the powder that granularity is 200 mesh is obtained, powder mass fraction is 5%
Dilute hydrochloric acid impregnates 8h, is then washed repeatedly with deionized water and is precipitated to neutrality, 20g is taken to be distributed to the mixing of 100mL second alcohol and waters
In solution, wherein ethyl alcohol and water volume ratio are 9:1,5g γ-(2,3- glycidoxy) propyl front three is then added while stirring
Oxysilane coupling agent, the ultrasound 50min at 40 DEG C, then in 50 DEG C of stirring and adsorbing 4h, adsorbed product after filtering and detaching according to
Secondary washed with 100ml toluene, absolute ethyl alcohol and deionized water removes extra silane coupling agent, is dried to get silicon at 110 DEG C
Alkane is attapulgite modified, and grinding is spare.
In 100 grams of 1- butyl -3- methyl-imidazoles villaumite is added in flask, 2 grams of paper pulp, at 90 DEG C, 80rpm rotating speeds stir
It mixes, until cellulose is completely dissolved to obtain ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is 0.2 times of ionic liquid cellulose solution quality, it is distributed to ion
It in liquid fiber element solution, is stirred under 90 DEG C, 80rpm rotating speeds after twenty minutes, (oil phase is pump for addition oil phase and surfactant
Oil, surfactant are Tween 80), the volume ratio of oil phase and ionic liquid cellulose solution is 4: 1, surfactant and oil phase
Mass ratio be 1: 40, stir 15 minutes under 300rpm rotating speeds, forms inverse suspension system, with every 10 clock 5 DEG C of speed of cooling
Rate is cooled to 30 DEG C, and cellulose solution condenses balling-up；Curing agent is added, and (curing agent is water, and volume is that ionic liquid cellulose is molten
2 times of liquid product), rotating speed is reduced to 200rpm after five minutes, is kept stirring 20 minutes, and cellulose solution cures rapidly, is formed concave-convex
Stick cellulose composite adsorption microballoon, temperature are down to room temperature, and microballoon is filtered out from reaction solution, with 1~2 times of volume go from
Then sub- water washing 3~6 times impregnates concave convex rod cellulose composite adsorption microballoon 48 hours in deionized water；By concave convex rod
Cellulose composite adsorption microballoon hygrometric state sieves, and obtains concave convex rod cellulose composite adsorption microballoon.
Embodiment 2：
By attapulgite through extruding, shearing, crushing, the powder that granularity is 200 mesh is obtained, powder mass fraction is 10%
Dilute hydrochloric acid impregnates 12h, is then washed repeatedly with deionized water and is precipitated to neutrality, 20g is taken to be distributed to the mixing of 100mL second alcohol and waters
In solution, wherein ethyl alcohol and water volume ratio are 9:1,4g N-2 (aminoethyl) 3- aminopropyl trimethoxies are then added while stirring
Silane coupling agent, the ultrasound 50min at 50 DEG C, then in 50 DEG C of stirring and adsorbing 4h, adsorbed product is used successively after filtering and detaching
100ml toluene, absolute ethyl alcohol and deionized water washing remove extra silane coupling agent, dry at 110 DEG C to change to get silane
Property attapulgite, grinding it is spare.
In being added 100 grams of 1- allyl -3- methylimidazoles acetate in flask, 6 grams of absorbent cotton, at 100 DEG C, 200rpm
Rotating speed stirs, until cellulose is completely dissolved to obtain ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is 0.4 times of ionic liquid cellulose solution quality, it is distributed to ion
In liquid fiber element solution, after being stirred 30 minutes under 100 DEG C, 200rpm rotating speeds, oil phase and surfactant is added, and (oil phase is
Mineral oil, surfactant are Span 85), the volume ratio of oil phase and ionic liquid cellulose solution is 6: 1, surfactant
Mass ratio with oil phase is 1: 100, is stirred 20 minutes under 500rpm rotating speeds, and inverse suspension system is formed, with every 10 clock cooling 5
DEG C rate be cooled to 50 DEG C, cellulose solution condenses balling-up；Curing agent is added, and (curing agent is ethyl alcohol, and volume is ionic liquid
3 times of cellulose solution volume), rotating speed is reduced to 200rpm after five minutes, is kept stirring 20 minutes, and cellulose solution cures rapidly,
Concave convex rod cellulose composite adsorption microballoon is formed, temperature is down to room temperature, microballoon is filtered out from reaction solution, with 1~2 times of body
Long-pending deionized water is washed 3~6 times, then impregnates concave convex rod cellulose composite adsorption microballoon 48 hours in deionized water；
Concave convex rod cellulose composite adsorption microballoon hygrometric state is sieved, concave convex rod cellulose composite adsorption microballoon is obtained.
