CN102553528B - Modified carbon nano tube material, method for removing mercury ions in water and method for regenerating modified carbon nano tube material - Google Patents
Modified carbon nano tube material, method for removing mercury ions in water and method for regenerating modified carbon nano tube material Download PDFInfo
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Abstract
The invention relates to a modified carbon nano tube material, a method for removing mercury ions in water and a method for regenerating the modified carbon nano tube material. The modified carbon nano tube material is a selenium modified nano particle load/iron oxide magnetic carbon nano tube composite material. According to the method for removing the mercury ions in the water, the modified carbon nano tube material is used as an adsorbent and is put into the water to be treated to adsorb the mercury ions in the water; and a method for preparing the modified carbon nano tube material comprises the following steps that: after being oxidized and activated by concentrated acid, a carbon nano tube material is coated with an iron oxide together with a ferric salt-containing solution on the surface of a carbon nano tube by a coprecipitation method and then is reacted with an aqueous solution containing Na2SeO3 and glucose to obtain the modified carbon nano tube material. The modified carbon nano tube material has high adsorptive capacity and selectivity on mercury, so that the solid-liquid separation of the adsorbent and the solution can be implemented conveniently under the action ofan additional magnetic field. After being treated, the modified carbon nano tube material can be recycled; compared with the conventional adsorption material, the modified carbon nano tube material has high recycling performance; and the used adsorbent is easy to separate and recover, so the water treatment cost is saved, the possibility of secondary pollution is reduced, and the modified carbon nano tube material has good economic and environmental benefits.
Description
Technical field
The present invention relates to a kind of modified carbon nano tube tube material and utilize it to remove method and the reclaiming method of mercury ion in the water, relate in particular to a kind of selenium modification carbon nano-tube material and utilize its method and reclaiming method of removing mercury ion in the water, belong to water-treatment technology field.
Background technology
Poisonous element mercury can enter into environment by Geological Reasons and artificial origin, the Trace Hg that is present in the environment can finally enter into water body by sedimentation etc., then through hydrobiological biological concentration and biomagnification, and generate organomercurial compound in its biochemical cycles process, toxicity strengthens nearly thousand times.So the Trace Hg of removing in the water body is of great significance with the human health tool preserving the ecological environment.
The Trace Hg that absorption method is removed in the water body has advantages of that additive method does not possess, as simple to operate, with low cost etc.CNT is the novel nano-material that was widely used in recent years, owing to having larger specific area and stable physicochemical properties, successfully has been used for removing in the middle of the research of water body pollutant.But the adsorbable multiple pollutant of CNT so that the selection specificity of material is not high, is restricted the adsorption capacity of mercury.Simultaneously, because CNT has certain hydrophobicity, quality is bulk, is not easy in the process of pollutant to be dispersed and to reclaim in removing water body, has increased difficulty and the cost used, thereby has also limited its range of application.In addition, the price of CNT is usually higher, can not recycle and limit CNT being widely used as adsorbent.
Summary of the invention
Technical problem to be solved by this invention is that the defective that overcomes prior art provides a kind of modified carbon nano tube tube material, and this material has the characteristics such as many walls porous, magnetic effect, high adsorption capacity, easy separation; In addition, the present invention also will further provide the renovation process that utilizes this modified carbon nano tube tube material to remove mercury ion in the water and it is provided as adsorbent.
Technical problem of the present invention is realized by following technical scheme.
A kind of modified carbon nano tube tube material, described modified carbon nano tube tube material are selenium decorated nanometer particle load/ferriferous oxide magnetic carbon-nano tube composite material.
A kind of method for preparing above-mentioned modified carbon nano tube tube material, it coats ferriferous oxide with coprecipitation method in carbon nano tube surface with solution containing iron salts with carbon nano-tube material behind the concentrated acid oxidized activating, again with contain Na
2SeO
3With the reactant aqueous solution of glucose, namely get selenium nano particles load/ferriferous oxide magnetic carbon-nano tube composite material.
