CN106179249A - A kind of preparation method of attapulgite cellulose composite adsorption microsphere - Google Patents
A kind of preparation method of attapulgite cellulose composite adsorption microsphere Download PDFInfo
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- CN106179249A CN106179249A CN201610701749.8A CN201610701749A CN106179249A CN 106179249 A CN106179249 A CN 106179249A CN 201610701749 A CN201610701749 A CN 201610701749A CN 106179249 A CN106179249 A CN 106179249A
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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 the preparation method of a kind of attapulgite cellulose composite adsorption microsphere, the method includes three below step: the pretreatment of attapulgite and surface modification；Prepared by ionic liquid cellulose solution；The preparation of attapulgite cellulose composite adsorption microsphere.Preparation process is simple and convenient, the ion liquid solvent safety non-toxic used, the attapulgite cellulose microsphere porous of preparation, dispersibility, biocompatibility and Heat stability is good, have high adsorption capacity to water pollutant, adsorption capacity is big, removal efficiency is high, stable in properties, it is easy to the advantages such as recovery；Solve attapulgite absorbability poor, reclaim difficulty; the problems such as cellulose adsorbent mechanical strength is weak, heat stability is low; raw material sources are extensive simultaneously; cheap; not producing secondary pollution, make full use of cellulose, attapulgite regenerated resources, practical value is high; can be used for the advanced treating of water pollutant, solve energy crisis and problem of environmental pollution.
Description
Technical field:
The present invention relates to sewage treatment area, be specifically related to the preparation side of a kind of attapulgite cellulose composite adsorption microsphere
Method.
Background technology:
Along with the high speed development of modern society, the environmental pollution that industrial wastewater and sanitary sewage etc. cause makes ecological environment meet with
To heavy damage.How economical, administer dirty water pollutant efficiently, oneself becomes environmental protection and the extremely urgent task of chemical industry
One of.
Attapulgite has the layer chain crystal structure of uniqueness and nano level fibrous crystal form, and inner duct is flourishing, than
Surface area is relatively big, and these impart the stronger absorption property of attapulgite and ion-exchange performance.Its to the heavy metal in waste water from
Organic pollution in son and water, makees as benzene-like compounds, phenolic compound, Crude Oil & Petroleum Products etc. have the strongest absorption
With.Additionally attapulgite itself is nontoxic, harmless, storage capacity is high, with low cost in nature, technological operation letter in water treatment procedure
Just, adsorption efficiency is high, nonstaining property and the advantage such as secondary pollution is few, makes attapulgite at the process table of trade effluent and sanitary sewage
Reveal the application potential of excellence.But attapulgite is as a kind of natural clay, when attapulgite is applied in waste water, water and organic
Pollutant are when attapulgite apparent competitive adsorbs, and hydrone is preferentially adsorbed, and occupies the avtive spot of attapulgite channel surfaces, makes
Obtain it low to organic pollutant removal rate, limit its application in adsorbing domain.Additionally due to its surface can be high so that concavo-convex
Rod is easily assembled agglomerating, and the attapulgite specific surface area after gathering has reduced, thus limits its absorbability, and its powder
Certain difficulty is there is also in shape form recovery problem after a procedure.
Cellulose is that nature contains the abundantest Renewable resource, is a kind of natural polysaccharide molecule, nontoxic, can be biological
Degraded, water-resistance is strong, has the hydrophilic of height, good biocompatibility, suitable loose structure, extremely low non-specific suction
Attached performance, containing numerous amino and hydroxyl on its 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 separates, the removing etc. of the isolated and purified and Wastewater Dyes of protein；But due to the intermolecular strong hydrogen of native cellulose
Key effect, forms the finest and close structure, causes the difficulty that cellulosic material is processed, and cellulose adsorbent exists mechanical strength
The problems such as weak, heat stability is low.
