CN103638902A - Lanthanum-loaded magnetic carbon aerogel microsphere defluorination adsorbent and preparation method - Google Patents
Lanthanum-loaded magnetic carbon aerogel microsphere defluorination adsorbent and preparation method Download PDFInfo
- Publication number
- CN103638902A CN103638902A CN201310638096.XA CN201310638096A CN103638902A CN 103638902 A CN103638902 A CN 103638902A CN 201310638096 A CN201310638096 A CN 201310638096A CN 103638902 A CN103638902 A CN 103638902A
- Authority
- CN
- China
- Prior art keywords
- lanthanum
- magnetic
- preparation
- adsorbent
- carbon aerogel
- 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
Images
Abstract
The invention provides a lanthanum-loaded magnetic carbon aerogel microsphere defluorination adsorbent and a preparation method. The method comprises the following steps: 1) adding carbon aerogel microspheres prepared by an inverse emulsion polymerization method in a ferric salt-containing solution, and preparing a magnetic Fe3O4-loaded binary mixture by a liquid-phase chemical precipitation method; 2) adding the magnetic loaded mixture in a lanthanum saline solution, standing, and preparing a ternary mixture; and 3) drying and calcining the ternary mixture, and preparing the microsphere adsorbent for defluorination. The microspheres prepared by the method provided by the invention has the maximum adsorption capacity of 113.5 mg/g, simple in recycling, and capable of being easily separated by adding magnets, thus omitting a cumbersome and energy-consuming suction-filtration separation or centrifugal separation process; and the microspheres are high in strength, breakage-free in long-time use, less in mass loss, free from dissolution and secondary pollution problem, safe and reliable, and suitable for being used for a long time and in cases with a high water stream pressure.
Description
Technical field
The invention belongs to sorbing material technical field, particularly a kind of year lanthanum magnetic carbon aerogel microball de-fluoridation adsorbent and preparation method.
Background technology
Fluorine is one of trace element of needed by human, in human body in main distribution and bone and tooth.Appropriate fluorine can strengthen the robustness of bone, has certain carious tooth effect of preventing and treating.The intake of adult's fluoride every day is generally 1.0-1.5mg, and the suitable fluorine mass concentration of drinking water is 0.5-1.0mg/L.But the fluorine of taking in too much can damage health again, cause fluorine dental plaque and fluorosis of bone, serious caused human lumbar leg ache, anchylosis, hunchback is paraplegia even, can also cause imbalance of thyroid function, renal dysfunction etc.
High-fluorine water is widely distributed in China, spreads all over 27 provinces, municipalities and autonomous regions, according to the investigation result of the Ministry of Public Health, shows: the whole nation approximately has 7,700 ten thousand people to drink the water that fluorinated volume surpasses 1.0mg/L, and wherein nearly 5,000,000 people's drinking water fluorinated volume surpasses 5.0mg/L.In China, Inner Mongolia investigation is found, the probability of suffering from slight fluorine dental plaque in the crowd of the well water of long-term drinking fluorinion concentration 10mg/L left and right has approached 50%, and drinking water fluorinated volume is that 5-6mg/L underground water can generally cause fluorine dental plaque in 10 years.In addition, zoopery shows, a large amount of absorptions that high fluorine can impel into aluminium with accumulate, easily cause senile dementia and human senility.
Therefore drink the health problem that high-fluorine water causes and caused national governments and the common people's concern.The World Health Organization (WHO) is 0.6-1.5mg/L by the limit value regulation of Fluorine of Drinking Water, and China is in the formal sanitary standard for drinking water (GB5479-2006) of implementing on July 1st, 2007, and the limit value of regulation Drinking Water fluorine is 1.0mg/L.The enforcement of strict standard, has higher requirement to high-fluorine water treatment technology.At present, drinking water defluorination method mainly contains chemical precipitation method, adsorption filtration method, in addition also have ion-exchange, electroosmose process, hyperfiltration, electrocoagulation, electric absorption method etc., wherein absorption method is because its removal efficiency is high, effect stability becomes conventional defluorination method.
The key of absorption method is the performance of sorbing material, and still, there are the following problems in the research and development of absorption method defluorination material and practical application at present:
(1) adsorption capacity of de-fluoridation adsorbent is low, causes a large amount of adsorbent of adsorption process consumption;
(2) some nanophase defluoridation adsorbent sizes are less, are not easy to Separation of Solid and Liquid after absorption completes, and at the design aspect of absorbing process and equipment, have difficulties;
(3) some nano adsorbers are by after molding bonded, and adsorbance sharply declines;
(4) the adsorbent intensity difference of some moulding, easily broken; When in adsorption tower/tank/post, filling is used, existence is because of adsorption bed deadweight, hydrostatic pressure, processing procedure water flow dynamic energy, the instantaneous high-velocity flow function of back flushing process cause the problem of absorbent particles fragmentation, can cause on the one hand adsorbent to run off, and system can not for a long time effectively be moved; Delivery turbidity raises in a short time on the other hand, and chemical element stripping discharges and causes safe drinking water hidden danger;
(5) some forming processes and moulding material contain harmful substance, can not ensure safe drinking water.
