CN106076274A - A kind of preparation method of the sulfhydrylation chitosan magnetic composite of heavy-metal ion removal - Google Patents
A kind of preparation method of the sulfhydrylation chitosan magnetic composite of heavy-metal ion removal Download PDFInfo
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- CN106076274A CN106076274A CN201610485863.1A CN201610485863A CN106076274A CN 106076274 A CN106076274 A CN 106076274A CN 201610485863 A CN201610485863 A CN 201610485863A CN 106076274 A CN106076274 A CN 106076274A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
Abstract
A kind of preparation method of the sulfhydrylation chitosan magnetic composite of heavy-metal ion removal, belong to field of environmental technology, the present invention uses biodegradable, eco-friendly mercapto-functionalized chitosan quaternary ammonium salt derivatives is carrier material, composite is prepared with inverse suspension crosslinking method coated ferriferrous oxide nanoparticle, this composite has Magneto separate function, multi-metal ion is respectively provided with preferable removal effect neutral under weak basic condition simultaneously, the present invention can remove contents of many kinds of heavy metal ion simultaneously, preparation method is easy to be reliable, production cycle is shorter, it is expected to be applied in the process of actual water.
Description
Technical field
The invention belongs to field of environmental technology, be specifically related to have Magneto separate function and there is the scavenging material of high efficiency
Technology of preparing.
Background technology
The problem of environmental pollution that in sewage, toxic heavy metal causes increasingly causes the concern of people.And along with industry
The fast-developing increasingly stringent with environmental requirement, water pollution control the most increasingly obtains government and industrial department is paid attention to closely.Weight
Metal ion is poisonous to human body, the most carcinogenic, and does not have biodegradability, accumulates in vivo, cause various not
With disease, therefore answer in strictly controlled environment the content of heavy metal ion (especially in water body).
The natural adsorbents such as chitosan can effectively remove the heavy metal in sewage and organic pollution, has good industry
Application prospect.Chitosan is the second largest natural polymer in addition to cellulose, its wide material sources, cheap, of many uses,
And belong to Renewable resource, for hydrophilic biopolymer and easily modified.Additionally, chitosan also have nontoxic, biological can
Degradability, biocompatibility, multifunctionality, high chemical reactivity, have good complexation and absorbability to metal ion.Contrast
Other adsorbent, chitosan derivative has that adsorption capacity is high, adsorptive selectivity is good, low cost, easily operated excellent
Point.Chitosan to the good absorption property of metal ion be due to: 1) hydrophilic of hydroxyl in polymer；2) exist in a large number
Adsorption function base (amide groups, amido and hydroxyl)；3) these adsorption function bases have good chemical reactivity, it is easy to modified；4)
Polymer chain has good motility.
Summary of the invention
It is an object of the invention to propose the adsorbent for heavy metal of a kind of high-efficiency environment friendly, especially can be simply and effectively
The sulfhydrylation chitosan magnetic composite of the environmental protection of heavy-metal ion removal (arsenic, hydrargyrum, lead, copper, magnesium, cadmium, zinc) simultaneously
Preparation method.
The present invention comprises the following steps:
1) mercapto-functionalized chitosan quaternary ammonium salt derivatives (cyshtcc) is dissolved in 2wt% acetum, stirs bar
Under part, add Fe3O4Nanoparticle, forms mixed liquor；
2) use inverse suspension crosslinking method, be added drop-wise to described mixed liquor to be made up of liquid paraffin, Span 80 and ethyl acetate
In mixed solution, emulsifying, obtain W/O emulsion；
3), after W/O emulsion being warming up to 40 DEG C, add formaldehyde, then add glutaraldehyde after being warming up to 50 DEG C, form mixed system；
4) with the pH value of the sodium hydrate aqueous solution described mixed system of regulation to 9～10, stirring is reacted to terminating, more successively with stone
Oil ether, acetone, ethanol and the washing of secondary water, take solid phase and be dried, obtain composite.