Summary of the invention:
It is an object of the invention to provide the preparation method of a kind of attapulgite cellulose composite adsorption microsphere, preparation process is simple
Convenient, the ion liquid solvent safety non-toxic of use, the attapulgite cellulose microsphere porous of preparation, dispersibility, biocompatibility
And Heat stability is good, water pollutant is had high adsorption capacity, adsorption capacity is big, removal efficiency is high, stable in properties, it is easy to return
The advantages such as receipts；Solving that attapulgite absorbability is poor, reclaim difficulty, cellulose adsorbent mechanical strength is weak, heat stability is low etc. asks
Topic, raw material sources are extensive simultaneously, cheap, do not produce secondary pollution, make full use of cellulose, attapulgite regenerated resources, real
With being worth height, 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 attapulgite cellulose composite adsorption microsphere, the method includes three below step:
A, the pretreatment of attapulgite and surface modification: powder body attapulgite mass fraction is that the dilute hydrochloric acid of 5-10% soaks 8-
After 12h, washing is to neutral, is distributed in ethanol and mixed solution that water volume ratio is 9:1, adds silane coupler, at 40-50
Adsorbing after ultrasonic 50min at DEG C, adsorbed product is separated is dried to obtain silane-modified attapulgite at 110 DEG C after purification, grinds
Standby；Described powder body attapulgite is 4: 1～6: 1 with the mass ratio of silane coupler；
B, the preparation of ionic liquid cellulose solution: in the ionic liquid of 100 weight portions, add the fibre of 2～6 weight portions
Dimension element, 90～110 DEG C of stirring mixing are completely dissolved to cellulose, obtain ionic liquid cellulose solution；
C, the preparation of attapulgite cellulose composite adsorption microsphere: add in the ionic liquid cellulose solution that step b obtains
The silane-modified attapulgite obtained in step a, silane-modified attapulgite quality is ionic liquid cellulose solution quality
0.2-0.4 times, 90～100 DEG C, after stirring 20～30 minutes under 80～200rpm rotating speeds, add oil phase and surfactant, oil
With the volume ratio 4: 1～6: 1 of ionic liquid cellulose solution, surfactant is 1: 40～1: 100 with the mass ratio of oil phase,
Stir 15～20 minutes, form inverse suspension system, by programmed cooling to 30～50 DEG C, add firming agent, the body of firming agent
Amass 2～3 times for ionic liquid cellulose solution volume, be kept stirring for 20 minutes, form attapulgite cellulose composite adsorption micro-
Ball；Being washed with deionized and soak, hygrometric state sieves, and obtains attapulgite cellulose composite adsorption microsphere.
Described programmed cooling refers to the speed of every 10min cooling 5 DEG C.
The preparation method of described attapulgite cellulose composite adsorption microsphere, specifically includes following steps:
A, attapulgite obtain, through extruding, shear, pulverizing, the powder body that granularity is 200 mesh, are the dilute of 5-10% with mass fraction
Soak with hydrochloric acid 8-12h is washed with deionized after being precipitated to neutrality again and is distributed to ethanol and water volume ratio is the mixed solution of 9:1
In, stirring adds silane coupler, ultrasonic 50min at 40-50 DEG C, 50 DEG C of stirring and adsorbing 4h, adsorbed product is divided through sucking filtration
Remove unnecessary silane coupler with toluene, dehydrated alcohol and deionized water wash successively after from, be dried at 110 DEG C, obtain
Silane-modified attapulgite, grinds standby；Described powder body attapulgite is 4: 1～6: 1 with the mass ratio of silane coupler；
B, the preparation of ionic liquid cellulose solution: in the ionic liquid of 100 weight portions, add the fibre of 2～6 weight portions
Dimension element, 90～110 DEG C of stirring mixing are completely dissolved to cellulose, and speed of agitator is 80～200rpm, obtains ionic liquid fiber
Cellulose solution；
C, the preparation of attapulgite cellulose composite adsorption microsphere: add in the ionic liquid cellulose solution that step b obtains
The silane-modified attapulgite obtained in step a, silane-modified attapulgite quality is ionic liquid cellulose solution quality
0.2-0.4 times, 90～100 DEG C, after stirring 20～30 minutes under 80～200rpm rotating speeds, add oil phase and surfactant, oil
With the volume ratio 4: 1～6: 1 of ionic liquid cellulose solution, surfactant is 1: 40～1: 100 with the mass ratio of oil phase,
Stir 15～20 minutes under 300～500rpm rotating speeds, form inverse suspension system, with the speed cooling of every 10min cooling 5 DEG C
To 30～50 DEG C, cellulose solution condenses balling-up；Adding firming agent, the volume of firming agent is ionic liquid cellulose solution volume
2～3 times；After 5 minutes, rotating speed reduces to 200rpm, is kept stirring for 20 minutes, and cellulose solution solidifies rapidly, forms attapulgite fine
Dimension element composite adsorption microsphere, room temperature to be down to, attapulgite cellulose composite adsorption microsphere is filtered out from reactant liquor, spends
Ionized water washs, and then microsphere is soaked 48 hours in deionized water；Hygrometric state sieves, and obtains attapulgite cellulose composite adsorption
Microsphere.