Carbon aerogels (Carbon Aerogels) is the nanometer porous property of a kind of novel light amorphous carbon cellulosic material, it is to have extremely-low density and porous solid material, porosity can reach 80%-99.8%, and aperture is generally 1-100nm, and specific area is at 500-1200 m
2between/g, the excursion of density can reach 0.001-0.5g/cm
3.Carbon aerogels can be prepared the microballoon of different-grain diameter, Chinese patent (publication number: CN 1011041430 A) patent has been announced a kind of preparation method of Spherical Carbon aeroge: take phenol-carbamide as raw material, prepolymerization forms colloidal sol, join containing in the decentralized photo of surfactant, be subject to stirring action to form suspension system, at 60-85 ℃, there is sol-gel transition globulate hydrogel, then hydrogel makes spherical organic aeroge through organic solvent conversion and supercritical drying, then is carried out Pintsch process and make Spherical Carbon aeroge.In sol-gel process, by control speed of agitator, can obtain sphere diameter is the carbon aerogels microballoon between 0.01-3mm.Carbon aerogels has mechanics, electricity and the chemical property of many excellences, can be widely used in the fields such as sorbing material, battery material, electrode material, chemical sensor.
Lanthanum is as a kind of rare earth element, and research shows, the oxide of rare earth element has higher adsorptive selectivity to fluorine ion, is loaded on carbon aerogels material and can improve this material to the adsorbance of fluorine and selective.For example, Chinese patent (publication number: CN 101234792 A) has been reported a kind of method of lanthanum-carried aluminium oxide removal fluorine ions in water body.Concrete grammar is: aluminium oxide and lanthanum salt mix and are incorporated in roasting at 170-400 ℃ by the mass ratio of 1-4:1.The aluminium oxide of the lanthanum-carried oxide making is obviously better than traditional sorbing material for the removal effect of fluorine ions in water body, and maximum adsorption capacity has reached 80.8mg/g.Chinese patent (publication number: CN 101780397 A) has been reported a kind of preparation method of the lanthanum-carried zeolite for defluorination: at raw material zeolite, add lanthanum chloride solution, concentrated ammonia liquor regulator solution pH with 28 wt%, dipping is removed filtrate after stirring, and dries high temperature sintering.The residual lanthanum ion of cooling rear cleaning, dries, and obtains the zeolite of lanthanum oxide-carrying.The zeolite of the lanthanum oxide-carrying that the method prepares has reached 7.69mg/g to the better maximum adsorption capacity of the removal effect of fluorine ion, and is applicable to the water quality of variable concentrations, different hardness.But above-mentioned method is all more loaded down with trivial details, and the adsorption capacity of fluorine ion is need to improve.
Environmental area magnetic microsphere material as adsorbent have that mass transfer rate is high, solid-liquid contact good, pressure drop is low, can delamination under additional magnetic fields etc. advantage, magnetic adsorbent can be used for the pollutant in adsorption aqueous solution and industrial waste gas.After having adsorbed, adsorbent can be in addition separated by simple magnetic process.
The magnetic nanoparticle of reporting at present is morely mainly nano zero valence iron, Fe
3o
4and γ-Fe
2o
3nano particle etc.Method toward carried metal on material with carbon element or metal oxide mainly contains synchronized loading method, liquid-phase chemistry deposition technique, infusion process, sol-gel process, hydrothermal synthesis method and gas chemistry sedimentation etc.For example, Chinese patent (publication number: CN 101503579 A) has been reported a kind of preparation method of carbon nano tube surface load magnetic alloy particle composite: CNT is distributed in the chloride solution of iron, cobalt, nickel through purifying, activation processing afterwards equably, in vigorous stirring process, to solution, slowly drip alkaline solution, alloy ratio when regulator solution pH value makes iron, cobalt, nickel ion according to obtain solution arrives carbon nano tube surface with the form co-precipitation of hydroxide.Utilize centrifugal or filter and take out sediment.By heat treatment under reducing atmosphere after drying precipitate, obtain the carbon nano tube compound material of load magnetic alloy nano particle.Chinese patent (publication number: CN 101823777 A) has been reported a kind of carried magnetic Fe
3o
4the preparation method of the mesoporous carbon CMK-3 of particle: take meso-porous carbon material CMK-3 as carrier, the magnetic reactive metal oxides tri-iron tetroxide of tool (Fe
3o
4) be load object, ethylene glycol is reducing agent, utilizes equi-volume impregnating and the method for roasting in inert gas, by Fe
3o
4particulate load enters in the mesopore orbit of mesoporous carbon CMK-3.