The present invention is to use a kind of mercapto-functionalized chitosan quaternary ammonium salt derivatives biodegradable, eco-friendly for carrying
Body material, prepares composite (cyshtcc-Fe with inverse suspension crosslinking method coated ferriferrous oxide nanoparticle3O4), research
Removal ability and the condition of use while its heavy metal ion (arsenic, hydrargyrum, lead, copper, magnesium, cadmium, zinc).Final prepared being combined
Material (cyshtcc-Fe3O4) there is Magneto separate function, under neutral and weak basic condition simultaneously to arsenic, hydrargyrum, lead, copper, magnesium,
Cadmium, zinc etc. 7 heavy metal species ion be respectively provided with preferable removal effect, best to the removal effect of lead, copper, clearance reach 95% with
On；When adsorbent amount reaches 1.5 g/L, lead, copper, magnesium, the clearance of cadmium are above 90%, to zinc, arsenic, the clearance of hydrargyrum
Also more than 80%；Removal efficiency raises with temperature and raises, and absorption is to complete in the short period.
It was verified that use weak basic condition to be more conducive to chitosan crosslinked generation when step 4).
The present invention can remove contents of many kinds of heavy metal ion simultaneously, and preparation method is easy to be reliable, and the production cycle is shorter, it is expected to should
In actual water processes.
Composite (cyshtcc-Fe obtained by the present invention3O4) be 8 at pH value, adsorbent amount be 1.5 g/L,
When ion initial concentration is 5 mg/L, arsenic, hydrargyrum, lead, copper, magnesium, cadmium, the removal efficiency of zinc are respectively 80.88%, 88.52%,
99.90%, 98.64%, 92.38%, 91.75 and 88.01%；The absorption of 5 metal ion species such as lead, copper, magnesium, cadmium, zinc is existed by material
Reach saturated in 10 min, slightly longer to the adsorption saturation time of arsenic, two kinds of ions of hydrargyrum；Adsorption efficiency is with temperature rising
Raise；The addition of ferroso-ferric oxide makes it have Magneto separate function, it is simple to subsequent treatment.Cyshtcc-Fe3O4It is expected to become a kind of
Efficiently have a Magneto separate function can the new green environment protection of simultaneously heavy-metal ion removal (arsenic, hydrargyrum, lead, copper, magnesium, cadmium, zinc)
Material.
Further, the mercapto-functionalized chitosan quaternary ammonium salt derivatives described in step 1) of the present invention and Fe3O4Nanometer
The mixing quality ratio of particle is 2: 1, uses supersound process during mixing.Absorbability and the Magneto separate energy of material can be met simultaneously
Power.
Step 2) in, the mixed volume ratio of described mixed liquor and liquid paraffin is 1: 1.
Step 2) in, it is 1.5% that described Span 80 accounts for the percent by volume of mixed solution, and it is molten that described ethyl acetate accounts for mixing
The percent by volume of liquid is 10 %.Experiment proves that the consumption of emulsifying agent is very few and is unfavorable for emulsifying, crosses and is difficult at most clean up, no
It is beneficial to the post processing of material；Ethyl acetate plays the effect of porogen, and experiment shows that under this ratio, adsorption effect is more preferably.
Step 2) in emulsification times be 0.5h.Facts have proved that 0.5 h can reach preferable emulsifying effectiveness.
In step 3), it is 8% that described formaldehyde accounts for the percent by volume of mixed system, and glutaraldehyde accounts for the volume hundred of mixed system
Proportion by subtraction is 4%.The effect of formaldehyde is short range crosslinking and glutaraldehyde is remotely crosslinking, cross-linking effect is used in combination more preferably, and relative to
Glutaraldehyde, the cost of formaldehyde is lower, it is possible to reduce industrial cost.
In described step 3), under conditions of rotating speed is 500 rpm, in 30min, formaldehyde is added in W/O emulsion.Turn
Speed higher and be slowly added dropwise for system crosslinking more uniform, prevent partial cross-linking from spending greatly.
In described step 3), glutaraldehyde, to be slowly added dropwise in mixed system, so that cross-linking reaction is complete, prevents office
Portion's degree of cross linking is excessive.
Accompanying drawing explanation
Fig. 1 is Fe3O4SEM figure.
Fig. 2 is cyshtcc-Fe3O4SEM figure.
Fig. 3 is Fe3O4And cyshtcc-Fe3O4FTIR figure.
Fig. 4 is Fe3O4And cyshtcc-Fe3O4VSM figure.
Fig. 5 is that ion initial concentration is to cyshtcc-Fe3O4That removes 7 heavy metal species ions affects figure.
Fig. 6 is that pH is to cyshtcc-Fe3O4That removes 7 heavy metal species ions affects figure.
Fig. 7 is that adsorbent amount is to cyshtcc-Fe3O4That removes 7 heavy metal species ions affects figure.
Fig. 8 is that temperature is to cyshtcc-Fe3O4That removes 7 heavy metal species ions affects figure.
