CN107486184A - It is a kind of to be used to remove sorbing material of inorganic mercury ion and methyl mercury compound and preparation method thereof in water body - Google Patents
It is a kind of to be used to remove sorbing material of inorganic mercury ion and methyl mercury compound and preparation method thereof in water body Download PDFInfo
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- CN107486184A CN107486184A CN201710929370.7A CN201710929370A CN107486184A CN 107486184 A CN107486184 A CN 107486184A CN 201710929370 A CN201710929370 A CN 201710929370A CN 107486184 A CN107486184 A CN 107486184A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
The invention provides a kind of preparation method for being used to remove the sorbing material of inorganic mercury ion and methyl mercury compound in water body, comprise the following steps：Polyvinyl alcohol aeroge reaction, obtains sorbing material in molybdenum disulfide precursor solution.The polyvinyl alcohol aeroge that molybdenum disulfide nano flower is modified is prepared using polyvinyl alcohol aeroge and molybdenum disulfide presoma solvent thermal reaction in the present invention；The polyvinyl alcohol aeroge for the molybdenum disulfide nano flower modification being prepared using the present invention can carry out good absorption as sorbing material to inorganic mercury ion in water and methyl mercury compound, adsorption rate is high, and secondary pollution will not be caused to water body, method is simple, and cost is low.
Description
Technical field
The present invention relates to water-treatment technology field, is used to remove inorganic mercury ion and methyl in water body more particularly, to one kind
Sorbing material of mercury compound and preparation method thereof.
Background technology
Water, it is the most important natural resources that biology is depended on for existence, is even more the important composition of ecological environment for the mankind
Part.Influenceed by mankind's activity, a large amount of undressed municipal refuse, contaminated soil, industrial wastewater and sanitary sewages
And atmospheric fallout is continually drained in water, cause the pollutant in water body in ascendant trend year by year.Nowadays, China is most absolutely
All there is more prominent quality problem to some extent in number city.Content of beary metal in water body recovery technology and deposit is drastically
Rise.
" mercury " that mercury, i.e. people are generally said, it is that unique liquid metals, toxicity are very big at room temperature.It is than great
(13.564), fusing point low (- 38.87 DEG C), boiling point high (356.95 DEG C) conduct electricity very well and the features such as the uniform coefficients of expansion,
Industry, agricultural, science and technology, communications and transportation, medical and health and national defence etc. have a wide range of applications in field.Mercury-containing waste water essentially from
Chemical industry for making chlorine and alkali factory (mercury process), non-ferrous metals smelting works' (flue gas washing), amalgam process recovery noble metal, insecticide factory (insecticide, kill
Microbial inoculum, mould inhibitor, seed selection agent etc.), chemical industry (catalyst), paper industry (bactericide, adhesion agent and flocculation remover etc.),
Electrical equipment and electronics industry (connection circuit, manufacture switch, bulb and battery etc.), petrochemical industry and plastics industry (catalyst),
Measure instrument, thermometer, pressure gauge production and medical (disinfectant, preservative etc.) industry, in addition also explosive, pharmacy, printing and dyeing,
Makeup, photograph industry and scientific research institution and hospital laboratory etc. also discharge a certain amount of mercury-containing waste water.Mercury-containing waste water is the world
One of maximum industrial wastewater of upper harm.The mercury and mercuric compounds being discharged into water body, formed respectively through physics, chemistry and biological agent
The mercury of kind form, can especially change into the very big methyl class compound (representative substances are methyl mercury) of toxicity, endanger water
Biology and the mankind.Mercury and mercuric compounds mainly enter in organism by alimentary canal, and its basic toxicity is mercury and zymoprotein
Sulfydryl combines, the metabolism of block cell.Inorganic ions mercury, with concentration highest in kidney, it is secondly liver, spleen, thyroid gland, enters
Human brain is then extremely difficult.Such as it is organic mercury, alkyl mercury tires out collection in liver and ranked first, and kidney takes second place, and brain tissue and testis occupy the 3rd
Position.It is exactly as caused by discharge of the mercury catalyst in chemical plant in water that nineteen fifty-three, which occurs in the minamata disease of Japan,.