Summary of the invention
The problem that the object of the invention is to exist for above-mentioned prior art provides a kind of year lanthanum magnetic carbon aerogel microball de-fluoridation adsorbent and preparation method.Year lanthanum magnetic carbon aerogel microball defluorination high adsorption capacity prepared by the inventive method, easily separated, mass loss is little, without stripping, non-secondary pollution problem, safe and reliable, be suitable for long-term and use in the situation that water flow pressure changes greatly.
For realizing object of the present invention, one aspect of the present invention provides a kind of year lanthanum magnetic carbon aerogel microball de-fluoridation adsorbent and preparation method, comprises as follows step in sequence:
1) adopt reversed emulsion polymerization to prepare carbon aerogels microballoon;
2) the carbon aerogels microballoon of preparing in step 1) is joined in the solution containing molysite, stir, be warming up to 80 ℃ and add alkali lye, reaction certain hour.By liquid chemical precipitation legal system, obtain carried magnetic Fe
3o
4binary mixture carbon aerogels;
3) by step 2) in the magnetic loading mixture of preparation join in lanthanum saline solution, place, prepare ternary mixture;
4) ternary mixture of preparing in step 3) is dried, calcines and form.
Wherein the carbon aerogels microballoon preparation process described in step 1) is as follows: resorcinol, formaldehyde, natrium carbonicum calcinatum are joined in proportion in appropriate distilled water and dissolved, proceed to certain volume containing in the decentralized photo of surfactant, at 80 ℃, control rotating speed and stir a period of time, obtain the organic Wet Gel Microsphere disperseing.The above-mentioned organic Wet Gel Microsphere of isolated by filtration, with distilled water washing 3-5 time.The organic Wet Gel Microsphere obtaining is inserted in acetone and carried out solvent exchange, then in fume hood, carry out normal temperature and pressure and be dried, finally under inert gas shielding, high temperature cabonization can obtain carbon aerogels microballoon.
Particularly, described carbon aerogels microballoon granularity pattern as shown in the ESEM of Fig. 1 (SEM) image, the about 10-80 μ of its granularity m, porosity is 80%-98%, typical pore-size is less than 50nm, specific area is up to 600-1000m
2/ g, density is 0.05-0.80g/cm
3.
Wherein, carbon aerogels microballoon and magnetic material Fe step 2)
3o
4the ratio of weight portion be 5-45:55-95.
Wherein, the concentration of the lanthanum saline solution described in step 3) is 0.1-1.5mol/L, and lanthanum salt is preferably lanthanum nitrate.
Particularly, be 24-72 hour standing time.
Particularly, also comprise ternary mixture is dried, wherein the dry temperature of processing is 60-120 ℃, and the time is 10-24 hour.
Especially, described calcination processing is that dried defluorination ternary mixture is put into Muffle furnace, is heated to 450-600 ℃, and 3-10 hour is processed in insulation.
The present invention provides a kind of defluorination being prepared from according to the method described above to carry lanthanum magnetic carbon aerogel microball adsorbent on the other hand.
The lanthanum magnetic carbon aerogel microball adsorbent tool that carries prepared by the present invention has the following advantages:
1, the ion selectivity of of the present invention year lanthanum magnetic carbon aerogel microball adsorbent is good, has higher selectively for its object removal ion (fluorine ion), and in water, other Common Anions all have no significant effect within the scope of drinking water;
2, defluorination of the present invention carries lanthanum magnetic carbon aeroge by effects such as covalent bond chemisorbed, electrostatic adsorption, ion-exchange absorption, fluorine compounds in absorption and fixedly drinking water, adsorption capacity to fluorine is high, at pH, be under neutrallty condition, the saturated adsorption capacity of magnetic carbon aerogel microball adsorbent is 113.5mg/g;
3, the magnetic of of the present invention year lanthanum magnetic carbon aerogel microball adsorbent is high, and its saturation magnetisation value is greater than 77emu/g---, is easy to separation after absorption;
4, the cohesive strength of of the present invention year lanthanum magnetic carbon aerogel microball adsorbent is high, and breaking strength is high, and more than dry state compressive strength reaches 45N, long-term use is not broken, is suitable for long-term and uses in the situation that water flow pressure changes greatly;
5, in the use procedure of of the present invention year lanthanum magnetic carbon aerogel microball adsorbent, mass loss is little, without stripping, and swelling not, nonhazardous, non-secondary pollution problem, after processing, water quality safety is reliable.
