CN102553526B - Method for removing mercury ions from water by using silver-modified magnetic carbon nanotube and regeneration method - Google Patents
Method for removing mercury ions from water by using silver-modified magnetic carbon nanotube and regeneration method Download PDFInfo
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Abstract
The invention discloses a method for removing mercury ions from water by using silver-modified magnetic carbon nanotubes and a regeneration method thereof. A trace amount of mercury ions (Hg2+) in a polluted water body are adsorbed by silver nanoparticle-loaded/iron oxide magnetic carbon nanotubes as adsorbent under the conditions that the temperature is 20 DEG C to 60 DEG C and the pH value is 3 to 8; and the adsorbent is recycled and regenerated by thermal desorption. The silver nanoparticle-loaded/iron oxide magnetic carbon nanotube has powerful capability and specificity of adsorbing mercury ions in water. With magnetic separation techniques, the process of separating the adsorbent from the water solution is greatly simplified, the probability of secondary pollution is reduced to the greatest extent, and the environmental benefit is improved.
Description
Technical field
The present invention relates to a kind of method and reclaiming method thereof of removing mercury ion in water, particularly a kind of method and reclaiming method thereof of utilizing magnetic carbon nano composite material to remove mercury ion in water.
Background technology
Mercury pollution has become the concern that the mercury in global environmental problem, especially water body is subject to people especially.Mercury in water body can be by aquatile enrichment, and generates the extremely strong organomercurial compound of toxicity by bio-transformation.Mercury and mercuric compounds has strong neurotoxicity and genetoxic, and the mercury of denier just can cause tissue damage or pathology, brings out chromosome damage and neurogenic disease.Industrial, mercury and mercuric compounds has a wide range of applications, and as chlor-alkali, papermaking, battery, electronics, metallurgy and medicine equipment etc., meanwhile, some using energy source processes also can cause certain mercury pollution, as coal fired power generation etc.The mercury that industrial process or using energy source process discharge is entered environment medium by all means, and human health and Environmental security are constituted a threat to.As can be seen here, mercury pollution source is ubiquitous, and meanwhile, mercury, as a Heavy Metallic Elements, can not effectively be degraded, can be for a long time, extensively exist in the middle of natural environment.The environmental administration of International Environmental Protection tissue and national governments has all carried out strict restriction to the mercury in varying environment medium, and wherein the mercury in water body is generally no more than 0.001 mg/L, and its maximum permissible concentration is well below other priority pollutants.So the mercury of effectively removing trace in water body is an instant environmental problem.
People have done a large amount of research work to the removal of mercury pollution and Mercury in Water Body for a long time, have developed mercury pollution control method and technology in a series of effective water.Use the more methods such as the precipitation method, counter-infiltration, filtration, ion-exchange, absorption that have, wherein absorption method is with low cost, simple to operate, is a kind of the most conventional mercury pollution control method.The most frequently used adsorbent has zeolite, molecular sieve, clay mineral and active carbon etc., and these adsorbents have stronger adsorption capacity owing to having compared with large specific area to water pollutant.But, in actual water body, conventionally have multiple pollutant, content will be far away higher than ion concentration of mercury, and these adsorbents is selectively conventionally poor, in Adsorption of Mercury ion, also can adsorb in a large number other coexisting ion or pollutant, occupy a large amount of adsorption sites, have a strong impact on the removal effect of adsorbent to mercury ion.Absorption has the adsorbents such as active carbon of a large amount of mercury ions could carry out separatedly with water body by long-time precipitation, and separation process is consuming time longer.Precipitating sludge after separation (adsorbent) generally can not carry out regeneration, and processes as danger wastes, slightly improper, and as easy as rolling off a log formation secondary pollution discharges in the middle of environment the mercury of absorption again.There is the subject matter of following several respects in the adsorbent therefore, removing for water mercury ion at present: (1) adsorption capacity is limited; (2) poor selectivity; (3) sorbing material and water body are not easily separated; (4) adsorbent is difficult to recycling; (5) absorption has the adsorbent of mercury ion to be difficult to process, and easily causes secondary pollution.Therefore, research and development adsorption capacity is large, selectively high, easily separated, recyclable and be not easy to cause the high-efficiency adsorbent of secondary pollution very necessary.