Embodiment 3：
By attapulgite through extruding, shearing, crushing, the powder that granularity is 200 mesh is obtained, powder mass fraction is 8%
Dilute hydrochloric acid impregnates 10h, is then washed repeatedly with deionized water and is precipitated to neutrality, 20g is taken to be distributed to the mixing of 100mL second alcohol and waters
In solution, wherein ethyl alcohol and water volume ratio are 9:1,3.3g vinyltrimethoxysilane coupling agents are then added while stirring,
The ultrasound 50min at 50 DEG C, then in 50 DEG C of stirring and adsorbing 4h, adsorbed product uses 100ml toluene, nothing successively after filtering and detaching
Water-ethanol and deionized water washing remove extra silane coupling agent, are dried at 110 DEG C to get silane-modified attapulgite,
It grinds spare.
In being added 100 grams of 1- allyl -3- methylimidazoles acetate in flask, 5 grams of purified cotton, at 100 DEG C, 150rpm
Rotating speed stirs, until cellulose is completely dissolved to obtain ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is 0.3 times of ionic liquid cellulose solution quality, it is distributed to ion
In liquid fiber element solution, after being stirred 25 minutes under 95 DEG C, 150rpm rotating speeds, oil phase and surfactant is added, and (oil phase is
Paraffin oil, surfactant are Span 85), the volume ratio of oil phase and ionic liquid cellulose solution is 5: 1, surfactant
Mass ratio with oil phase is 1: 60, is stirred 20 minutes under 400rpm rotating speeds, and inverse suspension system is formed, with every 10 clock cooling 5
DEG C rate be cooled to 40 DEG C, cellulose solution condenses balling-up；Curing agent is added, and (curing agent is acetone, and volume is ionic liquid
3 times of cellulose solution volume), rotating speed is reduced to 200rpm after five minutes, is kept stirring 20 minutes, and cellulose solution cures rapidly,
Concave convex rod cellulose composite adsorption microballoon is formed, temperature is down to room temperature, microballoon is filtered out from reaction solution, with 1~2 times of body
Long-pending deionized water is washed 3~6 times, then impregnates concave convex rod cellulose composite adsorption microballoon 48 hours in deionized water；
Concave convex rod cellulose composite adsorption microballoon hygrometric state is sieved, concave convex rod cellulose composite adsorption microballoon is obtained.
Embodiment 4：
By attapulgite through extruding, shearing, crushing, the powder that granularity is 200 mesh is obtained, powder mass fraction is 7%
Dilute hydrochloric acid impregnates 11h, is then washed repeatedly with deionized water and is precipitated to neutrality, 20g is taken to be distributed to the mixing of 100mL second alcohol and waters
In solution, wherein ethyl alcohol and water volume ratio are 9:1,4.4g N-2 (aminoethyl) 3- aminopropyl trimethoxies are then added while stirring
Base silane coupling agent, the ultrasound 50min at 45 DEG C, then in 50 DEG C of stirring and adsorbing 4h, adsorbed product after filtering and detaching successively
It is washed with 100ml toluene, absolute ethyl alcohol and deionized water and removes extra silane coupling agent, dried to get silane at 110 DEG C
Attapulgite modified, grinding is spare.