The specific embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Carrying lanthanum magnetic carbon aerogel microball de-fluoridation adsorbent and preparation method comprises the following steps:
1, prepare carbon aerogels microballoon
By resorcinol, formaldehyde, natrium carbonicum calcinatum in molar ratio 1:2:0.01 be dissolved in appropriate distilled water, stirring and dissolving, obtains the hydrosol.The solution after dissolving be transferred to volume ratio be 1:100 containing in the decentralized photo cyclohexane solution of SPAN-80, the rotating speed of 120r/min stirs at 80 ℃, until form, disperses organic wet gel particle.Organic wet gel particle that isolated by filtration obtains soaks to be placed on for 3 days through acetone and natural dryingly in fume hood obtains xerogel microballoon to constant weight, and xerogel microballoon is at N
2protect lower 850 ℃ of carbonization cracking within 5 hours, to obtain carbon aerogels microballoon.The particle diameter of this carbon aerogels microballoon is 40-60 μ m, and specific area is 605m
2/ g;
2, carbon aerogels micro-ball load magnetic Nano Fe
3o
4particle
By FeCl
2.4H
2o and FeCl
3.6H
2o joins in appropriate distilled water and dissolves with mol ratio 1:2, the carbon aerogels microballoon 2g that adds preparation in step 1, stir, while being warming up to 80 ℃, add 5ml ammoniacal liquor, continue the carbon aerogels microballoon that reaction obtains carried magnetic for 1 hour, utilize the separated magnetic carbon aerogel microball of magnet, distilled water washing is to neutral, 60 ℃ of oven dry, standby;
3, magnetic carbon aerogel microball is lanthanum-carried
The magnetic carbon aerogel microball making in step 2 is immersed in to the 0.5mol/L of proper volume
--in lanthanum nitrate hexahydrate, place 24 hours, utilize magnet separated, 60 ℃ of oven dry, activate 10 hours at 450 ℃, obtain can be used for the lanthanum-carried magnetic carbon aerogel microball that fluorine ions in water body is removed, and its saturation magnetisation value has reached 79.2 emu/g
---, dry state compressive strength > 45N;
Carry the application of lanthanum magnetic carbon aerogel microball adsorbent:
Get the lanthanum magnetic carbon aerogel microball adsorbent that carries that 0.1g makes and be placed in the solution that 100ml fluorinion concentration is 1-200mg/L, under room temperature, vibration absorption is after 24 hours, after utilizing magnet separation, measure solution fluorinion concentration and calculate adsorption capacity, according to Langmuir equation model, calculating this novel magnetic carbon aerogels microsphere adsorbing agent is 92mg/g to the maximum adsorption capacity of fluorine.
Embodiment 2
Carrying lanthanum magnetic carbon aerogel microball de-fluoridation adsorbent and preparation method comprises the following steps:
1, prepare carbon aerogels microballoon
By resorcinol, formaldehyde, natrium carbonicum calcinatum in molar ratio 1:2:0.02 be dissolved in appropriate distilled water, stirring and dissolving, obtains the hydrosol.The solution after dissolving be transferred to volume ratio be 2:100 containing in the decentralized photo cyclohexane solution of SPAN-80, the rotating speed of 240 r/min stirs at 70 ℃, until form, disperses organic wet gel particle.Organic wet gel particle that isolated by filtration obtains soaks to be placed on for 2 days through acetone and natural dryingly in fume hood obtains xerogel microballoon to constant weight, and xerogel microballoon is at N
2protect lower 950 ℃ of carbonization cracking within 4 hours, to obtain carbon aerogels microballoon.The particle diameter of this carbon aerogels microballoon is 30-45 μ m, and specific area is 550 m
2/ g;
2, carbon aerogels micro-ball load magnetic Nano Fe
3o
4particle
By FeSO
4.7H
2o and Fe
2(SO
4)
3with mol ratio 1:1, join in appropriate distilled water and dissolve, the carbon aerogels microballoon 3g that adds preparation in step 1, stir, while being warming up to 80 ℃, add appropriate 0.5mol/LNaOH solution, continue the carbon aerogels microballoon that reaction obtains carried magnetic for 1 hour, utilize the separated magnetic carbon aerogel microball of magnet, distilled water washing is to neutral, 60 ℃ of oven dry, standby;
3, magnetic carbon aerogel microball is lanthanum-carried
The magnetic carbon aerogel microball making in step 2 is immersed in the 0.5mol/L lanthanum sulfate solution of proper volume, place 48 hours, utilize magnet separated, 80 ℃ of oven dry, at 550 ℃, activate 8 hours, obtain can be used for the lanthanum-carried magnetic carbon aerogel microball that fluorine ions in water body is removed, its saturation magnetisation value has reached 77.4emu/g
---, dry state compressive strength > 45N;
Carry the application of lanthanum magnetic carbon aerogel microball adsorbent:
Get the lanthanum magnetic carbon aerogel microball adsorbent that carries that 0.1g makes and be placed in the solution that 100ml fluorinion concentration is 1-200mg/L, under room temperature, vibration absorption is after 24 hours, after utilizing magnet separation, measure solution fluorinion concentration and calculate adsorption capacity, according to Langmuir equation model, calculating this novel magnetic carbon aerogels microsphere adsorbing agent is 95mg/g to the maximum adsorption capacity of fluorine.