In step a, described silane coupler is selected from γ-(2,3-glycidoxy) propyl trimethoxy silicane, N-2
One in (aminoethyl) 3-aminopropyl trimethoxysilane, vinyltrimethoxy silane.
In step a, after granularity is the dilute hydrochloric acid that powder body attapulgite mass fraction the is 5-10% immersion 8-12h of 200 mesh,
Attapulgite obtains activating in fluffy similar colloidal sol form, and washing is carried out at surface modification through silane coupler to neutrality
Reason, attapulgite surface is become appropriateness lipophile from total hydrophilic, strengthens dispersibility in organic solvent, decrease attapulgite
Agglomeration, beneficially organic pollution attapulgite apparent competitive adsorb.
In step b, described ionic liquid is 1-butyl-3-Methylimidazole. villaumite or 1-pi-allyl-3-Methylimidazole. vinegar
Hydrochlorate；Described cellulose one in paper pulp, absorbent cotton, purified cotton or microcrystalline Cellulose.
Native cellulose has the construction features that degree of crystallinity is high, intermolecular and intramolecule contains a large amount of hydrogen bond so that it is difficult
It is dissolved in water and common are machine solvent.Ionic liquid is the green solvent of a kind of novel cellulose, can effectively destroy cellulose
Crystal structure, reduces its degree of crystallinity, is possible not only to effectively dissolve cellulose, it is also possible to provide good reaction ring for cellulose
Border.
In step c, described surfactant is Tween 80, Span 85 or its mixture；Described oil phase be pump oil,
Mineral oil, paraffin oil or Oleum Arachidis hypogaeae semen；Described firming agent is water, ethanol, acetone or its mixture.
Beneficial effects of the present invention is as follows:
(1) present invention utilizes solion directly to dissolve cellulose as solvent, and technique is simple, nontoxic, environmental pollution
Little, and can again recycle.
(2) by silane coupler, attapulgite is carried out surface modification, makes attapulgite surface polarity reduce, surface nature by
Total hydrophilic becomes appropriateness lipophile, strengthens dispersibility in organic solvent, decreases the agglomeration of attapulgite, is beneficial to
Organic pollution adsorbs at attapulgite apparent competitive.
(3) modified attapulgite is coupled by the present invention with two kinds of adsorbing materials of cellulose of ion liquid dissolving, produces collaborative
Effect, enhances attapulgite and the intermolecular compatibility of organic cellulose, improves the adhesion of molecular interface, promote fiber
Element microsphere shapes, and is effectively improved absorption property；In addition attapulgite component is embedded in the network structure of regenerated cellulose, is effectively improved
The mechanical strength of microsphere and heat stability；Meanwhile, cellulose provides good carrier function for attapulgite, avoids recessed further
Convex rod is assembled, the beneficially recovery of attapulgite adsorbent.
(4) attapulgite is nontoxic, harmless, storage capacity is high, with low cost；Cellulose is widely present in green plants, is certainly
The Renewable resource that so boundary is the abundantest, makes full use of attapulgite, cellulose not only conforms with the requirement of " Green Chemistry ", it is also possible to
Solve the impact that environmental pollution brings.Carry out compatibility by host materials such as cellulose and attapulgites, formed and have porous knot concurrently
Structure and compared with the adsorbing material of strong pollutant absorbability so as to get adsorbent there is high adsorption capacity, adsorption capacity is big, remove
The advantage that efficiency is high, stable in properties, it is easy to recycling.