In being added 100 grams of 1- butyl -3- methylimidazole villaumites in flask, 4 grams of microcrystalline cellulose, at 100 DEG C, 100rpm
Rotating speed stirs, until cellulose is completely dissolved to obtain ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is 0.4 times of ionic liquid cellulose solution quality, it is distributed to ion
In liquid fiber element solution, after being stirred 25 minutes under 95 DEG C, 180rpm rotating speeds, oil phase and surfactant is added, and (oil phase is
Peanut oil, surfactant are Tween 80), the volume ratio of oil phase and ionic liquid cellulose solution is 6: 1, surfactant with
The mass ratio of oil phase is 1: 40, is stirred 20 minutes under 450rpm rotating speeds, and inverse suspension system is formed, and is cooled down 5 DEG C with every 10 clock
Rate be cooled to 30 DEG C, cellulose solution condenses balling-up；Consolidating for 3 times that volume is ionic liquid cellulose solution volume is added
(curing agent is that volume ratio is 1 to agent:3 ethyl alcohol and acetone mixture), rotating speed is reduced to 200rpm after five minutes, is kept stirring 20
Minute, cellulose solution cures rapidly, forms concave convex rod cellulose composite adsorption microballoon, and temperature is down to room temperature, by microballoon from anti-
It answers in liquid and filters out, washed 3~6 times with the deionized water of 1~2 times of volume, it is then that concave convex rod cellulose composite adsorption is micro-
Ball impregnates 48 hours in deionized water；Concave convex rod cellulose composite adsorption microballoon hygrometric state is sieved, concave convex rod cellulose is obtained
Composite adsorption microballoon.
Embodiment 5：
By attapulgite through extruding, shearing, crushing, the powder that granularity is 200 mesh is obtained, powder mass fraction is 6%
Dilute hydrochloric acid impregnates 9h, is then washed repeatedly with deionized water and is precipitated to neutrality, 20g is taken to be distributed to the mixing of 100mL second alcohol and waters
In solution, wherein ethyl alcohol and water volume ratio are 9:1,5g vinyltrimethoxysilane coupling agents are then added while stirring,
Ultrasound 50min at 45 DEG C, then in 50 DEG C of stirring and adsorbing 4h, adsorbed product uses 100ml toluene, anhydrous successively after filtering and detaching
Ethyl alcohol and deionized water washing remove extra silane coupling agent, dry to get silane-modified attapulgite, grind at 110 DEG C
It grinds spare.
In being added 100 grams of 1- allyl -3- methylimidazoles acetate in flask, 5 grams of microcrystalline cellulose, at 100 DEG C,
150rpm rotating speeds stir, until cellulose is completely dissolved to obtain ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is 0.3 times of ionic liquid cellulose solution quality, it is distributed to ion
It in liquid fiber element solution, is stirred under 100 DEG C, 150rpm rotating speeds after twenty minutes, oil phase and surfactant is added, and (oil phase is
Peanut oil, surfactant are that mass ratio is 1：The mixture of 1 Tween 80 and Span 85), oil phase and ionic liquid cellulose
The volume ratio of solution is 5: 1, and the mass ratio of surfactant and oil phase is 1: 60, is stirred 20 minutes under 400rpm rotating speeds, shape
At inverse suspension system, 30 DEG C are cooled to 5 DEG C of rate of every 10 clock cooling, cellulose solution condenses balling-up；Volume, which is added, is
(curing agent is that volume ratio is 1 to 3 times of curing agent of ionic liquid cellulose solution volume:1 ethyl alcohol and acetone mixture), 5
Rotating speed is reduced to 200rpm after minute, is kept stirring 20 minutes, and cellulose solution cures rapidly, forms the compound suction of concave convex rod cellulose
Attached microballoon, temperature are down to room temperature, and microballoon is filtered out from reaction solution, and 3~6 are washed with the deionized water of 1~2 times of volume
It is secondary, then concave convex rod cellulose composite adsorption microballoon is impregnated 48 hours in deionized water；By the compound suction of concave convex rod cellulose
Attached microballoon hygrometric state screening, obtains concave convex rod cellulose composite adsorption microballoon.