Above-mentioned preparation method, specifically carry out as follows:
A, oxidized activating:
1. take by weighing carbon nano-tube material 0.5-1.0g, place 40-60 ml autoclave, adding 10-20 ml mass fraction is the red fuming nitric acid (RFNA) of 65-68%, the enclosed high pressure reactor;
The autoclave that 2. will fill above-mentioned reactant places baking oven, under 100-105 ℃ of condition, keeps 10-15 min, then is warming up to rapidly 150-160 ℃, and reaction 1.0-1.5 h after reacting completely, stops heating, naturally cools to room temperature;
3. take out in baking oven and the unlatching reactor, inclining the residue spent acid, is neutral take the washed with de-ionized water product to cleaning fluid;
4. with above-mentioned product oven dry 4-6 h under 100-110 ℃, make the carbon nano-tube material of activation, for subsequent use;
B, magnetic are modified:
1., the magnetic modification reaction of carbon nano-tube material is to carry out under the condition of ultrasonic wave and nitrogen protection, reaction temperature is 45-55 ℃;
2., take by weighing the carbon nano-tube material 0.5-1.0 g after the 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, the reaction system solid-to-liquid ratio, namely the g/ml of activated carbon nano-tube/mixed solution is 1:200; The solute mass range is in the mixed liquor: (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 system solution is placed reaction 10-15 min under the Ultrasonic Conditions; Ultrasound condition is: supersonic frequency 40KHz, ultrasonic power 250W, heating power 400W; The ammoniacal liquor that dropwise adds 8mol/L in the course of reaction remains between the 11-12 pH value of mixed liquor;
4., after ultrasonic reaction finishes, carry out thoroughly for further guaranteeing reaction, reaction system keeps 60-70min in 45-55 ℃ of water bath with thermostatic control, and the constant speed of carrying out 300-400r/min stirs;
5., the reaction finish after, use respectively distilled water and absolute ethanol washing 3-4 time, vacuum drying 8-10 h makes the ferriferous oxide magnetic carbon-nano tube composite material under 50 ℃ of conditions, and is for subsequent use;
C, selenium nano particles load:
1., get 0.0658 g Na
2SeO
3Placing volume with 0.198 g glucose is the autoclave inner canister of 40-60mL, then adds deionized water 12-20 ml, is stirred to dissolving.
2., add 0.2-2g step B gained modified carbon nano tube tube material, autoclave is airtight;
3., autoclave is placed baking oven, be warming up to 140 ℃, keep 10min;
4., then, at 180 ℃ of lower reaction 10h that continue;
5., be cooled to room temperature, water and absolute ethyl alcohol washed repeatedly after the brown precipitate thing filtered, and be colourless to cleaning solution, at 55 ℃ of lower oven dry 8h, makes modified Nano particle load/ferriferous oxide magnetic carbon-nano tube composite material.
A kind of method of removing mercury ion in the water, it places pending water with the adsorbed water mercury ion as adsorbent the modified carbon nano tube tube material, and described modified carbon nano tube tube material is selenium decorated nanometer particle load/ferriferous oxide magnetic carbon-nano tube composite material.
The method of mercury ion in the above-mentioned removal water, described adsorbent is the mercury ion in the Adsorption water under 20-60 ℃, the condition of pH5-9 in temperature.
The method of mercury ion in the above-mentioned removal water, when described absorption was carried out, the pH value of the mercurous aqueous solution was 5-9, regulated pH with the nitric acid of 1mol/L or the NaOH of hydrochloric acid and 1mol/L; Adsorption time is 0.5-1.0h; Described adsorbent is 1:1000-1500 with the g/ml ratio of water; (after measured, the initial concentration of mercury ion is 0.02-30 μ g/ml, and absorption end of a period concentration is: if initial concentration is lower limit, end of a period concentration is generally less than 1ng/mL, if initial concentration is the upper limit, end of a period concentration is generally less than 50ng/mL.)