Prior art discloses numerous methods for removing inorganic mercury ion and methyl mercury compound in water removal, including chemical precipitation
Method, ion-exchange, active carbon adsorption, chemical reduction reaction method, electrolysis etc..But chemical precipitation method not only use by sulfide
The more difficult control of amount, while sulphide tailings can bring very big toxicity, easily cause secondary pollution to water body；Ion-exchange operates
Very complicated, ion exchange resin cost is too high, and effect is undesirable；Removal efficiency of the active carbon adsorption for organic mercury
Preferably, it is limited for the removal efficiency of inorganic mercury；The inapplicable removal with organic mercury of chemical reduction reaction method；Electrolysis energy consumption
Greatly.Cost is high.
The content of the invention
In view of this, the technical problem to be solved in the present invention in provide it is a kind of be used to removing in water body inorganic mercury ion and
The preparation method of the sorbing material of methyl mercury compound, the sorbing material that method of the invention is prepared is for inorganic mercury ion
It can be adsorbed well with methyl mercury compound, adsorption rate is high, and will not cause secondary pollution to water body, and method is simple, into
This is low.
The invention provides a kind of system for being used to remove the sorbing material of inorganic mercury ion and methyl mercury compound in water body
Preparation Method, comprise the following steps：
Polyvinyl alcohol aeroge reaction, obtains sorbing material in molybdenum disulfide precursor solution.
Preferably, the polyvinyl alcohol aeroge is prepared as follows：
Polyvinyl alcohol and inorganic acid hydro-thermal reaction, obtain polyvinyl alcohol aeroge.
Preferably, the polyvinyl alcohol is polyvinyl alcohol water solution, and the mass concentration of the polyvinyl alcohol water solution is 3%
~7%；The inorganic acid is sulfuric acid；The concentration of the inorganic acid is 3~5mol/L.
Preferably, in addition to add the multi-walled carbon nanotube aqueous solution；The mass concentration of the multi-walled carbon nanotube aqueous solution
For 1%~3%.
Preferably, the concentration of the molybdenum disulfide precursor solution is 2~2.5mg/mL；The polyvinyl alcohol aeroge with
The mass ratio of molybdenum disulfide presoma is (0.2~0.5)：(0.04~0.05).
Preferably, protective agent is also added in the reaction；The protective agent is tri octyl phosphine；The protective agent and the solution
Volume ratio be (6~8)：(15000~25000).
Preferably, the reaction temperature is 200 DEG C；The reaction time is 24h.
Preferably, the molybdenum disulfide presoma is four thio ammonium molybdate；The solution is N,N-dimethylformamide.
The invention provides a kind of sorbing material for being used to remove inorganic mercury ion and methyl mercury compound in water body, by upper
The preparation method described in technical scheme is stated to be prepared.
The invention provides a kind of method for removing inorganic mercury ion and methyl mercury compound in water body to use above-mentioned technology
The sorbing material that preparation method described in scheme is prepared is inhaled to inorganic mercury ion and/or methyl mercury compound in water body
It is attached.
Compared with prior art, it is used to remove inorganic mercury ion and methyl mercury compound in water body the invention provides one kind
Sorbing material preparation method, comprise the following steps：Polyvinyl alcohol aeroge is in molybdenum disulfide precursor solution, reaction,
Obtain sorbing material.Two sulphur are prepared using polyvinyl alcohol aeroge and molybdenum disulfide presoma solvent thermal reaction in the present invention
Change the polyvinyl alcohol aeroge of molybdenum nano flower modification；The polyethylene for the molybdenum disulfide nano flower modification being prepared using the present invention
Alcohol aeroge can carry out good absorption, adsorption rate as sorbing material to inorganic mercury ion in water and methyl mercury compound
Height, and secondary pollution will not be caused to water body, method is simple, and cost is low.
Brief description of the drawings
Fig. 1 is the embodiment of the present invention 5, Pelteobagrus fulvidraco cub survival rate compares figure；
Fig. 2 is the Experimental results show figure of the embodiment of the present invention 7；Wherein (a) mercury ion Dynamic Absorption curve；(b) adsorb
Material measures the breadth coefficient to mercury ion under various circumstances；(c) methyl mercury compound clearance is tested；
Fig. 3 (a) is the antijamming capability measurement result of the sorbing material of the embodiment of the present invention 8；(b) embodiment of the present invention 8 is inhaled
The comparison figure of distribution coefficient of the enclosure material when recycling for 4 times；
Fig. 4 is spent admittedly for the molybdenum disulfide nano flower after the modification of the embodiment of the present invention 9 and the molybdenum disulfide nano being separately synthesized
Body, the adsorption capacity under phase homogenous quantities compare figure；
Fig. 5 is the scanning electron microscope (SEM) photograph of the aeroge that the embodiment of the present invention 2 is prepared under low resolution and high-resolution；
Fig. 6 is that monodispersed molybdenum disulfide nano spends high-resolution-ration transmission electric-lens figure.