CNT is as a kind of new functional material, there is unique tubular nanostructures, very large surface area and aspect ratio, very strong Surface binding energy and unsaturation, easily and other atoms and ions binding, there is very strong adsorptivity, sound construction, stable in properties, is a kind of comparatively ideal separation and concentration material, in removing water, aspect mercury ion, has potential using value.Although CNT has been used in the middle of water treatment,, identical with other adsorbent, CNT is poor to the adsorptive selectivity of mercury ion, is vulnerable to the interference of other high-load pollutant, adsorption capacity to mercury ion is limited, is difficult to meet the advanced treating requirement of mercury ion in water; Meanwhile, because CNT has certain hydrophobicity, be difficult for disperseing with separated in water, the operation easier of practical application is relatively large; In addition, the cost of CNT is higher, as can not recycling, can cause significantly improving of processing cost, limits it as the application prospect of superior adsorbent.Consider that it has the feature of larger specific area and stronger adsorption capacity as a kind of novel sorbing material, if can overcome above shortcoming, making full use of its physical chemistry structural advantage, improve the selective and adsorption capacity of its Adsorption of Mercury ion and realize and reclaiming and regeneration, will be expected to develop a kind of new and effective mercury ion sorbing material.
Summary of the invention
Technical problem to be solved by this invention is the defect that overcomes prior art, a kind of method of utilizing modified by silver magnetic carbon nano-tube material to remove mercury ion in water is provided; In addition, the present invention also will further provide the method for the carbon nano-tube modified material recovery regeneration of this magnetic.
Technical problem of the present invention is realized by following technical scheme.
A kind of modified by silver magnetic carbon nano-tube is removed the method for mercury ion in water, it is placed in pending water with adsorbed water mercury ion by the carbon nano-tube modified material of magnetic, described magnetic carbon nano-tube material is Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material, and this is a kind of many walls nanometer tubing.
Said method, described Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material is prepared by following steps: carbon nano-tube material after concentrated acid oxidized activating with solution containing iron salts with coprecipitation method at carbon nano tube surface supported ferriferous oxide, react with silver colloid again, make Nano silver grain be deposited on carbon nano-tube material surface.
Said method, the concrete preparation process of described Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material is as follows:
(1) activation:
1. take carbon nano-tube material 0.5-1.0g, be placed in 40-60mL autoclave, add the red fuming nitric acid (RFNA) that 10-20mL concentration mass fraction is 65-68%, enclosed high pressure reactor;
2. the autoclave that fills above-mentioned reactant is placed in to baking oven, under 100-105 ℃ of condition, maintains 10-15min, be then warming up to rapidly 150-160 ℃, reaction 1.0-1.5h, after reacting completely, stops heating, naturally cools to room temperature;
3. in baking oven, take out and open reactor, incline and residue spent acid, take washed with de-ionized water product to cleaning fluid as neutral;
4. above-mentioned product is dried to 4-6h at 100-110 ℃, make the multi-walled carbon nano-tubes after activation, standby;
(2) magnetic is modified:
1. magnetic modification reaction is to carry out under the condition of ultrasonic wave and nitrogen protection, and reaction temperature is 45-55 ℃;
2. take the carbon nano-tube material 0.5-1.0 g after activation, be suspended in the mixed solution that 100-200 ml contains (NH4) 2Fe (SO4) 26H2O and NH4Fe (SO4) 212H2O, reaction system solid-to-liquid ratio, the g/ml of activated carbon nano-tube/mixed solution is than being 1:200; In mixed liquor, solute quality is: (NH4) 2Fe (SO4) 26H2O is 0.36-3.2g, and NH4Fe (SO4) 212H2O is 0.53-4.7g; The mass ratio of solute (NH4) 2Fe (SO4) 26H2O and NH4Fe (SO4) 212H2O is 1.7:2.5;
3. above-mentioned system is placed under solution Ultrasonic Conditions and reacts 10-15min, wherein, supersonic frequency 40KHz, ultrasonic power 250W, heating power 400W; In course of reaction, dropwise add 8 mol/L ammoniacal liquor, make the pH value of mixed liquor remain on 11-12;
4. after ultrasonic reaction finishes, for further guaranteeing that reaction carries out thoroughly, reaction system is at 45-55 ℃ of water bath with thermostatic control 60-70min, and the constant speed of carrying out 300-400r/min stirs;