A kind of renovation process of modified carbon nano tube tube material, it uses acid solution wash-out modified carbon nano tube tube material to obtain regeneration.
Above-mentioned renovation process, described acid solution are that volume ratio is 5%(v/v) watery hydrochloric acid.
Above-mentioned renovation process, it carries out according to the following steps:
(1) modified carbon nano tube tube material and the solution after by externally-applied magnetic field adsorption reaction being finished carries out Separation of Solid and Liquid, and the water-outlet body of inclining is collected and adsorbed the modified carbon nano tube tube material that mercury is arranged;
(2) in the modified carbon nano tube tube material, add watery hydrochloric acid;
(3) rapid stirring reaction 5min under the 300-400 r/min rotating speed;
(5) immediately by the adsorbent behind the externally-applied magnetic field separation wash-out, pour out the upper strata dilute acid soln after reaction finishes;
(6) the modified carbon nano tube tube material after above-mentioned dilute acid soln is washed washs with deionization immediately, until cleaning solution is neutral;
(7) with the carbon nano-tube modified material of the magnetic behind the wash-out at 50 ℃ of lower vacuum drying 6 h, namely get the carbon nano-tube modified material of magnetic.
Above-mentioned renovation process, the carbon nano-tube modified material of the magnetic after the described absorption is 1:10 with the g/ml ratio of watery hydrochloric acid.
The present invention is coated on the carbon nano-tube material surface with oxides-containing iron, and the decorative material of preparation has stronger soft magnetic bodies character, under the effect of externally-applied magnetic field, is easy to realize the Separation of Solid and Liquid of adsorbent and polluted-water.And the modified carbon nano-tube material list behind the load selenium nano particles reveals the higher adsorption capacity of mercury ion in the water and stronger selective.Under the normal temperature, the sorbing material maximum adsorption capacity is 47.5 mg/g, is 2.65 times of the activated carbon nano-tube adsorption capacities of materials modified without selenium.By pickling, can be with the complete wash-out of mercury ion of absorption, and the adsorption capacities of materials of pickling is without obvious reduction.Simultaneously, adopt magnetic separation technique, greatly simplified the separation process of adsorption treatment water body mercury ion process, processing time and cost have been saved, the adsorbent of the poisonous element of absorption can be realized collecting more thoroughly, be convenient to subsequent processes, avoided preferably secondary pollution, have good economic benefit, environmental benefit and application value.
Description of drawings
Fig. 1 is loaded with nano selenium/magnetic carbon nano-tube material hysteresis curve figure;
Fig. 2 is loaded with nano selenium/magnetic carbon nano-tube material electronics flying-spot microscope (SEM) photo;
Fig. 3 is loaded with nano selenium/magnetic carbon nano-tube material electronics transmission microscopy (TEM) photo;
Fig. 4 is loaded with nano selenium/magnetic carbon nano-tube material X-ray diffraction (XRD) figure.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described in further details.
The activation of embodiment 1 CNT
1. get carbon nano-tube material 1.0g, place 60 ml autoclaves, adding 20 ml mass fractions is the red fuming nitric acid (RFNA) of 65-68%, the enclosed high pressure reactor;
2., the autoclave that will fill above-mentioned reactant places baking oven, under 100 ℃ of conditions, keeps 10 min, then is 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, inclining the residue spent acid, is neutral take the washed with de-ionized water product to cleaning fluid;
4., with above-mentioned product at 100 ℃ of lower oven dry 4 h, make the carbon nano-tube material of activation, for subsequent use.