Embodiment 3
Carrying lanthanum magnetic carbon aerogel microball de-fluoridation adsorbent and preparation method comprises the following steps:
1, prepare carbon aerogels microballoon
By resorcinol, formaldehyde, natrium carbonicum calcinatum in molar ratio 1:2:0.01 be dissolved in appropriate distilled water, stirring and dissolving, obtains the hydrosol.The solution after dissolving be transferred to volume ratio be 5:100 containing in the decentralized photo cyclohexane solution of SPAN-80, the rotating speed of 480 r/min stirs at 80 ℃, until form, disperses organic wet gel particle.Organic wet gel particle that isolated by filtration obtains soaks to be placed on for 3 days through acetone and natural dryingly in fume hood obtains xerogel microballoon to constant weight, and xerogel microballoon is at N
2protect lower 1050 ℃ of carbonization cracking within 3 hours, to obtain carbon aerogels microballoon.The particle diameter of this carbon aerogels microballoon is 20-32 μ m, specific area 500 m
2/ g;
2, carbon aerogels micro-ball load magnetic Nano Fe
3o
4particle
By FeSO
4.7H
2o and Fe
2(SO
4)
3with mol ratio 1:1, join in appropriate distilled water and dissolve, the carbon aerogels microballoon 4g that adds preparation in step 1, stir, while being warming up to 80 ℃, add 30ml ammoniacal liquor, continue the carbon aerogels microballoon that reaction obtains carried magnetic for 1.5 hours, utilize the separated magnetic carbon aerogel microball of magnet, distilled water washing is to neutral, 60 ℃ of oven dry, standby;
3, magnetic carbon aerogel microball is lanthanum-carried
The magnetic carbon aerogel microball making in step 2 is immersed in 1 mol/L lanthanum nitrate hexahydrate of proper volume, place 72 hours, utilize magnet separated, 80 ℃ of oven dry, at 600 ℃, activate 6 hours, obtain can be used for the lanthanum-carried magnetic carbon aerogel microball that fluorine ions in water body is removed, its saturation magnetisation value has reached 79emu/g
---, dry state compressive strength > 46N;
Carry the application of lanthanum magnetic carbon aerogel microball adsorbent:
Get the lanthanum magnetic carbon aerogel microball adsorbent that carries that 0.1g makes and be placed in the solution that 100ml fluorinion concentration is 1-200mg/L, under room temperature, vibration absorption is after 24 hours, after utilizing magnet separation, measure solution fluorinion concentration and calculate adsorption capacity, according to Langmuir equation model, calculating this novel magnetic carbon aerogels microsphere adsorbing agent is 97mg/g to the maximum adsorption capacity of fluorine.
Embodiment 4
Carrying lanthanum magnetic carbon aerogel microball de-fluoridation adsorbent and preparation method comprises the following steps:
1, prepare carbon aerogels microballoon
By resorcinol, formaldehyde, natrium carbonicum calcinatum in molar ratio 1:2:0.01 be dissolved in appropriate distilled water, stirring and dissolving, obtains the hydrosol.The solution after dissolving be transferred to volume ratio be 2:100 containing in the decentralized photo cyclohexane solution of SPAN-80, the rotating speed of 480 r/min stirs at 80 ℃, until form, disperses organic wet gel particle.Organic wet gel particle that isolated by filtration obtains soaks to be placed on for 3 days through acetone and natural dryingly in fume hood obtains xerogel microballoon to constant weight, and xerogel microballoon is at N
2protect lower 950 ℃ of carbonization cracking within 5 hours, to obtain carbon aerogels microballoon.The particle diameter of this carbon aerogels microballoon is 20-25 μ m, and specific area is 550 m
2/ g;
2, carbon aerogels micro-ball load magnetic Nano Fe
3o
4particle
By FeCl
2.4H
2o and FeCl
3.6H
2o joins in appropriate distilled water and dissolves with mol ratio 1:2, the carbon aerogels microballoon 2g that adds preparation in step 1, stir, while being warming up to 80 ℃, add 10ml ammoniacal liquor, continue the carbon aerogels microballoon that reaction obtains carried magnetic for 2 hours, utilize the separated magnetic carbon aerogel microball of magnet, distilled water washing is to neutral, 60 ℃ of oven dry, standby;
3, magnetic carbon aerogel microball is lanthanum-carried
The magnetic carbon aerogel microball making in step 2 is immersed in the 1mol/L lanthanum sulfate solution of proper volume, place 72 hours, utilize magnet separated, 120 ℃ of oven dry, at 650 ℃, activate 4 hours, obtain can be used for the lanthanum-carried magnetic carbon aerogel microball that fluorine ions in water body is removed, its saturation magnetisation value has reached 79.2emu/g
---, dry state compressive strength > 48N;
Carry the application of lanthanum magnetic carbon aerogel microball adsorbent:
Get the lanthanum magnetic carbon aerogel microball adsorbent that carries that 0.1g makes and be placed in the solution that 100ml fluorinion concentration is 1-200mg/L, under room temperature, vibration absorption is after 24 hours, after utilizing magnet separation, measure solution fluorinion concentration and calculate adsorption capacity, according to Langmuir equation model, calculating this novel magnetic carbon aerogels microsphere adsorbing agent is 113.5 mg/g to the maximum adsorption capacity of fluorine.