Embodiment
The invention provides a kind of system for being used to remove the sorbing material of inorganic mercury ion and methyl mercury compound in water body
Preparation Method, comprise the following steps：
Polyvinyl alcohol aeroge reaction, obtains sorbing material in molybdenum disulfide precursor solution.
Source of the invention for the polyvinyl alcohol aeroge can be commercially available, or ability without limiting
It is prepared by method known to field technique personnel.
According to the present invention, preferably it is prepared as follows：
Polyvinyl alcohol and inorganic acid hydro-thermal reaction, obtain polyvinyl alcohol aeroge.
In the present invention, the polyvinyl alcohol is polyvinyl alcohol water solution, the mass concentration of the polyvinyl alcohol water solution
Preferably 3%~7%；More preferably 4%~6%；Most preferably 5%.
The inorganic acid is sulfuric acid；The concentration of the inorganic acid is 3~5mol/L；More preferably 4~5mol/L.
According to the present invention, preferable scheme is：
3%~7% 15~25mL of polyvinyl alcohol water solution, add the 3~5mol/L mL of inorganic acid 0.5~1.5；More
Preferably：
3%~7% 20~25mL of polyvinyl alcohol water solution, add 3~5mol/L 1~1.5mL of inorganic acid.
According to the present invention, in addition to add the multi-walled carbon nanotube aqueous solution；The quality of the multi-walled carbon nanotube aqueous solution
Concentration is preferably 1%~3%；More preferably 2%~3%.
Source of the invention for the polyvinyl alcohol, inorganic acid and multi-walled carbon nanotube is without limiting, this area skill
Known to art personnel.Can be commercially available.
In the present invention, the hydro-thermal reaction reaction temperature is 180~200 DEG C；The reaction time is 18~24h.
Reaction of the present invention is preferably carried out in a kettle.
Polyvinyl alcohol aeroge is dried to obtain after reaction.
Mode of the invention for the drying is preferably freeze-dried, the present invention is for the freezing without limiting
Dry design parameter is well known to those skilled in the art without limiting.
It is that polyvinyl alcohol self-crosslinking aeroge is prepared after drying.
The polyvinyl alcohol aeroge that the present invention is prepared possesses the good characteristic of aeroge, as density is small, specific surface area
It is big etc..In addition, product possesses good mechanical performance, when colloid is compressed into deformation quantity 50%, remain to keep colloid complete
Property, and when pressure is revoked, colloid can recover original geometric size.After compression circulation 20 times, colloid is in itself simultaneously
It will not be destroyed.Its excellent mechanical performance, laid the first stone for its application in production and living.
Polyvinyl alcohol aeroge reaction, obtains sorbing material in molybdenum disulfide precursor solution.
It is preferred that it is specially：
The N,N-dimethylformamide (DMF) that dry polyvinyl alcohol aeroge is immersed in molybdenum disulfide presoma is molten
In liquid, and solution is transferred in reactor, using solvent-thermal method, reacted in reactor, you can generate the absorption of mercury contaminants
Material.
In the present invention, the concentration of the molybdenum disulfide precursor solution is preferably 2~2.5mg/mL；More preferably 2.2
~2.4mg/mL.
In the present invention, the molybdenum disulfide presoma is preferably four thio ammonium molybdate；The solution includes but is not limited to
For N,N-dimethylformamide.
The present invention for the source of the four thio ammonium molybdate and DMF without limit, it is commercially available i.e.
Can.
According to the present invention, the mass ratio of the polyvinyl alcohol aeroge and molybdenum disulfide presoma be preferably (0.2~
0.5)：(0.04~0.05)；More preferably (1.5~1.8)：(0.045~0.048).
In the present invention, protective agent is preferably also added in the reaction；The protective agent is preferably tri octyl phosphine；
It is preferred that it is specially：
Solvent is added in reactor, adds molybdenum disulfide presoma, protective agent is added, stirring, adds aeroge reaction.
In the present invention, the volume ratio of the protective agent and the solution is preferably (6~8)：(15000~25000)；
More preferably (7~8)：(20000~25000).