1., the magnetic modification reaction is to carry out under the condition of ultrasonic wave and nitrogen protection, reaction temperature is 50 ℃;
2., take by weighing carbon nano-tube material 1.0 g after the activation, be suspended in 200 ml and contain 1.7g (NH
4)
2Fe (SO
4)
26H
2O and 2.5gNH
4Fe (SO
4)
212H
2In the mixed solution of O, the mass fraction of iron in the reaction system mixed liquor/(iron+CNT) is 35%, and it is carbon nano-tube modified that product is designated as 35%Fe magnetic;
3., above-mentioned system solution is placed under the Ultrasonic Conditions react 10min; Ultrasonic Conditions is: supersonic frequency 40KHz, ultrasonic power 250W, heating power 400W.Dropwise add 8mol/L ammoniacal liquor in the course of reaction, the pH value of mixed liquor is remained between the 11-12;
4., after ultrasonic reaction finishes, carry out thoroughly for further guaranteeing reaction, reaction system keeps 60min in 50 ℃ of waters bath with thermostatic control, and the constant speed of carrying out 300r/min stirs;
5., the reaction finish after, use respectively distilled water and absolute ethanol washing 3-4 time, vacuum drying 8h under 50 ℃ of conditions makes the ferriferous oxide magnetic carbon-nano tube composite material, and is for subsequent use.
Embodiment 3 selenium nano particles loads
1., get 0.0658 g Na
2SeO
3Placing internal capacity with 0.198 g glucose is the autoclave inner canister of 60mL, then adds deionized water 20 ml, is stirred to dissolving; The inner canister material is polytetrafluoroethylene (PTFE);
2., add 0.2 g embodiment, 2 gained ferriferous oxide magnetic carbon-nano tube composite materials in the PTFE inner canister, build seal cover, screw the autoclave stainless steel outer sleeve, sealing;
3., above-mentioned autoclave is placed baking oven, be warming up to 140 ℃, keep 10min;
4. then, at 180 ℃ of lower reaction 10h;
5. be cooled to room temperature, water and absolute ethyl alcohol washed repeatedly after the brown precipitate thing filtered, and be colourless to cleaning solution, at 55 ℃ of lower oven dry 8h, makes selenium nano particles load/ferriferous oxide magnetic carbon-nano tube composite material.
Embodiment 4 selenium nano particles loads
Get 0.0658 g Na
2SeO
3Placing internal capacity with 0.198 g glucose is the autoclave liner cup of 60mL, then adds deionized water 20 ml, is stirred to dissolving; The inner canister material is polytetrafluoroethylene (PTFE);
2. add 2 g embodiment, 2 gained ferriferous oxide magnetic carbon-nano tube composite materials in PTFE liner cup, build seal cover, screw the autoclave stainless steel outer sleeve, sealing;
3. above-mentioned autoclave is placed baking oven, be warming up to 140 ℃, keep 10min;
4., at 180 ℃ of lower reaction 10h;
5. be cooled to room temperature, water and absolute ethyl alcohol washed repeatedly after the brown precipitate thing filtered, and be colourless to cleaning solution, at 55 ℃ of lower oven dry 8h, makes selenium nano particles load/ferriferous oxide magnetic carbon-nano tube composite material.
Mercury ion in the embodiment 5 Adsorption contaminant water
Take the selenium nano particles load of embodiment 3 preparation/ferriferous oxide magnetic carbon-nano tube composite material as adsorbent, the Trace Mercury ion in the Adsorption contaminant water.Adsorption experiment carries out in the 50mL closed container at 20 ℃, and the mercury ion initial concentration is 50 μ g/mL, and pH value of solution is 7, and the adsorbent dosage is 0.02g, and the volume of contaminant water is 25mL, and adsorption time is 60 min, and maximal absorptive capacity is 47.5.
Adsorbance described in this specification represents the quality of every gram adsorbent Adsorption of Mercury, and unit is mg/g.
Mercury ion in the embodiment 6 Adsorption contaminant water
Take embodiment 4 preparation the selenium nano particles load/the ferriferous oxide magnetic carbon-nano tube composite material is as adsorbent, adsorption conditions is with embodiment 5, the maximal absorptive capacity of adsorbent is 30.0.
The comparative example 5, and as seen, in the selenium nano particles loading process, the mass fraction that suitably improves selenium/(selenium+magnetic carbon nano-tube material) can improve sorbing material to the adsorption capacity of mercury ion in the water.