Embodiment 5
Carrying lanthanum magnetic carbon aerogel microball de-fluoridation adsorbent and preparation method comprises the following steps:
1, prepare carbon aerogels microballoon
By resorcinol, formaldehyde, natrium carbonicum calcinatum in molar ratio 1:2:0.01 be dissolved in appropriate distilled water, stirring and dissolving, obtains the hydrosol.The solution after dissolving be transferred to volume ratio be 10:100 containing in the decentralized photo cyclohexane solution of SPAN-80, the rotating speed of 480 r/min stirs at 80 ℃, until form, disperses organic wet gel particle.Organic wet gel particle that isolated by filtration obtains soaks to be placed on for 3 days through acetone and natural dryingly in fume hood obtains xerogel microballoon to constant weight, and xerogel microballoon is at N
2protect lower 1050 ℃ of carbonization cracking within 2 hours, to obtain carbon aerogels microballoon.The particle diameter of this carbon aerogels microballoon is 16-25 μ m, and specific area is 660 m
2/ g;
2, carbon aerogels micro-ball load magnetic Nano Fe
3o
4particle
By FeCl
2.4H
2o and FeCl
3.6H
2o joins in appropriate distilled water and dissolves with mol ratio 1:2, the carbon aerogels microballoon 6g that adds preparation in step 1, stir, while being warming up to 80 ℃, add 20ml ammoniacal liquor, continue the carbon aerogels microballoon that reaction obtains carried magnetic for 4 hours, utilize the separated magnetic carbon aerogel microball of magnet, distilled water washing is to neutral, 60 ℃ of oven dry, standby;
3, magnetic carbon aerogel microball is lanthanum-carried
The magnetic carbon aerogel microball making in step 2 is immersed in the 1mol/L lanthanum nitrate hexahydrate of proper volume, place 24 hours, utilize magnet separated, 80 ℃ of oven dry, at 500 ℃, activate 6 hours, obtain can be used for the lanthanum-carried magnetic carbon aerogel microball that fluorine ions in water body is removed.Its saturation magnetisation value has reached 78.5emu/g
---, dry state compressive strength > 48N;
Carry the application of lanthanum magnetic carbon aerogel microball adsorbent:
Get the lanthanum magnetic carbon aerogel microball adsorbent that carries that 0.1 g makes and be placed in the solution that 100ml fluorinion concentration is 1-200mg/L, under room temperature, vibration absorption is after 24 hours, after utilizing magnet separation, measure solution fluorinion concentration and calculate adsorption capacity, according to Langmuir equation model, calculating this novel magnetic carbon aerogels microsphere adsorbing agent is 106mg/g to the maximum adsorption capacity of fluorine.
Claims (9)
1. a preparation method of carrying lanthanum magnetic carbon aerogel microball de-fluoridation adsorbent, comprises as follows step in sequence:
1) reversed emulsion polymerization is prepared to carbon aerogels microballoon and joined in the solution containing molysite, stir, be warming up to 80 ℃ and add alkali lye, reaction certain hour, obtains carried magnetic Fe by liquid chemical precipitation legal system
3o
4binary mixture;
2) the magnetic loading mixture of preparing in step 1) is joined in lanthanum saline solution, place, prepare ternary mixture;
3) by step 2) in the ternary mixture of preparation be dried, calcine and form.
2. preparation method as claimed in claim 1, it is characterized in that the carbon aerogels microballoon described in step 1) can complete by following process: resorcinol, formaldehyde, natrium carbonicum calcinatum are joined in proportion in appropriate distilled water and dissolved, proceed to certain volume containing in the decentralized photo of surfactant, at 80 ℃, control rotating speed and stir a period of time, obtain the organic Wet Gel Microsphere disperseing; The above-mentioned organic Wet Gel Microsphere of isolated by filtration, with distilled water washing 3 ~ 5 times; The organic Wet Gel Microsphere obtaining is inserted in acetone and carried out solvent exchange, then in fume hood, carry out normal temperature and pressure and be dried, finally under inert gas shielding, high temperature cabonization can obtain carbon aerogels microballoon.