In the present invention, the reaction temperature is 180~200 DEG C；The reaction time is 18~24h.
The invention provides a kind of system for being used to remove the sorbing material of inorganic mercury ion and methyl mercury compound in water body
Preparation Method, comprise the following steps：Polyvinyl alcohol aeroge reaction, obtains sorbing material in molybdenum disulfide precursor solution.This
Molybdenum disulfide nano flower modification is prepared using polyvinyl alcohol aeroge and molybdenum disulfide presoma solvent thermal reaction in invention
Polyvinyl alcohol aeroge；The polyvinyl alcohol aeroge for the molybdenum disulfide nano flower modification being prepared using the present invention is as absorption
Material can carry out good absorption to inorganic mercury ion in water and methyl mercury compound, and adsorption rate is high, and will not to water body
Secondary pollution is caused, method is simple, and cost is low.
The invention provides a kind of sorbing material for being used to remove inorganic mercury ion and methyl mercury compound in water body, by upper
The preparation method described in technical scheme is stated to be prepared.
The invention provides a kind of method for removing inorganic mercury ion and methyl mercury compound in water body to use above-mentioned technology
The sorbing material that preparation method described in scheme is prepared is inhaled to inorganic mercury ion and/or methyl mercury compound in water body
It is attached.
Polyvinyl alcohol aeroge possesses excellent mechanical performance, so, the sorbing material that the present invention prepares can be according to need
Cut into different size.Sorbing material after cutting is immersed in the water body being mercury-contaminated, shakes certain time, you can right
Water body completes purification.
According to method proposed by the present invention by after water body purification, adsorbent can be pressed from both sides out with tweezers, you can realize pollution
The separation of thing and water body.And can be by sorbing material being immersed in dilute hydrochloric acid solution so that it is recycled.Experiment card
Bright, by the purification-recovery-decontamination cycle of 4 times, the absorption property of sorbing material in itself does not have the sign decayed.Illustrate this
The sorbing material property synthesized in invention is stable, therefore is also beneficial to the control of cost.
After being purified using the sorbing material synthesized in the present invention to water body, the basic life of life of aquatile is lived
It is dynamic to be unaffected.Its survival rate can compare favourably with the biological survival rate in normal water body.Illustrate what is synthesized in the present invention
Sorbing material possesses excellent clean-up effect, while itself is nontoxic, will not cause secondary pollution to water body.Experimental result table
Sorbing material that is bright, being synthesized in the present invention, not only to inorganic mercury ion (Hg2+) possess good absorbent properties, while to methyl
Mercury compound (MeHg+) there is very high absorption efficiency.
In order to further illustrate the present invention, with reference to embodiments to provided by the present invention for removing inorganic mercury in water body
Sorbing material of ion and methyl mercury compound and preparation method thereof is described in detail.
Embodiment 1
1mL 4mol/L sulfuric acid is added in the polyvinyl alcohol water solution 20mL of 5% mass concentration, then utilizes hydro-thermal
Method reacts 24h in 200 DEG C of reactor, freeze-drying, you can generation polyvinyl alcohol aeroge.The polyethylene that 0.2g is dried
Alcohol aeroge is immersed in 20mL DMFs (DMF) solution of 45.5mg four thio ammonium molybdates, and solution is turned
Move in reactor, using solvent-thermal method, react 24h in 200 DEG C of reactor, you can generate the adsorption material of mercury contaminants
Material.
Embodiment 2
1mL 4mol/L sulfuric acid is added in the polyvinyl alcohol water solution 20mL of 5% mass concentration, and 1mL concentration is
The 2% multi-walled carbon nanotube aqueous solution, 24h then is reacted in 200 DEG C of reactor using hydro-thermal method, is freeze-dried, you can
Generate polyvinyl alcohol aeroge.The 0.3g polyvinyl alcohol aeroges dried are immersed in the 20mL of 45.5mg four thio ammonium molybdates
In DMF (DMF) solution, 7 μ L tri octyl phosphines, stirring are added, and solution is transferred in reactor, is utilized
Solvent-thermal method, react 24h in 200 DEG C of reactor, you can generate the sorbing material of mercury contaminants.