In a word, preparation process of the present invention is simple and convenient, the ion liquid solvent safety non-toxic of use, by modified attapulgite with
The two kinds of adsorbing material couplings of the cellulose of ion liquid dissolving, generation cooperative effect, the attapulgite cellulose microsphere porous of preparation,
Dispersibility, biocompatibility and Heat stability is good, have to water pollutant that high adsorption capacity, adsorption capacity be big, removal efficiency
High, stable in properties, it is easy to the advantages such as recovery；Solve attapulgite absorbability poor, reclaim difficulty, cellulose adsorbent mechanical strength
The problems such as weak, heat stability is low, raw material sources are extensive simultaneously, cheap, do not produce secondary pollution, make full use of cellulose,
Attapulgite regenerated resources, practical value is high, can be used for the advanced treating of water pollutant, solves energy crisis and environmental pollution
Problem.
Detailed description of the invention:
The following is and the present invention is further illustrated rather than limitation of the present invention.
Embodiment 1:
By attapulgite through extruding, shear, pulverizing, obtaining the powder body that granularity is 200 mesh, powder body mass fraction is 5%
Dilute hydrochloric acid soaks 8h, is then precipitated to neutrality with deionized water cyclic washing, takes 20g and be distributed to the mixing of 100mL second alcohol and water
In solution, wherein ethanol and water volume ratio are 9:1, add 5g γ-(2,3-glycidoxy) propyl group front three the most while stirring
TMOS coupling agent, ultrasonic 50min at 40 DEG C, then 50 DEG C of stirring and adsorbing 4h, adsorbed product depends on after sucking filtration separates
Secondary 100ml toluene, dehydrated alcohol and deionized water wash remove unnecessary silane coupler, be dried, obtain silicon at 110 DEG C
Alkane is attapulgite modified, grinds standby.
Adding 1-butyl-3-methyl-imidazoles villaumite 100 grams in flask, paper pulp 2 grams, at 90 DEG C, 80rpm rotating speed stirs
Mix, be completely dissolved to cellulose and obtain ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is ionic liquid cellulose solution quality 0.2 times, it is distributed to ion
In liquid fiber cellulose solution, at 90 DEG C, after stirring 20 minutes under 80rpm rotating speed, (oil phase is pump for addition oil phase and surfactant
Oil, surfactant are Tween 80), oil phase is 4: 1 with the volume ratio of ionic liquid cellulose solution, surfactant and oil phase
Mass ratio be 1: 40, stir 15 minutes under 300rpm rotating speed, form inverse suspension system, lower the temperature the speed of 5 DEG C with every 10 clocks
Rate is cooled to 30 DEG C, and cellulose solution condenses balling-up；(firming agent is water, and volume is that ionic liquid cellulose is molten to add firming agent
Long-pending 2 times of liquid), after 5 minutes, rotating speed reduces to 200rpm, is kept stirring for 20 minutes, and cellulose solution solidifies rapidly, is formed concavo-convex
Rod cellulose composite adsorption microsphere, temperature is down to room temperature, filtered out by microsphere from reactant liquor, with 1～2 times of volume go from
Sub-water washs 3～6 times, then attapulgite cellulose composite adsorption microsphere is soaked 48 hours in deionized water；By attapulgite
Cellulose composite adsorption microsphere hygrometric state sieves, and obtains attapulgite cellulose composite adsorption microsphere.
Embodiment 2:
By attapulgite through extruding, shear, pulverizing, obtaining the powder body that granularity is 200 mesh, powder body mass fraction is 10%
Dilute hydrochloric acid soaks 12h, is then precipitated to neutrality with deionized water cyclic washing, takes 20g and be distributed to the mixing of 100mL second alcohol and water
In solution, wherein ethanol and water volume ratio are 9:1, add 4g N-2 (aminoethyl) 3-aminopropyl trimethoxy the most while stirring
Silane coupler, ultrasonic 50min at 50 DEG C, then 50 DEG C of stirring and adsorbing 4h, adsorbed product is used after sucking filtration separates successively
100ml toluene, dehydrated alcohol and deionized water wash remove unnecessary silane coupler, be dried, obtain silane and change at 110 DEG C
Property attapulgite, grinds standby.