3. preparation method as claimed in claim 1 or 2, is characterized in that step 2) middle carbon aerogels microballoon and magnetic material Fe
3o
4the ratio of weight portion be 5-45:55-95.
4. preparation method as claimed in claim 1 or 2, is characterized in that step 2) described in carbon aerogels micro-ball load magnetic Fe
3o
4reaction time be 1-4 hour.
5. preparation method as claimed in claim 1 or 2, the concentration that it is characterized in that the lanthanum saline solution described in step 3) is 0.5-1.5 mol/L.
6. preparation method as claimed in claim 1 or 2, is characterized in that the time that the binary mixture described in step 3) is placed in lanthanum saline solution is 24-72 hour.
7. preparation method as claimed in claim 1 or 2, is characterized in that baking temperature described in step 4) is 60-120 ℃, and be 10-24 hour drying time.
8. preparation method as claimed in claim 1 or 2, is characterized in that calcining heat described in step 4) is 450-600 ℃, and calcination time is 3-10 hour.
9. for a year lanthanum magnetic carbon aerogel microball adsorbent for fluoride ion removing, it is characterized in that being prepared from according to the arbitrary described method of claim 1 ~ 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310638096.XA CN103638902A (en) | 2013-12-03 | 2013-12-03 | Lanthanum-loaded magnetic carbon aerogel microsphere defluorination adsorbent and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310638096.XA CN103638902A (en) | 2013-12-03 | 2013-12-03 | Lanthanum-loaded magnetic carbon aerogel microsphere defluorination adsorbent and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103638902A true CN103638902A (en) | 2014-03-19 |
Family
ID=50244269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310638096.XA Pending CN103638902A (en) | 2013-12-03 | 2013-12-03 | Lanthanum-loaded magnetic carbon aerogel microsphere defluorination adsorbent and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103638902A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107282022A (en) * | 2017-08-18 | 2017-10-24 | 江苏海普功能材料有限公司 | De-fluoridation adsorbent and preparation method thereof |
| CN107497394A (en) * | 2017-07-19 | 2017-12-22 | 南昌航空大学 | A kind of Fe Mg La tri compound fluorine ion absorbers and preparation method thereof |
| CN109289814A (en) * | 2018-10-16 | 2019-02-01 | 大连工业大学 | It is a kind of for adsorbing the magnetic carbon aerogels and preparation method thereof of antibiotic in waste water |
| CN113559797A (en) * | 2021-08-09 | 2021-10-29 | 云南大学 | Biochar aerogel material and preparation method and application thereof |
| CN114307877A (en) * | 2021-12-28 | 2022-04-12 | 清华大学 | Rare earth metal hydroxide composite aerogel and preparation method and application thereof |
| CN114950367A (en) * | 2022-03-11 | 2022-08-30 | 深圳信息职业技术学院 | Method for efficiently treating low-fluorine wastewater by using magnetic microporous lanthanum formate adsorbent |
| CN115106051A (en) * | 2022-06-30 | 2022-09-27 | 燕山大学 | Rapid settling defluorinating agent and preparation method and application method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5472767A (en) * | 1977-11-22 | 1979-06-11 | Unitika Ltd | Treating method of regenerating desorptive solution for active carbon |
| CN101234792A (en) * | 2008-02-25 | 2008-08-06 | 南京大学 | Method for removing fluorine ion from water by using oxide of lanthanum-carried aluminum oxide |
| CN101780397A (en) * | 2010-01-29 | 2010-07-21 | 广东药学院 | Preparation method of lanthanum oxide-carrying zeolite for removing fluorine |
-
2013
- 2013-12-03 CN CN201310638096.XA patent/CN103638902A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5472767A (en) * | 1977-11-22 | 1979-06-11 | Unitika Ltd | Treating method of regenerating desorptive solution for active carbon |
| CN101234792A (en) * | 2008-02-25 | 2008-08-06 | 南京大学 | Method for removing fluorine ion from water by using oxide of lanthanum-carried aluminum oxide |
| CN101780397A (en) * | 2010-01-29 | 2010-07-21 | 广东药学院 | Preparation method of lanthanum oxide-carrying zeolite for removing fluorine |
Non-Patent Citations (3)
| Title |
|---|
| JIANMIN ZENG ET AL: ""Adsorption of fluorine from agueous solution by chitosan magnetic microspheres of loading lanthanum"", 《ADVANCED MATERIAL RESEARCH》 * |
| YUNING JIN ET AL: ""Photocatalysis-enhanced electrosorption process for degradation of high-concentration dye wastewater on TiO2/carbon aerogel"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 孙文童 等: ""平板炭气凝胶电极电吸附除氟技术的研究"", 《2013中国环境科学学会学术年会论文集》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497394A (en) * | 2017-07-19 | 2017-12-22 | 南昌航空大学 | A kind of Fe Mg La tri compound fluorine ion absorbers and preparation method thereof |