Fig. 9 is that time of contact is to cyshtcc-Fe3O4That removes 7 heavy metal species ions affects figure.
Detailed description of the invention
One, preparation technology:
1, synthesis chitosan quaternary ammonium salt derivatives (HTCC):
0.5g white flock chitosan is dispersed in 15mL isopropanol, chitosan system in the pasty state after being uniformly dispersed.By 2.0
The 2 of g, 3-epoxypropyltrimethylchloride chloride (GTA) is dissolved in 5 mL isopropanols, and at 80 DEG C, 2h drips off it slow
Drop to, in pasty state chitosan system, react 6 h, make precipitant with dehydrated alcohol and be precipitated out by product, through sucking filtration, be dried,
Obtain chitosan quaternary ammonium salt derivatives HTCC.
2, mercapto-functionalized quaternary ammonium salt derivative (cyshtcc) is prepared:
Take 0.5g HTCC to be dissolved in 50ml aqueous solution, add 1.4mmol (0.16g) N-hydroxysuccinimidyl acyl after dissolving sub-
Amine (NHS) and 1.3mmol (0.24g) 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC), subsequently
Adding 0.5 g Cys, mix homogeneously, regulation system pH is to react 24 h under 5, room temperature, centrifugal, supernatant dialysis 2
My god, lyophilization i.e. obtains mercapto-functionalized chitosan quaternary ammonium salt derivatives (cyshtcc).
3, coprecipitation prepares Fe3O4Nanoparticle:
Fe will be contained2+Solution and containing Fe3+Solution with Fe2+And Fe3+Mol ratio is that 1: 2 mixing is reacted, with concentration for 1
The ammonia of mol/L adjusts pH value to 13, after no longer having black precipitate to produce, then washs to reaction the pH of system with anaerobic water
It is worth to 7～8, lyophilization, obtains Fe3O4 Nanoparticle.
4, composite (cyshtcc-Fe is prepared3O4):
1) under ultrasound condition, chitosan quaternary ammonium salt derivatives (cyshtcc) mercapto-functionalized for 20mg is dissolved in 20 mL dense
In the degree acetum for 2wt%, under stirring condition, add 10mg Fe3O4Nanoparticle, forms mixed liquor.
2) use inverse suspension crosslinking method, by step 1) prepare 20 mL mixed liquors be added drop-wise to by 20 mL liquid paraffin,
In the mixed solution of 0.6 mL Span 80 and 4 mL ethyl acetate composition, after emulsifying 0.5h, obtaining W/O emulsion, wherein Span 80 accounts for
1.5 % v/v, ethyl acetate account for 10 % v/v.
3), after 45 mL W/O emulsions being warming up to 40 DEG C, under conditions of rotating speed is 500 r/min, add in 30min
Entering 3.6 mL formaldehyde, then be added dropwise over 1.8 mL glutaraldehydes after being warming up to 50 DEG C, form mixed system, wherein formaldehyde accounts for mixture
The percent by volume of system is 8%, and it is 4% that glutaraldehyde accounts for the percent by volume of mixed system.
4) with sodium hydrate aqueous solution regulating step 3) pH value of mixed system that obtains to 9～10, be 175 at rotating speed
Under conditions of r/min, stirring reaction 3h, then wash with petroleum ether, acetone, ethanol and secondary water successively, drying, obtain purification
Material (cyshtcc-Fe3O4).
Two, the sign of composite:
Using model is that the scanning electron microscope (SEM) of S-4800 II is to Fe3O4The scavenging material made with process above
(cyshtcc-Fe3O4) characterize.
From figure 1 it appears that Fe prepared by coprecipitation3O4 Nanoparticle presents spherical microscopic appearance, and size is relatively
For homogeneous, nanometer particle size is at 20-30 nm, and owing to specific surface energy is higher, sample is reunited substantially；Fig. 2 is scavenging material
(cyshtcc-Fe3O4) sign of composite, figure it is seen that chitosan has successfully been coated on the table of nano-iron particle
Face.
The nanoparticle made is characterized by fourier infrared spectrometer (FTIR) respectively that use model to be TENSOR27.
Curve in comparison diagram 3, cyshtcc and Fe3O4Characteristic peak appeared at scavenging material (cyshtcc-Fe3O4) FTIR
In figure, 2603cm−1 (stretching vibration peak of the SH after mercapto-functionalized), 1479cm−1 (quaternary ammonium salt-modified rear CH2Flexible
Vibration peak), 590cm−1 (stretching vibration peak of Fe O in ferroso-ferric oxide), this result further illustrates cyshtcc and Fe3O4
Successful crosslinking.