Embodiment 7
Take the selenium nano particles load of embodiment 3 preparation/ferriferous oxide magnetic carbon-nano tube composite material as adsorbent, under 40 ℃, 60 ℃ conditions, carry out respectively adsorption experiment, other adsorption conditions records maximal absorptive capacity and is respectively 52.6 and 59.8 with embodiment 5.
The comparative example 5, and as seen, in certain temperature range, selenium nano particles load/ferriferous oxide magnetic carbon-nano tube composite material becomes large to the adsorption capacity of mercury ion in the water along with the rising of temperature.
Embodiment 8
Take the selenium nano particles load of embodiment 3 preparation/ferriferous oxide magnetic carbon-nano tube composite material as adsorbent, under pH 5, pH9 condition, adsorb respectively respectively, other adsorption conditions records maximal absorptive capacity and is respectively 32.7 and 47.0 with embodiment 5.
The comparative example 5, and is as seen, under neutral and weak basic condition, high under the absorption property weaker acid condition of mercury ion in selenium nano particles load/ferriferous oxide magnetic carbon-nano tube composite material adsorbed water.
Embodiment 9
Take the selenium nano particles load of embodiment 3 preparation/ferriferous oxide magnetic carbon-nano tube composite material as adsorbent, vibration absorption 20min, 100min, other adsorption conditions records maximal absorptive capacity and is respectively 30.2 and 47.5 with embodiment 5.
The comparative example 5, as seen, selenium nano particles load of the present invention/ferriferous oxide magnetic carbon-nano tube composite material to mercury ion in the water be adsorbed on 60min after substantially reach adsorption equilibrium.
Take the selenium nano particles load of embodiment 3 preparation/ferriferous oxide magnetic carbon-nano tube composite material as adsorbent, add the Na of 1000 μ g/mL in the polluted-water that contains 20 ng/mL mercury ions
+, K
+, Ca
2+, Mg
2+, Zn
2+, Mn
2+, Ni
2+, Cu
2+, Cd
2+, Al
3+And Fe
3+Ion, adsorption conditions be with embodiment 5, investigates the higher concentration common metal ion to the impact of mercury adsorption process, and the result shows, common metal ion is on the not obviously impact of absorption of selenium nano particles load/ferriferous oxide magnetic carbon-nano tube composite material.As seen, the applied sorbing material of the present invention has superior selective and antijamming capability to the absorption of mercury ion in the water.
Embodiment 11
Adsorbent behind the Adsorption of Mercury ion is carried out wash-out regeneration.Adopting 10mL5%HCl (v/v) be eluant, eluent, stirs 5min in the 50mL beaker, removes eluent, take deionized water washing selenium nano particles load/ferriferous oxide magnetic carbon-nano tube composite material 3-4 time to cleaning solution as neutrality.Vacuum drying 8h under 50 ℃ of conditions, selenium nano particles load/ferriferous oxide magnetic carbon-nano tube composite material after obtaining to reclaim.
Embodiment 12
The selenium nano particles load of reclaiming take embodiment 11/ferriferous oxide magnetic carbon-nano tube composite material is as adsorbent, mercury ion in the Adsorption water body, adsorption conditions is with embodiment 5, record recovery the selenium nano particles load/ferriferous oxide magnetic carbon-nano tube composite material maximal absorptive capacity is 44.7.The magnetic of the selenium nano particles load that mensuration embodiment 11 reclaims/ferriferous oxide magnetic carbon-nano tube composite material, the result shows that magnetic is without obvious reduction.
As seen, it is that eluant, eluent is regenerated that described selenium nano particles load/ferriferous oxide magnetic carbon-nano tube composite material can adopt watery hydrochloric acid, and regeneration still has more superior mercury ion absorption property and stronger magnetic, satisfies the requirement that recycles.
Embodiment 13
The activated carbon nano-tube material that makes with embodiment 1 is not in the situation that carry out magnetic and modify directly as the mercury ion in the adsorbent Adsorption water, adsorption conditions is with embodiment 5, and recording the activated carbon nano-tube material sorbent is 17.9 to the maximal absorptive capacity of mercury ion.