Embodiment 6：
By attapulgite through extruding, shearing, crushing, the powder that granularity is 200 mesh is obtained, powder mass fraction is 8%
Dilute hydrochloric acid impregnates 10h, is then washed repeatedly with deionized water and is precipitated to neutrality, 20g is taken to be distributed to the mixing of 100mL second alcohol and waters
In solution, wherein ethyl alcohol and water volume ratio are 9:1,5g γ-(2,3- glycidoxy) propyl front three is then added while stirring
Oxysilane coupling agent, the ultrasound 50min at 50 DEG C, then in 50 DEG C of stirring and adsorbing 4h, adsorbed product after filtering and detaching according to
Secondary washed with 100ml toluene, absolute ethyl alcohol and deionized water removes extra silane coupling agent, is dried to get silicon at 110 DEG C
Alkane is attapulgite modified, and grinding is spare.
In being added 100 grams of 1- butyl -3- methylimidazole villaumites in flask, 5 grams of microcrystalline cellulose, at 100 DEG C, 180rpm
Rotating speed stirs, until cellulose is completely dissolved to obtain ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is 0.3 times of ionic liquid cellulose solution quality, it is distributed to ion
It in liquid fiber element solution, is stirred under 100 DEG C, 180rpm rotating speeds after twenty minutes, oil phase and surfactant is added, and (oil phase is
Paraffin oil, surfactant are that mass ratio is 1：The mixture of 1 Tween 80 and Span 85), oil phase and ionic liquid cellulose
The volume ratio of solution is 5: 1, and the mass ratio of surfactant and oil phase is 1: 80, is stirred 15 minutes under 400rpm rotating speeds, shape
At inverse suspension system, 30 DEG C are cooled to 5 DEG C of rate of every 10 clock cooling, cellulose solution condenses balling-up；Volume, which is added, is
(curing agent is that volume ratio is 1 to 3 times of curing agent of ionic liquid cellulose solution volume:1 ethyl alcohol and aqueous mixtures), 5 points
Rotating speed is reduced to 200rpm after clock, is kept stirring 20 minutes, and cellulose solution cures rapidly, forms concave convex rod cellulose composite adsorption
Microballoon, temperature are down to room temperature, and microballoon is filtered out from reaction solution, are washed 3~6 times with the deionized water of 1~2 times of volume,
Then concave convex rod cellulose composite adsorption microballoon is impregnated 48 hours in deionized water；Concave convex rod cellulose composite adsorption is micro-
Ball hygrometric state sieves, and obtains concave convex rod cellulose composite adsorption microballoon.
Embodiment 7：Concave convex rod cellulose composite adsorption microballoon prepared by the present invention is used for pollutant adsorption treatment：
The concave convex rod cellulose composite adsorption microballoon that is prepared respectively with embodiment 1-6, does not change naturally silane-modified concave convex rod
Property concave convex rod and natural, unmodified cellulose be adsorbent, be respectively the phenol of 5mg/L with initial concentration, catechol, to benzene
Diphenol, methylene blue, methyl orange, copper ion, cadmium ion, lead ion carry out adsorption treatment as pollutant.The specific method is as follows：
It is that adsorbent, solid-to-liquid ratio 1g is added in 5mg/L organic pollutions to initial concentration：50mL, with 200r/ at 25 DEG C
Min rotating speed constant temperature oscillations adsorb 12h, filter to take filtrate, measure adsorbance, as a result referring to table 1.