It is tested by the oscillation sample gaussmeter (VSM) using model to be EV7, shows Fe in Fig. 43O4Only
Formed material (cyshtcc-Fe3O4) hysteresis curve figure, due to the cladding of cyshtcc, magnetic saturation intensity contrast Fe3O4Slightly drop
Low, magnetic saturation intensity is 42.26 emu/g, illustrates that this composite can be separated by externally-applied magnetic field in water processes.
Three, the research of composite heavy-metal ion removal efficiency:
1, the impact of initial concentration:
The atomic fluorescence spectrophotometer using model to be general analysis PF7 measures fluorescence intensity, calculates adsorption rate according to standard curve.Change
Becoming the initial concentration of each ion in water body to be clean and, from 1 to 15 mg/L, calculate composite adsorption efficiency, result is shown in Fig. 5.From
It can be seen that in concentration less than 5mg/L, arsenic, hydrargyrum, lead, copper, magnesium, cadmium, zinc 7 heavy metal species ion are all had relatively by material in Fig. 5
Good removal efficiency, when initial concentration is more than 10mg/L, removal efficiency reduces substantially.
2, the impact of pH:
Changing pH in water body to be clean and, from 3 to 11, calculate composite adsorption efficiency, result is shown in Fig. 6.As can be seen from Figure 6:
When in water body to be clean, pH value is at 6-11, composite all has preferably removal to hydrargyrum, lead, copper, magnesium, cadmium, 6 kinds of ions of zinc
Effect, composite has preferable removal effect when pH value is 6-8 to arsenic (III), the most apparently, when water body to be clean
When middle pH value is 8, composite is best to the removal efficiency of 7 kinds of ions.
3, the impact of adsorbent amount:
Adsorbent amount is 5 to the Adsorption Effect of 7 heavy metal species ions at fixing water body intermediate ion initial concentration to be clean
Under conditions of mg/L, pH are 8, the consumption changing adsorbent finally calculates adsorption efficiency from 0.5 to 3 g/L, and result is shown in Fig. 7.From
Fig. 7 can be seen that, the removal efficiency of each ion is increased along with the increase of adsorbent amount by material, but goes after 1.5 g/L
Becoming slow except efficiency rises, comprehensive removal efficiency, adsorption capacity and economic benefit consider, finally determine that adsorbent amount is
1.5 g/L。
4, the impact of temperature:
Changing the temperature of water body to be clean from 293K to 313K, calculate the efficiency of composite heavy-metal ion removal, result is shown in
Fig. 8., the removal efficiency of each ion along with the rising of temperature raised by composite, i.e. when 313 K from figure all in all
Removal efficiency is the highest, and it is the strongest that this is likely due to the highest Brownian movement of temperature, adds the contact probability of ion and adsorbent.
5, the impact of time of contact:
Fig. 9 is the time composite to be removed the impact of 7 kinds of ions, and as can be seen from the figure material is to lead, copper, magnesium, cadmium, zinc etc.
The absorption of 5 metal ion species reaches saturated in 10 min, slightly longer to the adsorption saturation time of arsenic, two kinds of ions of hydrargyrum.Always
Apparently, the composite energy of preparation is respectively provided with preferable removal effect to 7 heavy metal species ions within a short period of time to body.
Sum up:
Composite prepared by the inventive method in the short period of time can simultaneously heavy metal ion (arsenic, hydrargyrum, lead, copper, magnesium,
Cadmium, zinc) it is respectively provided with preferable removal effect, can be expected to produce in batches to be applied to the process of actual water, be expected to become one and have
The new high-efficiency green material for water treatment of Magneto separate function.
Claims (8)
1. the preparation method of the sulfhydrylation chitosan magnetic composite of a heavy-metal ion removal, it is characterised in that include with
Lower step:
1) mercapto-functionalized chitosan quaternary ammonium salt derivatives is dissolved in 2wt% acetum, under stirring condition, adds
Fe3O4Nanoparticle, forms mixed liquor；
2) use inverse suspension crosslinking method, be added drop-wise to described mixed liquor to be made up of liquid paraffin, Span 80 and ethyl acetate
In mixed solution, emulsifying, obtain W/O emulsion；
3), after W/O emulsion being warming up to 40 DEG C, add formaldehyde, then add glutaraldehyde after being warming up to 50 DEG C, form mixed system；
4) with the pH value of the sodium hydrate aqueous solution described mixed system of regulation to 9～10, stirring is reacted to terminating, more successively with stone
Oil ether, acetone, ethanol and the washing of secondary water, take solid phase and be dried, obtain composite.