The ferriferous oxide magnetic carbon-nano tube composite material that makes with embodiment 2 is removed mercury ion in the water as adsorbent, adsorption conditions is pH 4,60 ℃, when adsorbent dosage 0.02g, 100min (optimal adsorption condition), the maximal absorptive capacity that records the carbon nano-tube material Adsorption of Mercury ion that magnetic modifies is 27.5.
Comparative example 5 and embodiment 6, visible by can obviously improve the adsorption capacity to mercury ion in magnetic carbon nano-tube area load nanometer selenium.
Claims (8)
1. a modified carbon nano tube tube material is characterized in that, described modified carbon nano tube tube material is the composite of ferriferous oxide magnetic carbon nano-tube load selenium nano particles;
The composite of described ferriferous oxide magnetic carbon nano-tube load selenium nano particles is that carbon nano-tube material is coated ferriferous oxide with coprecipitation method in carbon nano tube surface with solution containing iron salts behind the concentrated acid oxidized activating, again with contain Na
2SeO
3With the reactant aqueous solution of glucose, namely get the composite of ferriferous oxide magnetic carbon nano-tube load selenium nano particles;
Modification is carried out as follows:
A, oxidized activating:
1. take by weighing carbon nano-tube material 0.5-1.0g, place 40-60 mL autoclave, adding 10-20 mL mass fraction is the red fuming nitric acid (RFNA) of 65-68%, the enclosed high pressure reactor;
The autoclave that 2. will fill reactant places baking oven, under 100-105 ℃ of condition, keeps 10-15 min, then is warming up to rapidly 150-160 ℃, and reaction 1.0-1.5 h after reacting completely, stops heating, naturally cools to room temperature;
3. take out in baking oven and the unlatching reactor, inclining the residue spent acid, is neutral take the washed with de-ionized water product to cleaning fluid;
4. the product that 3. step is obtained makes the carbon nano-tube material of activation at 100-110 ℃ of lower oven dry 4-6 h, and is for subsequent use;
B, magnetic are modified:
1., the magnetic modification reaction of carbon nano-tube material is to carry out under the condition of ultrasonic wave and nitrogen protection, reaction temperature is 45-55 ℃;
2., take by weighing the carbon nano-tube material 0.5-1.0 g after the 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, the reaction system solid-to-liquid ratio, namely the g/mL of activated carbon nano-tube and mixed solution is 1:200; The solute mass range is in the mixed solution: (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., the system solution that 2. the magnetic modification step is obtained places reaction 10-15 min under the Ultrasonic Conditions; Ultrasound condition is: supersonic frequency 40KHz, ultrasonic power 250W, heating power 400W; The ammoniacal liquor that dropwise adds 8mol/L in the course of reaction remains between the 11-12 pH value of mixed liquor;
4., after ultrasonic reaction finishes, carry out thoroughly for further guaranteeing reaction, reaction system keeps 60-70min in 45-55 ℃ of water bath with thermostatic control, and the constant speed of carrying out 300-400r/min stirs;
5., the reaction finish after, use respectively distilled water and absolute ethanol washing 3-4 time, vacuum drying 8-10 h makes the ferriferous oxide magnetic carbon-nano tube composite material under 50 ℃ of conditions, and is for subsequent use;
C, selenium nano particles load:
1., get 0.0658 g Na
2SeO
3Placing volume with 0.198 g glucose is the autoclave inner canister of 40-60mL, then adds deionized water 12-20 mL, is stirred to dissolving;
2., add the ferriferous oxide magnetic carbon nano-tube material of 0.2-2g step B gained, autoclave is airtight;
3., autoclave is placed baking oven, be warming up to 140 ℃, keep 10min;
4., then, at 180 ℃ of lower reaction 10h that continue;
5., be cooled to room temperature, water and absolute ethyl alcohol washed repeatedly after the brown precipitate thing filtered, and be colourless to cleaning solution, at 55 ℃ of lower oven dry 8h, makes the ferriferous oxide magnetic carbon nano-tube load selenium nano particles composite of modification.