Addition 1-pi-allyl-3-Methylimidazole. acetate 100 grams in flask, absorbent cotton 6 grams, at 100 DEG C, 200rpm
Rotating speed stirs, and is completely dissolved to cellulose and obtains ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is ionic liquid cellulose solution quality 0.4 times, it is distributed to ion
In liquid fiber cellulose solution, at 100 DEG C, after stirring 30 minutes under 200rpm rotating speed, (oil phase is for addition oil phase and surfactant
Mineral oil, surfactant are Span 85), oil phase is 6: 1 with the volume ratio of ionic liquid cellulose solution, surfactant
It is 1: 100 with the mass ratio of oil phase, stirs 20 minutes under 500rpm rotating speed, form inverse suspension system, with every 10 clock coolings 5
DEG C speed be cooled to 50 DEG C, cellulose solution condense balling-up；(firming agent is ethanol, and volume is ionic liquid to add firming agent
3 times of cellulose solution volume), after 5 minutes, rotating speed reduces to 200rpm, is kept stirring for 20 minutes, and cellulose solution solidifies rapidly,
Forming attapulgite cellulose composite adsorption microsphere, temperature is down to room temperature, is filtered out by microsphere from reactant liquor, with 1～2 times of body
Long-pending deionized water wash 3～6 times, then soak 48 hours in deionized water by attapulgite cellulose composite adsorption microsphere；
Attapulgite cellulose composite adsorption microsphere hygrometric state is sieved, obtains attapulgite cellulose composite adsorption microsphere.
Embodiment 3:
By attapulgite through extruding, shear, pulverizing, obtaining the powder body that granularity is 200 mesh, powder body mass fraction is 8%
Dilute hydrochloric acid soaks 10h, is then precipitated to neutrality with deionized water cyclic washing, takes 20g and be distributed to the mixing of 100mL second alcohol and water
In solution, wherein ethanol and water volume ratio are 9:1, add 3.3g vinyltrimethoxy silane coupling agent the most while stirring,
Ultrasonic 50min at 50 DEG C, then 50 DEG C of stirring and adsorbing 4h, adsorbed product uses 100ml toluene, nothing after sucking filtration separates successively
Water-ethanol and deionized water wash remove unnecessary silane coupler, be dried, obtain silane-modified attapulgite at 110 DEG C,
Grind standby.
Addition 1-pi-allyl-3-Methylimidazole. acetate 100 grams in flask, purified cotton 5 grams, at 100 DEG C, 150rpm
Rotating speed stirs, and is completely dissolved to cellulose and obtains ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is ionic liquid cellulose solution quality 0.3 times, it is distributed to ion
In liquid fiber cellulose solution, at 95 DEG C, after stirring 25 minutes under 150rpm rotating speed, (oil phase is for addition oil phase and surfactant
Paraffin oil, surfactant are Span 85), oil phase is 5: 1 with the volume ratio of ionic liquid cellulose solution, surfactant
It is 1: 60 with the mass ratio of oil phase, stirs 20 minutes under 400rpm rotating speed, form inverse suspension system, with every 10 clock coolings 5
DEG C speed be cooled to 40 DEG C, cellulose solution condense balling-up；(firming agent is acetone, and volume is ionic liquid to add firming agent
3 times of cellulose solution volume), after 5 minutes, rotating speed reduces to 200rpm, is kept stirring for 20 minutes, and cellulose solution solidifies rapidly,
Forming attapulgite cellulose composite adsorption microsphere, temperature is down to room temperature, is filtered out by microsphere from reactant liquor, with 1～2 times of body
Long-pending deionized water wash 3～6 times, then soak 48 hours in deionized water by attapulgite cellulose composite adsorption microsphere；
Attapulgite cellulose composite adsorption microsphere hygrometric state is sieved, obtains attapulgite cellulose composite adsorption microsphere.