The different adsorbents of table 1 are to pollutant adsorption treatment
The concave convex rod cellulose composite adsorption microballoon and silane-modified bumps that as can be seen from Table 1 prepared by embodiment 1-6
Stick, natural, unmodified attapulgite are compared with natural, unmodified cellulose, and the removal efficiency for contaminating phenols in water object can be improved 3-5 times
More than；It is up to 97-99% to water Methylene Blue removal efficiency；75% or more has also been reached to methyl orange removal efficiency；To a huge sum of money
The adsorbing and removing of category also has better effects, and removal efficiency is between 55-77%；And natural, unmodified concave convex rod and natural, unmodified
Cellulose is to reach 35% or more to the removal efficiency of pollutant.As can be seen from the above data, the concave convex rod that prepared by the present invention
Cellulose composite adsorption microballoon absorption property is good, preferable to pollutant removal.
The present invention obtains modified attapulgite and cellulose compatibility with porous structure, the adsorbing medium of large specific surface area,
By learning from other's strong points to offset one's weaknesses, synergistic effect is generated, improves absorption to pollutant, accumulation ability, property is stablized, is easily recycled again sharp
With；Raw material sources are extensive simultaneously, cheap, do not generate secondary pollution, practical value is high, can be used for the depth of water pollutant
Processing.
Claims (5)
1. a kind of preparation method of concave convex rod cellulose composite adsorption microballoon, which is characterized in that this method includes following three steps
Suddenly：
A, washing is to neutrality after the dilute hydrochloric acid that powder concave convex rod is 5-10% with mass fraction impregnates 8-12h, be distributed to ethyl alcohol and
Water volume ratio is 9:In 1 mixed solution, silane coupling agent is added, is adsorbed after ultrasound 50min at 40-50 DEG C, adsorbed product
Through isolating and purifying, silane-modified attapulgite is dried to obtain at 110 DEG C, grinding is spare；The powder concave convex rod with it is silane coupled
The mass ratio of agent is 4: 1~6: 1；
B, the cellulose of 2~6 parts by weight is added in the ionic liquid of 100 parts by weight, 90~110 DEG C are stirred to cellulose
It is completely dissolved, obtains ionic liquid cellulose solution；
C, the silane-modified attapulgite obtained in step a is added in the ionic liquid cellulose solution that step b is obtained, silane changes
Property attapulgite quality be 0.2-0.4 times of ionic liquid cellulose solution quality, 90~100 DEG C, under 80~200rpm rotating speeds
After stirring 20~30 minutes, oil phase and surfactant is added, the volume ratio 4: 1~6 of oil phase and ionic liquid cellulose solution:
1, the mass ratio of surfactant and oil phase is 1: 40~1: 100, stirs 15~20 minutes, forms inverse suspension system, pass through
Program is cooled to 30~50 DEG C, and curing agent is added, and the volume of curing agent is 2~3 times of ionic liquid cellulose solution volume, is protected
Stirring 20 minutes is held, concave convex rod cellulose composite adsorption microballoon is formed；It is washed with deionized and impregnates, hygrometric state screening obtains
Concave convex rod cellulose composite adsorption microballoon.
2. the preparation method of concave convex rod cellulose composite adsorption microballoon according to claim 1, which is characterized in that program drops
Temperature refers to the rate of every 5 DEG C of 10min coolings.
3. the preparation method of concave convex rod cellulose composite adsorption microballoon according to claim 1, which is characterized in that step a
In, the silane coupling agent is selected from γ-(2,3- glycidoxy) propyl trimethoxy silicane, N-2 (aminoethyl) 3- ammonia third
One kind in base trimethoxy silane, vinyltrimethoxysilane.
4. the preparation method of concave convex rod cellulose composite adsorption microballoon according to claim 1, which is characterized in that step b
In, the ionic liquid is 1- butyl -3- methylimidazole villaumites or 1- allyl -3- methylimidazole acetate；The fibre
The one kind of dimension element in paper pulp, absorbent cotton, purified cotton or microcrystalline cellulose.
5. the preparation method of concave convex rod cellulose composite adsorption microballoon according to claim 1, which is characterized in that step c
In, the surfactant is or mixtures thereof Tween 80, Span 85；The oil phase is pump oil, mineral oil, paraffin oil
Or peanut oil；The curing agent is or mixtures thereof water, ethyl alcohol, acetone.
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