Preparation method the most according to claim 1, it is characterised in that the mercapto-functionalized chitosan season described in step 1)
Ammonium salt derivatives and Fe3O4The mixing quality ratio of nanoparticle is 2: 1, uses supersound process during mixing.
Preparation method the most according to claim 1, it is characterised in that step 2) in, described mixed liquor and the mixing of liquid paraffin
Volume ratio is 1: 1.
4. according to preparation method described in claim 1 or 3, it is characterised in that step 2) in, described Span 80 accounts for mixed solution
Percent by volume is 1.5%, and it is 10 % that described ethyl acetate accounts for the percent by volume of mixed solution.
Preparation method the most according to claim 1, it is characterised in that step 2) in emulsification times be 0.5h.
The most according to claim 1, preparation method, it is characterised in that in described step 3), described formaldehyde accounts for the body of mixed system
Long-pending percentage ratio is 8%, and it is 4% that glutaraldehyde accounts for the percent by volume of mixed system.
7. according to preparation method described in claim 1 or 6, it is characterised in that in described step 3), at the bar that rotating speed is 500 rpm
Under part, in 30min, formaldehyde is added in W/O emulsion.
The most according to claim 7, preparation method, it is characterised in that in described step 3), glutaraldehyde is to be slowly added dropwise
In mixed system.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106770730A (en) * | 2016-11-30 | 2017-05-31 | 青岛理工大学 | A kind of methyl mercury and ethyl sclera remodeling method |
| CN108654575A (en) * | 2018-06-14 | 2018-10-16 | 何丽丽 | A kind of preparation and its application of magnetism episulfide resin functional material |
| CN112915972A (en) * | 2021-01-22 | 2021-06-08 | 广州大学 | high-Cr (VI) adsorption amount core-shell structure high-molecular magnetic nanosphere and preparation method and application thereof |
| CN115254043A (en) * | 2022-07-28 | 2022-11-01 | 武汉纺织大学 | Modified cucurbit [ n ] urea-chitosan composite aerogel bead as well as preparation method and application thereof |
| CN116809032A (en) * | 2023-07-03 | 2023-09-29 | 中国热带农业科学院南亚热带作物研究所 | Sulfhydryl modified chitosan porous microsphere and preparation method and application thereof |
| CN117358206A (en) * | 2023-10-17 | 2024-01-09 | 江苏举世检测有限公司 | Heavy metal adsorbent for river channel deep treatment and preparation process thereof |
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|---|---|---|---|---|
| CN106770730A (en) * | 2016-11-30 | 2017-05-31 | 青岛理工大学 | A kind of methyl mercury and ethyl sclera remodeling method |
| CN106770730B (en) * | 2016-11-30 | 2019-01-22 | 青岛理工大学 | A kind of methyl mercury and ethyl sclera remodeling method |
| CN108654575A (en) * | 2018-06-14 | 2018-10-16 | 何丽丽 | A kind of preparation and its application of magnetism episulfide resin functional material |
| CN108654575B (en) * | 2018-06-14 | 2021-03-12 | 华玻视讯(珠海)科技有限公司 | Preparation and application of magnetic episulfide resin functional material |
| CN112915972A (en) * | 2021-01-22 | 2021-06-08 | 广州大学 | high-Cr (VI) adsorption amount core-shell structure high-molecular magnetic nanosphere and preparation method and application thereof |
| CN115254043A (en) * | 2022-07-28 | 2022-11-01 | 武汉纺织大学 | Modified cucurbit [ n ] urea-chitosan composite aerogel bead as well as preparation method and application thereof |
| CN116809032A (en) * | 2023-07-03 | 2023-09-29 | 中国热带农业科学院南亚热带作物研究所 | Sulfhydryl modified chitosan porous microsphere and preparation method and application thereof |
| CN117358206A (en) * | 2023-10-17 | 2024-01-09 | 江苏举世检测有限公司 | Heavy metal adsorbent for river channel deep treatment and preparation process thereof |
| CN117358206B (en) * | 2023-10-17 | 2024-03-29 | 江苏举世检测有限公司 | Heavy metal adsorbent for river channel deep treatment and preparation process thereof |
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