2. method of removing mercury ion in the water, it is characterized in that, it is to place pending water with the adsorbed water mercury ion as adsorbent modified carbon nano tube tube material claimed in claim 1, and described modified carbon nano tube tube material is ferriferous oxide magnetic carbon nano-tube load selenium nano particles composite.
3. the method for mercury ion in the described removal water according to claim 2 is characterized in that, described adsorbent is the mercury ion in the Adsorption water under 20-60 ℃, the condition of pH5-9 in temperature.
4. the method for mercury ion in the described removal water according to claim 3 is characterized in that, when described absorption was carried out, the numerical value of pH was 5-9 in the water, and pH adopts the nitric acid of 1mol/L or the NaOH of hydrochloric acid and 1mol/L to regulate; Adsorption time is 0.5-1.0h; Described adsorbent is 1:1000-1500 with the g/mL ratio of water.
5. the renovation process of modified carbon nano tube tube material as claimed in claim 1 is characterized in that, it uses acid solution wash-out modified carbon nano tube tube material to obtain regeneration.
6. renovation process according to claim 5 is characterized in that, described acid solution is that volume ratio is 5%(v/v) watery hydrochloric acid.
7. renovation process according to claim 6 is characterized in that, it carries out according to the following steps:
(1) modified carbon nano tube tube material and the solution after by externally-applied magnetic field adsorption reaction being finished carries out Separation of Solid and Liquid, and the water-outlet body of inclining is collected and adsorbed the modified carbon nano tube tube material that mercury is arranged;
(2) in the modified carbon nano tube tube material, add watery hydrochloric acid;
(3) rapid stirring reaction 5min under the 300-400 r/min rotating speed;
(4) immediately by the adsorbent behind the externally-applied magnetic field separation wash-out, pour out the upper strata dilute acid soln after reaction finishes;
(5) the modified carbon nano tube tube material after above-mentioned dilute acid soln is washed washs with deionization immediately, until cleaning solution is neutral;
(6) with the carbon nano-tube modified material of the magnetic behind the wash-out at 50 ℃ of lower vacuum drying 6 h, namely get the carbon nano-tube modified material of magnetic.
8. renovation process according to claim 7 is characterized in that, the modified carbon nano tube tube material that described absorption has mercury and the g/mL of watery hydrochloric acid are than being 1:10.
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| US10730034B2 (en) | 2017-08-28 | 2020-08-04 | Viviron Technology LLC | Iron-selenide-oxide sorbent composition for removing mercury (Hg) vapor from a gaseous stream; methods of use and methods of manufacture |
| CN109250773A (en) * | 2018-10-30 | 2019-01-22 | 李忠 | A kind of sewage treatment composite nano materials and preparation method thereof |
| CN109569551A (en) * | 2018-11-27 | 2019-04-05 | 中国科学院北京综合研究中心 | A kind of preparation method and regeneration method of the nano ceramic material loading nanometer selenium |
| CN109772275B (en) * | 2019-01-07 | 2021-12-07 | 中科京投环境科技江苏有限公司 | Mercury adsorbent and preparation method thereof |
| CN109772274B (en) * | 2019-01-07 | 2021-12-07 | 中科京投环境科技江苏有限公司 | Mercury-containing wastewater treatment method |
| CN112275319B (en) * | 2020-11-03 | 2023-06-06 | 扬州工业职业技术学院 | Organic selenium catalyst loaded with carbon nano tubes and preparation method and application thereof |
| CN113198432B (en) * | 2021-06-18 | 2023-07-21 | 江苏乾汇和环保再生有限公司 | Preparation method of biomass activated carbon |
| CN115845789A (en) * | 2022-09-13 | 2023-03-28 | 浙江慧科环保科技有限公司 | Preparation method of sulfur deposition type iron-based heavy metal adsorption material |
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