Embodiment 3
1mL 3mol/L sulfuric acid is added in the polyvinyl alcohol water solution 20mL of 3% mass concentration, and 1mL concentration is
The 2% multi-walled carbon nanotube aqueous solution, 24h then is reacted in 200 DEG C of reactor using hydro-thermal method, is freeze-dried, you can
Generate polyvinyl alcohol aeroge.The 0.5g polyvinyl alcohol aeroges dried are immersed in the 20mL N of 42mg four thio ammonium molybdates,
In dinethylformamide (DMF) solution, 6 μ L tri octyl phosphines, stirring are added, and solution is transferred in reactor, utilization is molten
The hot method of agent, reacts 24h in 200 DEG C of reactor, you can generates the sorbing material of mercury contaminants.
Embodiment 4
1mL 5mol/L sulfuric acid is added in the polyvinyl alcohol water solution 20mL of 7% mass concentration, and 1mL concentration is
The 2.5% multi-walled carbon nanotube aqueous solution, 24h then is reacted in 200 DEG C of reactor using hydro-thermal method, be freeze-dried, i.e.,
Polyvinyl alcohol aeroge can be generated.The 0.4g polyvinyl alcohol aeroges dried are immersed in the 20mL of 48mg four thio ammonium molybdates
In DMF (DMF) solution, 7 μ L tri octyl phosphines, stirring are added, and solution is transferred in reactor, is utilized
Solvent-thermal method, react 24h in 200 DEG C of reactor, you can generate the sorbing material of mercury contaminants.
Embodiment 5
Before and after the sorbing material that lake water is prepared using the embodiment of the present invention 1~2 purifies, the survival rate of Pelteobagrus fulvidraco cub
As shown in table 1.
All water for raising Pelteobagrus fulvidraco cub are all from the lake water in Changchun Nan lake park.Fish cub is divided into four groups, often
Group ten, every fish raising is in single beaker and controls the water volume in beaker identical.To increase experimental reliability, reduce
Experimental error, the individual difference of every fish will be controlled in certain limit.The quality control of fish is between 400~500mg.
A groups：200mL clean waters and a fish cub are added in each beaker；
B groups：200mL clean waters and a fish cub are added in each beaker.40mg mercury chloride solid dissolving is in other 3mL
In water, it is 10000 ppb to take 0.2mL solution to be added in beaker now mercury ion ultimate density；
C groups:200mL clean waters and a fish cub are added in each beaker.40mg mercury chloride solid dissolving is in other 3mL
In water.The sorbing material of 200mg (weight in wet base) embodiment 1~2 is added in above-mentioned solution and shakes solution 24h.After this is purified
Solution take 0.2mL to be added in each beaker.
D groups：200mL clean waters and a fish cub are added in each beaker.It is another to take 3mL clean waters addition 200mg (wet
The sorbing material concussion processing 24h of embodiment 1~2 again).The solution after 0.2mL processing is taken to be added in each beaker.
In whole experiment process, above-mentioned four groups of beakers are deposited at room temperature.
The survival condition of fish cub is observed at any time and is recorded.As shown in figure 1, Fig. 1 is the embodiment of the present invention 5, yellow forehead
Fish cub survival rate compares figure；Test result indicates that in B groups, under the poisoning effect of high concentration mercury ion, all fish cubs exist
It is all dead in 3.5h.And in C groups and D groups, fish cub can keep higher survival rate, illustrate sorbing material toxicity itself
It is very low, and there is very strong adsorption capacity for mercury ion, the mercury ion of high concentration can be down to very low scope.
Final statistical result is as shown in table 1,
Survival results before and after the sorbing material that the lake water of table 1 is prepared using the embodiment of the present invention 2 purifies
Embodiment 6
Before and after the sorbing material purification being prepared using the embodiment of the present invention 1~4, inorganic ion concentration of mercury such as table in water
Shown in 2.
Water quality result before and after the sorbing material that table 2 is prepared using the embodiment of the present invention 1~4 purifies
Embodiment 7
1g sorbing material (weight in wet base) is launched in the water for being 10000ppb to 30mL ion concentration of mercury, concussion solution is certain
Time, the ion concentration of mercury tested using inductively coupled plasma method in solution.It can be found that in short 40min,
99% mercury ion is all adsorbed by material.Mercury ion least concentration can be down to instrument minimum detection limit (0.1ppb).