5. after having reacted, use respectively distilled water and absolute ethanol washing 3-4 time, vacuum drying 8-10h under 50 ℃ of conditions, makes the carbon nano-tube modified material of ferriferous oxide magnetic;
(3) silver particles load:
1. take the carbon nano-tube modified material of 0.2-0.3g ferriferous oxide magnetic, in the DMF/H2O of 50 ml mixed liquor, at supersonic frequency 40KHz, ultrasonic power 250W, ultrasonic dispersion 1 h under room temperature 20-25 ℃ of condition, the volume ratio of DMF and H2O is 1:1; Described DMF is DMF;
2. in 500 ml beakers, add respectively 100mL containing 0.017-0.034 g AgNO3 solution with containing the solution of 0.0882-0.1764 g trisodium citrate, vigorous stirring is fully mixed;
3. freshly prepared 500mmol/LNaBH4 solution, is placed in ice-water bath, standby;
4. under the condition of vigorous stirring, with pipettor, dropwise to filling in the beaker of AgNO3 solution and citric acid three sodium solution, add 1-2 ml NaBH4 solution, continue to stir 5min, make silver colloidal solution;
5. the mixed liquor of the carbon nano-tube modified material of oxides-containing iron magnetic of ultrasonic dispersion 1h is joined in the silver colloidal solution that continues vigorous stirring, stir 12h;
6. after having reacted, use respectively distilled water and absolute ethanol washing 3-4 time, vacuum drying 8-10h under 55 ℃ of conditions, makes Nano silver grain load/ferriferous oxide magnetic carbon-nano tube composite material.
Remove a method for mercury ion in water, it is placed in pending water with adsorbed water mercury ion using the carbon nano-tube modified material of magnetic as adsorbent, and described magnetic carbon nano-tube material is Nano silver grain load/ferriferous oxide magnetic carbon-nano tube composite material.
Said method, described magnetic carbon nano-tube material mercury ion in Adsorption water under 20-60 ℃, pH3-8 condition, adsorption time 0.5-1.5h.
Said method, the numerical value of described pH is 3-8, adopts the nitric acid of 1mol/L or the NaOH of hydrochloric acid and 1mol/L to regulate; The concentration of mercury ion is 0.02-180 μ g/mL, the g/ml of the magnetic carbon nano-tube material that uses and water than being 1:1000-1500.
A renovation process for Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material, it carries out according to the following steps:
(1) the arbitrary utmost point externally-applied magnetic field by bar magnet carries out Separation of Solid and Liquid by Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material and solution after Adsorption of Mercury ion, incline and the water body after adsorption treatment, collect Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material that absorption contains mercury ion;
(2), by the Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material 1.0g collecting, at 55 ℃, dry;
(3) by Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material of drying in Muffle furnace, logical nitrogen protection;
(4) rising muffle furnace to 200 ℃, keeps 20min;
(5) reaction naturally cools to room temperature after finishing;
(6) to be cooled to room temperature, cut off nitrogen, take out, i.e. Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material after recyclable thermal desorption.
The present invention utilizes multi-walled carbon nano-tubes porous media material as support skeleton, the ferriferous oxide of take carries out magnetic modification as soft magnetic bodies, again by the magnetic carbon nano-tube area load Nano silver grain of preparation, under the effect of externally-applied magnetic field, be easy to realize the Separation of Solid and Liquid of adsorbent and polluted-water; Magnetic carbon nano-tube material adsorption capacity after load Nano silver grain has had raising extremely significantly, meanwhile, has obviously improved the specificity to mercury ion absorption.Under normal temperature, affiliated material can reach 218.7mg/g to mercury ion maximum adsorption capacity, is 12 times of carbon nano-tube material maximum adsorption capacity of activation.In water, a large amount of other common ions that exist have no significant effect the absorption of mercury ion.By adopting magnetic separation technique, greatly simplified the separation process of adsorbent and the aqueous solution, saved processing time and cost.Magnetic separation process fast, thoroughly, has been created condition for reclaiming the subsequent processes of adsorbent.Reclaiming method of the present invention has avoided causing the possibility of secondary pollution to greatest extent, has good environmental economical profit and application prospect widely.