Embodiment 4:
By attapulgite through extruding, shear, pulverizing, obtaining the powder body that granularity is 200 mesh, powder body mass fraction is 7%
Dilute hydrochloric acid soaks 11h, is then precipitated to neutrality with deionized water cyclic washing, takes 20g and be distributed to the mixing of 100mL second alcohol and water
In solution, wherein ethanol and water volume ratio are 9:1, add 4.4g N-2 (aminoethyl) 3-aminopropyl trimethoxy the most while stirring
Base silane coupling agent, ultrasonic 50min at 45 DEG C, then 50 DEG C of stirring and adsorbing 4h, adsorbed product through sucking filtration separate after successively
Remove unnecessary silane coupler with 100ml toluene, dehydrated alcohol and deionized water wash, be dried at 110 DEG C, obtain silane
Attapulgite modified, grind standby.
Addition 1-butyl-3-Methylimidazole. villaumite 100 grams in flask, microcrystalline Cellulose 4 grams, at 100 DEG C, 100rpm
Rotating speed stirs, and is completely dissolved to cellulose and obtains ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is ionic liquid cellulose solution quality 0.4 times, it is distributed to ion
In liquid fiber cellulose solution, at 95 DEG C, after stirring 25 minutes under 180rpm rotating speed, (oil phase is for addition oil phase and surfactant
Oleum Arachidis hypogaeae semen, 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, stirs 20 minutes under 450rpm rotating speed, forms inverse suspension system, lowers the temperature 5 DEG C with every 10 clocks
Speed be cooled to 30 DEG C, cellulose solution condense balling-up；Addition volume is consolidating of 3 times of ionic liquid cellulose solution volume
Agent (firming agent be volume ratio be ethanol and the acetone mixture of 1:3), after 5 minutes, rotating speed reduces to 200rpm, is kept stirring for 20
Minute, cellulose solution solidifies rapidly, forms attapulgite cellulose composite adsorption microsphere, and temperature is down to room temperature, by microsphere from instead
Answer in liquid and filter out, with the deionized water wash 3 of 1～2 times of volume～6 times, then by micro-for attapulgite cellulose composite adsorption
Ball soaks 48 hours in deionized water；Attapulgite cellulose composite adsorption microsphere hygrometric state is sieved, obtains attapulgite cellulose
Composite adsorption microsphere.
Embodiment 5:
By attapulgite through extruding, shear, pulverizing, obtaining the powder body that granularity is 200 mesh, powder body mass fraction is 6%
Dilute hydrochloric acid soaks 9h, is then precipitated to neutrality with deionized water cyclic washing, takes 20g and be distributed to the mixing of 100mL second alcohol and water
In solution, wherein ethanol and water volume ratio are 9:1, add 5g vinyltrimethoxy silane coupling agent the most while stirring,
Ultrasonic 50min at 45 DEG C, then 50 DEG C of stirring and adsorbing 4h, adsorbed product after sucking filtration separates successively with 100ml toluene, anhydrous
Ethanol and deionized water wash remove unnecessary silane coupler, be dried, obtain silane-modified attapulgite, grind at 110 DEG C
Grind standby.
Addition 1-pi-allyl-3-Methylimidazole. acetate 100 grams in flask, microcrystalline Cellulose 5 grams, at 100 DEG C,
150rpm rotating speed stirs, and is completely dissolved to cellulose and obtains ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is ionic liquid cellulose solution quality 0.3 times, it is distributed to ion
In liquid fiber cellulose solution, at 100 DEG C, after stirring 20 minutes under 150rpm rotating speed, (oil phase is for addition oil phase and surfactant
Oleum Arachidis hypogaeae semen, surfactant be mass ratio be the mixture of Tween 80 and the Span 85 of 1:1), oil phase and ionic liquid cellulose
The volume ratio of solution is 5: 1, and surfactant is 1: 60 with the mass ratio of oil phase, stirs 20 minutes, shape under 400rpm rotating speed
Becoming inverse suspension system, be cooled to 30 DEG C with the speed of every 10 clocks cooling 5 DEG C, cellulose solution condenses balling-up；Adding volume is
The firming agent of 3 times of ionic liquid cellulose solution volume (firming agent be volume ratio be ethanol and the acetone mixture of 1:1), 5
After minute, rotating speed reduces to 200rpm, is kept stirring for 20 minutes, and cellulose solution solidifies rapidly, forms the compound suction of attapulgite cellulose
Attached microsphere, temperature is down to room temperature, is filtered out by microsphere from reactant liquor, with the deionized water wash 3～6 of 1～2 times of volume
Secondary, then attapulgite cellulose composite adsorption microsphere is soaked 48 hours in deionized water；Inhale compound for attapulgite cellulose
Attached microsphere hygrometric state sieves, and obtains attapulgite cellulose composite adsorption microsphere.