| CN107497394B (en) * | 2017-07-19 | 2019-10-15 | 南昌航空大学 | A kind of Fe-Mg-La tri compound fluorine ion absorber and preparation method thereof |
| CN107282022A (en) * | 2017-08-18 | 2017-10-24 | 江苏海普功能材料有限公司 | De-fluoridation adsorbent and preparation method thereof |
| CN109289814A (en) * | 2018-10-16 | 2019-02-01 | 大连工业大学 | It is a kind of for adsorbing the magnetic carbon aerogels and preparation method thereof of antibiotic in waste water |
| CN109289814B (en) * | 2018-10-16 | 2021-08-27 | 大连工业大学 | Magnetic carbon aerogel for adsorbing antibiotics in wastewater and preparation method thereof |
| CN113559797A (en) * | 2021-08-09 | 2021-10-29 | 云南大学 | Biochar aerogel material and preparation method and application thereof |
| CN113559797B (en) * | 2021-08-09 | 2022-04-12 | 云南大学 | Biochar aerogel material and preparation method and application thereof |
| CN114307877A (en) * | 2021-12-28 | 2022-04-12 | 清华大学 | Rare earth metal hydroxide composite aerogel and preparation method and application thereof |
| CN114950367A (en) * | 2022-03-11 | 2022-08-30 | 深圳信息职业技术学院 | Method for efficiently treating low-fluorine wastewater by using magnetic microporous lanthanum formate adsorbent |
| CN115106051A (en) * | 2022-06-30 | 2022-09-27 | 燕山大学 | Rapid settling defluorinating agent and preparation method and application method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xiao et al. | Adsorption of organic dyes from wastewater by metal-doped porous carbon materials | |
| CN103638902A (en) | Lanthanum-loaded magnetic carbon aerogel microsphere defluorination adsorbent and preparation method | |
| He et al. | Review of fluoride removal from water environment by adsorption | |
| Chen et al. | Removal of fluoride from water using aluminum hydroxide-loaded zeolite synthesized from coal fly ash | |
| Gai et al. | A comprehensive review of adsorbents for fluoride removal from water: performance, water quality assessment and mechanism | |
| Huang et al. | Potential of removing Cd (II) and Pb (II) from contaminated water using a newly modified fly ash | |
| CN103301809B (en) | Magnetic carrier iron ordered mesoporous carbon, preparation method and application thereof | |
| CN105381780B (en) | A kind of magnetic adsorbent for adsorbing superconduction Magneto separate arsenic removal antimony and preparation method thereof | |
| Li et al. | Fabrication of carboxyl and amino functionalized carbonaceous microspheres and their enhanced adsorption behaviors of U (VI) | |
| Guo et al. | Fabrication of efficient alginate composite beads embedded with N-doped carbon dots and their application for enhanced rare earth elements adsorption from aqueous solutions | |
| Chen et al. | Application of metal oxide heterostructures in arsenic removal from contaminated water | |
| Jian et al. | Excellent fluoride removal performance by electrospun La–Mn bimetal oxide nanofibers | |
| Yang et al. | One-pot synthesis of arginine modified hydroxyapatite carbon microsphere composites for efficient removal of U (VI) from aqueous solutions | |
| Guo et al. | A comparison of Ni-Co layered double oxides with memory effect on recovering U (VI) from wastewater to hydroxides | |
| Zhang et al. | Advanced treatment of phosphorus-containing tail water by Fe–Mg–Zr layered double hydroxide beads: performance and mechanism | |
| CN102600790A (en) | Nanometer cerium oxide hydrate-based arsenic removing material, preparation method thereof and application in arsenic removing | |
| CN108262002B (en) | Preparation method and application of Fe-Ti binary oxide adsorbent for removing antimony | |
| Jung et al. | Entrapment of powdered drinking water treatment residues in calcium-alginate beads for fluoride removal from actual industrial wastewater | |
| CN109012565A (en) | A kind of method of the magnetic carbon material Adsorption heavy metal ions in wastewater of nitrating | |
| CN104971688B (en) | A kind of preparation method of nano magnetic particle adsorbent | |
| CN110756165B (en) | Preparation method of carboxyl carbon spheres for adsorbing heavy metal ions and products thereof | |
| CN107511130A (en) | A kind of zeolite-loaded nano-tourmaline material and its preparation method and application | |
| Yu et al. | Steam-treated CeO2-ZrO2/activated carbon fibers for the efficient removal of Pb (II) from aqueous solutions | |
| CN102728300A (en) | MnO2-doped composite magnetic nanometer adsorbent, its preparation method and its application | |
| CN101905103A (en) | Method for manufacturing composite millipore filter element for efficiently removing arsenic and fluoride in drinking water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140319 |