Accompanying drawing explanation
Fig. 1 is Nano silver grain load/ferriferous oxide magnetic carbon-nano tube composite material hysteresis curve figure;
Fig. 2 is Nano silver grain load/ferriferous oxide magnetic carbon-nano tube composite material electronic scanner microscope (SEM) photo;
Fig. 3 is Nano silver grain load/ferriferous oxide magnetic carbon-nano tube composite material projection electron microscope (TEM) photo;
Fig. 4 is Nano silver grain load/ferriferous oxide magnetic carbon-nano tube composite material X-ray diffraction (XRD) figure.
The specific embodiment
Below in conjunction with concrete enforcement, the present invention is described in further details.
Embodiment 1 CNT activation
1. get carbon nano-tube material 1.0g, be placed in 60mL autoclave, add the red fuming nitric acid (RFNA) that 20mL concentration mass fraction is 65-68%, enclosed high pressure reactor;
2. the autoclave that fills above-mentioned reactant is placed in to baking oven, under 100 ℃ of conditions, maintains 10min, be then warming up to rapidly 150 ℃, reaction 1.0h, after reacting completely, stops heating, naturally cools to room temperature;
3. in baking oven, take out and open reactor, incline and residue spent acid, take washed with de-ionized water product to cleaning fluid as neutral;
4. above-mentioned product is dried to 4h at 100 ℃, make the multi-walled carbon nano-tubes after activation, standby.
Magnetic modification reaction is to carry out under the condition of ultrasonic wave and nitrogen protection, and reaction temperature is 50 ℃;
Get the carbon nano-tube material 1.0g after activation, be suspended in the aqueous solution that 200mL contains 1.7g (NH4) 2Fe (SO4) 26H2O and 2.5gNH4Fe (SO4) 212H2O, the mass fraction of iron in reaction system mixed solution/(iron+CNT) is 35%, and it is carbon nano-tube modified that product is designated as 35%Fe magnetic;
It is 40KHz that above-mentioned system is placed in supersonic frequency, and ultrasonic power is 250W, under the Ultrasonic Conditions that heating power is 400W, reacts 10min, dropwise adds 8mol/L ammoniacal liquor in course of reaction, makes the pH value of mixed liquor remain on 11-12;
After phonoresponse finishes, reaction system is at 50 ℃ of water bath with thermostatic control 60min, and the constant speed of carrying out 300r/min stirs;
5. after having reacted, use respectively distilled water and absolute ethanol washing 3-4 time, vacuum drying 8h under 50 ℃ of conditions, makes the carbon nano-tube modified material of 35%Fe magnetic.
Embodiment 3 Nano silver grain loads
Get the carbon nano-tube modified material of 0.2g embodiment 2 gained ferriferous oxide magnetic, ultrasonic in the DMF/H2O of 50 ml mixed liquor, ultrasonic at supersonic frequency 40KHz, ultrasonic power 250W, carries out under the condition that room temperature is 20 ℃, disperses 1 h.The volume ratio of DMF and H2O is 1:1;
2. the solution containing 0.1764 g trisodium citrate containing 0.034 g AgNO3 solution and 100mL that adds respectively 100mL in 500 ml beakers, vigorous stirring is fully mixed;
3. fresh configuration 500mmol/L NaBH4 solution, is placed in ice-water bath, standby;
4. under the condition of strong stirring, with pipettor, dropwise to filling in the beaker of AgNO3 solution and citric acid three sodium solution, add 2 ml500mmol/L NaBH4 solution, continue to stir 5min, make silver colloidal solution;
5. the mixed liquor of the carbon nano-tube modified material of oxides-containing iron magnetic of ultrasonic dispersion 1h is joined in the silver colloidal solution that continues vigorous stirring, stir 12h;
6. after should completing, use respectively distilled water and absolute ethanol washing 3-4 time, vacuum drying 8h under 55 ℃ of conditions, make and be labeled as 10% Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material (in reaction solution, the mass fraction of silver/(silver+magnetic carbon nano-tube) is 10%, therefore be 10% Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material by Product Labeling).