Embodiment 6:
By attapulgite through extruding, shear, pulverizing, obtaining the powder body that granularity is 200 mesh, powder body mass fraction is 8%
Dilute hydrochloric acid soaks 10h, is then precipitated to neutrality with deionized water cyclic washing, takes 20g and be distributed to the mixing of 100mL second alcohol and water
In solution, wherein ethanol and water volume ratio are 9:1, add 5g γ-(2,3-glycidoxy) propyl group front three the most while stirring
TMOS coupling agent, ultrasonic 50min at 50 DEG C, then 50 DEG C of stirring and adsorbing 4h, adsorbed product depends on after sucking filtration separates
Secondary 100ml toluene, dehydrated alcohol and deionized water wash remove unnecessary silane coupler, be dried, obtain silicon at 110 DEG C
Alkane is attapulgite modified, grinds standby.
Addition 1-butyl-3-Methylimidazole. villaumite 100 grams in flask, microcrystalline Cellulose 5 grams, at 100 DEG C, 180rpm
Rotating speed stirs, and is completely dissolved to cellulose and obtains ionic liquid cellulose solution.
By the modified attapulgite that the quality of above-mentioned preparation is ionic liquid cellulose solution quality 0.3 times, it is distributed to ion
In liquid fiber cellulose solution, at 100 DEG C, after stirring 20 minutes under 180rpm rotating speed, (oil phase is for addition oil phase and surfactant
Paraffin oil, surfactant be mass ratio be the mixture of Tween 80 and the Span 85 of 1:1), oil phase and ionic liquid cellulose
The volume ratio of solution is 5: 1, and surfactant is 1: 80 with the mass ratio of oil phase, stirs 15 minutes, shape under 400rpm rotating speed
Becoming inverse suspension system, be cooled to 30 DEG C with the speed of every 10 clocks cooling 5 DEG C, cellulose solution condenses balling-up；Adding volume is
The firming agent of 3 times of ionic liquid cellulose solution volume (firming agent be volume ratio be ethanol and the aqueous mixtures of 1:1), 5 points
After clock, rotating speed reduces to 200rpm, is kept stirring for 20 minutes, and cellulose solution solidifies rapidly, forms attapulgite cellulose composite adsorption
Microsphere, temperature is down to room temperature, filtered out by microsphere from reactant liquor, with the deionized water wash 3 of 1～2 times of volume～6 times,
Then attapulgite cellulose composite adsorption microsphere is soaked 48 hours in deionized water；By micro-for attapulgite cellulose composite adsorption
Ball hygrometric state sieves, and obtains attapulgite cellulose composite adsorption microsphere.
Embodiment 7: the attapulgite cellulose composite adsorption microsphere present invention prepared is used for pollutant adsorption treatment:
The attapulgite cellulose composite adsorption microsphere prepared with embodiment 1-6 respectively, silane-modified attapulgite, natural do not change
Property attapulgite and natural, unmodified cellulose are adsorbent, respectively phenol with initial concentration as 5mg/L, catechol, to benzene
Diphenol, methylene blue, methyl orange, copper ion, cadmium ion, lead ion carry out adsorption treatment as pollutant.Concrete grammar is as follows:
Being addition adsorbent in 5mg/L organic pollution to initial concentration, solid-to-liquid ratio is 1g:50mL, with 200r/ at 25 DEG C
Min rotating speed constant temperature oscillation absorption 12h, crosses leaching filtrate, records adsorbance, and result sees table 1.