2. solution allocation method in Fig. 2 b：PH value is respectively configured and is 3 and 10 two kinds of each 3mL of solution, and prepares Chang Chunnan
Lake park lake water is some, and Shanghai City east seawater in bay is some, artificially adds a certain amount of mercury chloride in above-mentioned several liquid, makes mercury
Ion ultimate density is 10000ppb, and adds 50mg sorbing material in respective solution respectively, shakes solution.After 24h,
The ion concentration of mercury tested using inductively coupled plasma method in solution.According to the value of formula 1, respectively calculation of distribution coefficient.
Formula 1：
Wherein, C0And CeIt is starting and the ultimate density of mercury ion respectively；V represents handled sewage volume (mL)；M generations
The quality (g) of sorbing material under table drying regime.
3. in being tested except methyl mercury, a certain amount of methyl mercury standard solution is taken, is configured to 100ng/mL concentration.Take
200mg (weight in wet base) sorbing material is added into the above-mentioned solution of 3mL, concussion solution 24h.Utilize inductively coupled plasma-matter
Compose the concentration of combined instrument test wherein mercury.Parallel testing is averaged and calculates standard deviation (Fig. 2 c) three times.
Fig. 2 is the Experimental results show figure of the embodiment of the present invention 7；Wherein (a) mercury ion Dynamic Absorption curve；(b) adsorb
Material measures the breadth coefficient to mercury ion under various circumstances；(c) methyl mercury compound clearance is tested.
It can be seen that, in short 40min, sorbing material can purify 99% mercury ion from Fig. 2 (a)；And in Fig. 2
(b) in, pH is 3 or 10, and all the distribution coefficient of mercury ion is had no significant effect, illustrates that sorbing material can be in wide in range pH scopes
Interior normal work, and in composition increasingly complex natural lake water and seawater, it is still unaffected to the distribution coefficient of mercury ion,
Illustrate that sorbing material can complete purification under relative complex environment.In Fig. 2 (c), for the such high concentrations of 100ng/L
In the presence of methyl mercury compound, sorbing material can adsorb more than 90% methyl mercury compound.
Embodiment 8
The antijamming capability of sorbing material to being synthesized in the present invention is measured.In potassium (K+), sodium (Na+), calcium (Ca2 +), magnesium (Mg2+), lead (Pb2+), cadmium (Cd2+), nickel (Ni2+), manganese (Mn2+), zinc (Zn2+), chromium (Cr2+), copper (Cu2+), iron (Fe3+)
In the presence of all polyions (above ion concentration is 10ppm), the order of magnitude of its distribution coefficient to mercury ion has no shadow
Ring, as a result as shown in figure 3, Fig. 3：A) the mercury ion distribution coefficient measure under numerous other ion interferences；B) sorbing material 4 times
Distribution coefficient measure during recycling.
Aspect is recycled in material, the scavenging material after use is soaked into 24h in watery hydrochloric acid, its detergent power can
Be restored (Fig. 3 b)；Fig. 3 (a) is the antijamming capability measurement result of the sorbing material of the embodiment of the present invention 8；(b) it is of the invention
The comparison figure of distribution coefficient of the sorbing material of embodiment 8 when recycling for 4 times.As seen from Figure 3, in numerous other interference
The distribution coefficient of mercury ion does not receive influence under ion interference, and the material after purification soaks 24h, adsorption cleaning in watery hydrochloric acid
Ability can be restored.
Embodiment 9
Molybdenum disulfide nano flower is modification on polyvinyl alcohol aeroge surface.This modification is to molybdenum disulfide nano material
Very crucial effect is played in the performance of the adsorption capacity of material.Compared in experiment the present invention modification after molybdenum disulfide nano flower and
The molybdenum disulfide nano flower solid being separately synthesized, the adsorption capacity under phase homogenous quantities, as a result as shown in figure 4, Fig. 4 is the present invention
After modification molybdenum disulfide nano flower and be separately synthesized molybdenum disulfide nano flower solid, the adsorption capacity ratio under phase homogenous quantities
Compared with figure；As seen from Figure 4, it is greatly improved by modification, the adsorption efficiency of molybdenum disulfide nano flower.Fig. 5 is
The scanning electron microscopic picture for the aeroge that the present invention is prepared under low resolution and high-resolution；As seen from Figure 5, curing
Molybdenum nanometer floral material is uniform extensively in aeroge surface distributed, good dispersion；Fig. 6 is that monodispersed molybdenum disulfide nano spends high score
Distinguish transmission electron microscope picture.As seen from Figure 6, molybdenum disulfide nano flower has the structure of many folds in itself, and this also further increases
Its big surface area, advantage is provided for the absorption of mercury contaminants.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method for being used to remove the sorbing material of inorganic mercury ion and methyl mercury compound in water body, its feature exist
In comprising the following steps：
Polyvinyl alcohol aeroge reaction, obtains sorbing material in molybdenum disulfide precursor solution.