Embodiment 4 Nano silver grain loads
1., get the carbon nano-tube modified material of 0.2g embodiment 2 gained ferriferous oxide magnetic, in the DMF/H2O of 50 ml mixed liquor at ultrasonic dispersion 1 h.Supersonic frequency is 40KHz, and ultrasonic power is 250W, 20 ℃ of room temperatures.The volume ratio of DMF and H2O is 1:1;
2., in 500 ml beakers, add respectively 100mL to contain 0.017 g AgNO3 solution and 100mL containing the solution of 0.0882 g trisodium citrate, vigorous stirring is fully mixed;
3., fresh preparation 500mmol/LNaBH4 solution, be placed in ice-water bath, standby;
4., under the condition of vigorous stirring, with liquid-transfering gun, dropwise to filling in the beaker of AgNO3 solution and citric acid three sodium solution, add 2 ml 500mmol/L NaBH4 solution, continue to stir 5min, make silver colloidal solution;
5., the mixed liquor of the carbon nano-tube modified material of oxides-containing iron magnetic of ultrasonic dispersion 1h is joined in the silver colloidal solution that continues vigorous stirring to stirring 12h;
6., should complete after, use respectively distilled water and absolute ethanol washing 3-4 time, vacuum drying 8h under 55 ℃ of conditions, makes and is labeled as 5% Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material.
Embodiment 5 removes mercury ion in water
10% Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material prepared by the embodiment 3 of take is adsorbent, the Trace Mercury ion in Adsorption water.At 20 ℃ of room temperatures, in 50mL closed container, carry out, mercury ion initial concentration is 250 μ g/mL, and pH value of solution is 7, and adsorbent addition is 0.02g, and the volume of solution is 25mL.Adsorption time is 60min, and maximal absorptive capacity is 218.7.
Adsorbance described in this description represents the quality of every gram of adsorbent Adsorption of Mercury, and unit is mg/g.
Embodiment 6
5% Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material prepared by the embodiment 4 of take is adsorbent, and adsorption conditions is with embodiment 5, and the maximal absorptive capacity of adsorbent is 181.3.
Comparative example 5 and 6, visible, the mass fraction that suitably improves within the specific limits silver/(silver+magnetic carbon nano-tube) in reaction solution can the adsorption capacity of reinforced composite to mercury ion in water.
Embodiment 7
The 10% Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material of embodiment 3 preparation of take is adsorbent, under 40 ℃ and 60 ℃ of conditions, adsorbs respectively, and other adsorption conditions, with embodiment 5, records maximal absorptive capacity and is respectively 277.7 and 232.6.
Comparative example 5 and 7, visible, in certain temperature range, Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material is that adsorbent strengthens along with the rising of temperature to some extent to the adsorption capacity of mercury ion in water, but excess Temperature, adsorption capacity has the trend of reduction.
Embodiment 8
10% Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material prepared by the embodiment 3 of take is adsorbent, adsorbs respectively under pH3 and pH8 condition, and other adsorption conditions, with embodiment 5, records maximal absorptive capacity and is respectively 215.1 and 196.8.
Comparative example 5 and 8, visible, under the condition of pH3-8, the change of pH has no significant effect the adsorption capacity of mercury ion in water Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material.
Embodiment 9
10% Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material prepared by the embodiment 3 of take is adsorbent, vibration absorption 20min and 100min, and other adsorption conditions, with embodiment 5, records maximal absorptive capacity and is respectively 165.5 and 218.8.
Comparative example 5 and 9, visible, within the scope of certain hour, suitably increase adsorption time and can improve adsorbance, adsorbent of the present invention to mercury ion in water be adsorbed on 1.5h after substantially reach adsorption equilibrium.
10% Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material prepared by the embodiment 3 of take is adsorbent, to Na+, the K+, Ca2+, Mg2+, Zn2+, Mn2+, Ni2+, Cu2+, Cd2+, Al3+ and the Fe3+ ion that add 1000 μ g/mL in the polluted-water that contains 20 ng/mL mercury ions, adsorption conditions is with embodiment 5, investigate the impact of higher concentration common metal ion on mercury adsorption process, result shows, common metal ion has no significant effect the adsorption capacity of adsorbent.Visible, though Nano silver grain of the present invention load/ferriferous oxide magnetic carbon nano-tube material has superior selective and specificity to the absorption of mercury ion in water.