The different adsorbent of table 1 is to pollutant adsorption treatment
The attapulgite cellulose composite adsorption microsphere that as can be seen from Table 1 prepared by embodiment 1-6 is concavo-convex with silane-modified
Attapulgite excellent, natural, unmodified is compared with natural, unmodified cellulose, and the removal efficiency of phenols dye thing in water can be improved 3-5 times
Above；Water Methylene Blue removal efficiency is up to 97-99%；Methyl orange removal efficiency has also been reached more than 75%；To a huge sum of money
The adsorbing and removing belonged to also has better effects, and removal efficiency is between 55-77%；And natural, unmodified attapulgite and natural, unmodified
The removal efficiency of pollutant is and reaches more than 35% by cellulose.As can be seen from the above data, the attapulgite that prepared by the present invention
Cellulose composite adsorption microsphere absorption property is good, preferable to pollutant removal.
The present invention, by modified attapulgite and cellulose compatibility, obtains having loose structure, the adsorbing medium that specific surface area is big,
By learning from other's strong points to offset one's weaknesses, produce cooperative effect, improve the absorption to pollutant, accumulation ability, stable in properties, it is easy to reclaim profit again
With；Raw material sources are extensive simultaneously, cheap, do not produce secondary pollution, and practical value is high, can be used for the degree of depth of water pollutant
Process.
Claims (5)
1. the preparation method of an attapulgite cellulose composite adsorption microsphere, it is characterised in that the method includes that three below walks
Rapid:
A, powder body attapulgite mass fraction are that the dilute hydrochloric acid of 5-10% soaks after 8-12h washing to neutral, be distributed to ethanol and
Water volume ratio is in the mixed solution of 9:1, adds silane coupler, adsorbs, adsorbed product at 40-50 DEG C after ultrasonic 50min
Separated purification, is dried to obtain silane-modified attapulgite, grinds standby at 110 DEG C；Described powder body attapulgite is with silane coupled
The mass ratio of agent is 4: 1～6: 1；
B, in the ionic liquid of 100 weight portions add 2～6 weight portions cellulose, 90～110 DEG C stirring mixing to cellulose
It is completely dissolved, obtains ionic liquid cellulose solution；
Adding the silane-modified attapulgite obtained in step a in the ionic liquid cellulose solution that c, step b obtain, silane changes
Property attapulgite quality is 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, addition oil phase and surfactant, oil phase and the volume ratio 4: 1～6 of ionic liquid cellulose solution:
1, surfactant is 1: 40～1: 100 with the mass ratio of oil phase, stirs 15～20 minutes, forms inverse suspension system, passes through
Programmed cooling, to 30～50 DEG C, adds firming agent, and the volume of firming agent is 2～3 times of ionic liquid cellulose solution volume, protects
Hold stirring 20 minutes, form attapulgite cellulose composite adsorption microsphere；Being washed with deionized and soak, hygrometric state sieves, and obtains
Attapulgite cellulose composite adsorption microsphere.
The preparation method of attapulgite cellulose composite adsorption microsphere the most according to claim 1, it is characterised in that program drops
Temperature refers to the speed of every 10min cooling 5 DEG C.
The preparation method of attapulgite cellulose composite adsorption microsphere the most according to claim 1, it is characterised in that step a
In, described silane coupler is selected from γ-(2,3-glycidoxy) propyl trimethoxy silicane, N-2 (aminoethyl) 3-ammonia third
One in base trimethoxy silane, vinyltrimethoxy silane.
The preparation method of attapulgite cellulose composite adsorption microsphere the most according to claim 1, it is characterised in that step b
In, described ionic liquid is 1-butyl-3-Methylimidazole. villaumite or 1-pi-allyl-3-Methylimidazole. acetate；Described fibre
Dimension element one in paper pulp, absorbent cotton, purified cotton or microcrystalline Cellulose.
The preparation method of attapulgite cellulose composite adsorption microsphere the most according to claim 1, it is characterised in that step c
In, described surfactant is Tween 80, Span 85 or its mixture；Described oil phase is pump oil, mineral oil, paraffin oil
Or Oleum Arachidis hypogaeae semen；Described firming agent is water, ethanol, acetone or its mixture.
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