2. preparation method according to claim 1, it is characterised in that the polyvinyl alcohol aeroge is made as follows
It is standby：
Polyvinyl alcohol and inorganic acid hydro-thermal reaction, obtain polyvinyl alcohol aeroge.
3. preparation method according to claim 2, it is characterised in that the polyvinyl alcohol is polyvinyl alcohol water solution, institute
The mass concentration for stating polyvinyl alcohol water solution is 3%~7%；The inorganic acid is sulfuric acid；The concentration of the inorganic acid be 3~
5mol/L。
4. preparation method according to claim 2, it is characterised in that also include adding the multi-walled carbon nanotube aqueous solution；Institute
The mass concentration for stating the multi-walled carbon nanotube aqueous solution is 1%~3%.
5. preparation method according to claim 1, it is characterised in that the concentration of the molybdenum disulfide precursor solution is 2
~2.5mg/mL；The mass ratio of the polyvinyl alcohol aeroge and molybdenum disulfide presoma is (0.2~0.5)：(0.04~
0.05)。
6. preparation method according to claim 1, it is characterised in that protective agent is also added in the reaction；The protective agent
For tri octyl phosphine；The volume ratio of the protective agent and the solution is (6~8)：(15000~25000).
7. preparation method according to claim 1, it is characterised in that the reaction temperature is 200 DEG C；The reaction time
For 24h.
8. preparation method according to claim 1, it is characterised in that the molybdenum disulfide presoma is tetrathio molybdic acid
Ammonium；The solution is DMF.
9. a kind of sorbing material for being used to remove inorganic mercury ion and methyl mercury compound in water body, it is characterised in that by right
It is required that the preparation method described in 1~8 any one is prepared.
A kind of 10. method for removing inorganic mercury ion and methyl mercury compound in water body, it is characterised in that using claim 1
The sorbing material that preparation method described in~8 any one is prepared is to inorganic mercury ion in water body and/or methyl mercury chemical combination
Thing is adsorbed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115608324A (en) * | 2022-09-22 | 2023-01-17 | 宁德师范学院 | Organic-inorganic hybrid mesoporous mercury ion adsorption material and preparation method thereof |
| CN116159547A (en) * | 2023-04-07 | 2023-05-26 | 国科大杭州高等研究院 | Molybdenum disulfide/polymer gel ball adsorption material with double-network structure, and preparation method and application thereof |
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|---|---|---|---|---|
| US6080281A (en) * | 1994-04-18 | 2000-06-27 | Attia; Yosry A. | Scrubbing of contaminants from contaminated air streams with aerogel materials with optional photocatalytic destruction |
| CN106115869A (en) * | 2016-06-28 | 2016-11-16 | 常州大学 | The nitrogen-doped graphene aeroge of one-step synthesis method is applied to electro-adsorption mercury ions in waste water |
| CN106799245A (en) * | 2017-02-09 | 2017-06-06 | 河南师范大学 | The 3DMoS of efficient degradation waste water from dyestuff2/ RGO composite aerogel catalysis materials and preparation method thereof |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080281A (en) * | 1994-04-18 | 2000-06-27 | Attia; Yosry A. | Scrubbing of contaminants from contaminated air streams with aerogel materials with optional photocatalytic destruction |
| CN106115869A (en) * | 2016-06-28 | 2016-11-16 | 常州大学 | The nitrogen-doped graphene aeroge of one-step synthesis method is applied to electro-adsorption mercury ions in waste water |
| CN106799245A (en) * | 2017-02-09 | 2017-06-06 | 河南师范大学 | The 3DMoS of efficient degradation waste water from dyestuff2/ RGO composite aerogel catalysis materials and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115608324A (en) * | 2022-09-22 | 2023-01-17 | 宁德师范学院 | Organic-inorganic hybrid mesoporous mercury ion adsorption material and preparation method thereof |
| CN116159547A (en) * | 2023-04-07 | 2023-05-26 | 国科大杭州高等研究院 | Molybdenum disulfide/polymer gel ball adsorption material with double-network structure, and preparation method and application thereof |
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