Embodiment 11
Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material after Adsorption of Mercury ion in embodiment 5 is carried out to the de-regeneration of heat.After dry at 55 ℃ of Nano silver grain load/ferriferous oxide magnetic carbon nano-tube materials after Adsorption of Mercury ion, under high pure nitrogen (flow 0.5L/min) protection, be placed in tubular type Muffle furnace desorb 20min at 200 ℃.Be down to after room temperature, take out, obtain the Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material after reclaiming.
Embodiment 12
Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material that the embodiment 11 of take reclaims is adsorbent, the mercury ion in Adsorption water body, and adsorption conditions is with embodiment 5, and the magnetic carbon nano-tube material sorbent maximal absorptive capacity that records recovery is 158.8.
Visible, after described Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material adopts the method for thermal desorption to regenerate, adsorption capacity to mercury ion slightly declines compared with raw material, but still has very large adsorption capacity and superior mercury ion absorption property and stronger magnetic.
Embodiment 13
The activated carbon nano-tube material that the embodiment 1 of usining makes is direct as the mercury ion in adsorbent Adsorption water in the situation that not carrying out magnetic modification, adsorption conditions is with embodiment 5, and recording activated carbon nano-tube material sorbent is 17.9 to the maximal absorptive capacity of mercury ion.
The carbon nano-tube modified material of ferriferous oxide magnetic that the embodiment 2 of usining makes is as the mercury ion in adsorbent Adsorption water, pH4, temperature is 40 ℃, and other adsorption conditionses are with embodiment 5, and the carbon nano-tube modified material sorbent of ferriferous oxide magnetic recording is 26.5 to the maximal absorptive capacity of mercury ion.
Comparative example 7 and 13, visible by load Nano silver grain, can greatly improve original activated carbon nano-tube material and the adsorption capacity of iron oxide magnetic carbon nano-tube material to mercury ion, load Nano silver grain/magnetic carbon-nano tube composite material maximal absorptive capacity is 277.7mg/g, is respectively former activated carbon nano-tube material and the carbon nano-tube modified material maximum adsorption capacity of magnetic 15.5 times and 10.5 times.
Claims (4)
1. a modified by silver magnetic carbon nano-tube is removed the method for mercury ion in water, it is characterized in that, modified by silver magnetic carbon nano-tube is placed in to pending water with adsorbed water mercury ion, and described modified by silver magnetic carbon nano-tube is Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material;
Described Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material is prepared by following steps: carbon nano-tube material is coated ferriferous oxide with coprecipitation method in carbon nano tube surface with solution containing iron salts after concentrated acid oxidized activating, react with silver colloid again, make Nano silver grain be deposited on carbon nano-tube material surface;
Concrete preparation process is:
(1) activation:
1. take carbon nano-tube material 0.5-1.0g, be placed in 40-60mL autoclave, add the red fuming nitric acid (RFNA) that 10-20mL concentration mass fraction is 65-68%, enclosed high pressure reactor;
2. the autoclave that fills above-mentioned reactant is placed in to baking oven, under 100-105 ℃ of condition, maintains 10-15min, be then warming up to rapidly 150-160 ℃, reaction 1.0-1.5h, after reacting completely, stops heating, naturally cools to room temperature;
3. in baking oven, take out and open reactor, incline and residue spent acid, take washed with de-ionized water product to cleaning fluid as neutral;
4. above-mentioned product is dried to 4-6h at 100-110 ℃, make the multi-walled carbon nano-tubes after activation, standby;
(2) magnetic is modified:
1. magnetic modification reaction is to carry out under the condition of ultrasonic wave and nitrogen protection, and reaction temperature is 45-55 ℃;
2. take the carbon nano-tube material 0.5-1.0g after activation, be suspended in 100-200 mL and contain (NH
4)
2fe (SO
4)
26H
2o and NH
4fe (SO
4)
212H
2in the mixed solution of O, reaction system solid-to-liquid ratio, the g/mL of activated carbon nano-tube/mixed solution is 1:200; In mixed liquor, solute mass range is: (NH
4)
2fe (SO
4)
26H
2o is 0.36-3.2g, NH
4fe (SO
4)
212H
2o is 0.53-4.7g; Solute (NH
4)
2fe (SO
4)
26H
2o and NH
4fe (SO
4)
212H
2the mass ratio of O is 1.7:2.5;
3. above-mentioned solution system is placed under the Ultrasonic Conditions of supersonic frequency 40KHz, ultrasonic power 250W, heating power 400W and reacts 10-15min, in course of reaction, dropwise add 8mol/L ammoniacal liquor, make the pH value of mixed liquor remain on 11-12;
1. after ultrasonic reaction finishes, reaction system is at 45-55 ℃ of water bath with thermostatic control 60-70min, and the constant speed of carrying out 300-400r/min stirs;
5. after having reacted, use respectively distilled water and absolute ethanol washing 3-4 time, vacuum drying 8-10h under 50 ℃ of conditions, makes the carbon nano-tube modified material of ferriferous oxide magnetic;
(3) silver particles load:
1. take the carbon nano-tube modified material of 0.2-0.3g ferriferous oxide magnetic, at the DMF/H of 50 mL
2in O mixed liquor, supersonic frequency 40KHz, ultrasonic power 250W, ultrasonic dispersion 1 h, DMF and H under the condition of room temperature 20-25 ℃
2the volume ratio of O is 1:1; Described DMF is DMF;
2. in 500 mL beakers, add respectively 100mL to contain 0.017-0.034 g AgNO
3solution and 100mL are containing the solution of 0.0882-0.1764 g trisodium citrate, and vigorous stirring is fully mixed;
3. freshly prepared 500mmol/LNaBH
4solution, is placed in ice-water bath, standby;
4. under the condition of vigorous stirring, with pipettor dropwise to filling AgNO
3in the beaker of solution and citric acid three sodium solution, add 1-2 mL NaBH
4solution, continues to stir 5min, makes silver colloidal solution;
5. the mixed liquor of the carbon nano-tube modified material of oxides-containing iron magnetic of ultrasonic dispersion 1h is joined in the silver colloidal solution that continues vigorous stirring, stir 12h;
6. after having reacted, use respectively distilled water and absolute ethanol washing 3-4 time, vacuum drying 8-10h under 55 ℃ of conditions, makes Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material.
2. method according to claim 1, is characterized in that, described Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material is the mercury ion in Adsorption water under 20-60 ℃, pH3-8 condition.
3. method according to claim 2, is characterized in that, described pH numerical value is 3-8, and pH adopts the nitric acid of 1mol/L or the NaOH of hydrochloric acid and 1mol/L to regulate; In described water, the concentration of mercury ion is 0.02-180 μ g/mL, and described modified by silver magnetic carbon nano-tube is with the g/mL of pending water than being 1:1000-1500, and adsorption time is 0.5-1.5h.
4. as a renovation process for Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material used in claim 1,2 or 3, it is characterized in that, it carries out according to the following steps:
(1) the arbitrary utmost point externally-applied magnetic field by bar magnet carries out Separation of Solid and Liquid by Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material and solution after absorption Adsorption of Mercury ion, incline and the water body after adsorption treatment, collect Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material that absorption contains mercury ion;
(2), by the Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material 1.0g collecting, at 55 ℃, dry;
(3) by Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material of drying in Muffle furnace, logical nitrogen protection;
(4) rising muffle furnace to 200 ℃, keeps 20min;
(5) reaction naturally cools to room temperature after finishing;
(6) to be cooled to room temperature, cut off nitrogen, take out, i.e. Nano silver grain load/ferriferous oxide magnetic carbon nano-tube material after recyclable thermal desorption.
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| CN111036175B (en) * | 2019-12-16 | 2022-02-22 | 合肥学院 | Active carbon-Ag2O-CuO-Bi2O3Adsorbing material and preparation method and application thereof |
| CN115487787B (en) * | 2022-10-10 | 2023-08-01 | 扬州工业职业技术学院 | Preparation method of supported chelating resin-based water treatment adsorption material |
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