CN109012610A - The preparation method of cerium modified chitosan dephosphorization granule adsorbent - Google Patents
The preparation method of cerium modified chitosan dephosphorization granule adsorbent Download PDFInfo
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- 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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- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a kind of preparation methods of cerium modified chitosan dephosphorization granule adsorbent, including step 1: Chitosan powder is completely dissolved in acetum；Step 2: cerous nitrate aqueous solution and constant speed stirring is added；Step 3: standing after bubble eliminates, form a film after being cast in culture dish in baking oven inner gel；Step 4: impregnating culture dish with sodium hydroxide solution, diaphragm takes off film, distillation water washing diaphragm to neutrality, drying after heaving；Step 5: diaphragm is added in crosslinking agent, is crosslinked in thermostat water bath；Step 6: being washed with distilled water crosslinking agent extra on crosslinker solution diaphragm and drying, grinding and sieving；Step 7: the particle after sieving being protonated at room temperature with hydrochloric acid solution, and is dried after being washed with distilled water to neutrality, the cerium modified chitosan dephosphorization granule adsorbent is obtained.Not only dephosphorizing rate is high by the present invention, large amount of adsorption, and tp removal rate influenced by temperature and pH it is smaller.
Description
Technical field
The present invention relates to water-treatment technology field more particularly to a kind of preparations of cerium modified chitosan dephosphorization granule adsorbent
Method.
Background technique
Phosphorus is the deciding factor for leading to water eutrophication, while phosphorus is also the indispensable important nutrition member of life
Element, and it is non-renewable.Phosphorus is one of tellurian important element, and the separation and recovery of phosphor in sewage is both to realize that phosphor resource can be held
The demand of supervention exhibition, and improve the effective measures of water eutrophication problem.
Recently as economic fast development, a large amount of phosphorus-containing wastewaters are discharged into environment, and water body is caused to generate eutrophication.
Statistics indicate that about 56% waters is all because nitrogen and phosphorus pollution is to the life of the mankind and aquatile in Chinese Main Lakes
Growth produces great negative effect.The sewage treatment plant of urbanization at present phosphorus content is easier to up to standard, and country sewage nitrogen phosphorus contains
Amount is universal higher, be difficult by traditional biological phosphate-eliminating it is up to standard, therefore, the dephosphorization technique that exploiting economy is efficient, without secondary pollution
Research emphasis as current water treatment technology.
Currently, common phosphorus removing method mainly has chemical precipitation method, bioanalysis, ion-exchange, membrane separation process, absorption
Method.
The common coagulating sedimentation agent of chemical precipitation method has the mixture etc. of lime, alum, iron chloride, lime and iron chloride,
With simple and easy to do, the advantages of high treating effect, but longtime running can cause pH value of waste water to rise, and generate a large amount of sludge,
Great inconvenience is brought to the processing of sludge, be easy to cause secondary pollution.
Bioanalysis has good phosphor-removing effect, and is not required to add precipitating reagent, but require to manage stringenter, higher cost.
The exchange capacity of ion-exchange dephosphorization is more stable, but due to after regeneration exchange capacity decrease, and it is right
It is higher in processing high-concentration phosphorus-containing wastewater operating cost, therefore also non-scale application at present.
Membrane separation process is suitable for the lower phosphorus-containing wastewater of concentration, and treatment effect is stablized, and effluent quality can reach national discharge
Standard, but it is at high cost, and equipment is expensive, and be easy to cause secondary pollution.
Absorption method is due to having small occupied area, simple process, easy to operate, reusable, without secondary pollution excellent
Gesture is widely used and approves in water treatment field in recent years.
Absorption method dephosphorization be using certain porous or bigger serface solid matter in water phosphate anion it is affine
Power, come the technology of phosphorus removal from wastewater realized.Adsorbent plays an important role in absorption method, and phosphorus is inhaled by the physics of adsorbent surface
Attached, ion exchange or coprecipitation process, realization phosphorus can be provided further by desorption processing recycling phosphorus from the separation in sewage
Source, currently, common dephosphorization material has clay, chitosan, industry byproduct and active carbon.Therefore, it in absorption method research, seeks
Looking for new and effective environmental-friendly adsorbent is dephosphorization key point.
Chitosan receives more and more attention due to it has many advantages, such as biocompatibility, nontoxic, biological degradability.So
And due to lacking positive point, chitosan is lower to the adsorption capacity of phosphorus.It, can in order to improve it to phosphatic adsorption capacity
Using a variety of chemical modification methods such as chemical crosslinking and introducing metal ion.Loaded metal ion is carried out to chitosan to be modified,
The metal ion that can be loaded has lanthanum, iron, zirconium, neodymium etc..
Rare element be reserves in nature, distribution rare (general crustal abundance is 100ppm or less) and the mankind apply compared with
Few element general name.In recent years, the material for loading rare metal ion is widely used in excessive phosphorus in removal water body.China
Rare earth resources reserves very abundant, currently, rare earth element is pushed away due to its unique physicochemical properties in various fields
Extensively with use.In chitosan molecule chain, amino and hydroxyl can be raw by coordination with transition and rare earth ion
At chitosan metal complexes, such complex is larger with relative molecular mass, contains metal ion, certain condition
The features such as available chelating cyclic structure.Wherein, cerium ion rich reserves, it is cheap, it is acidproof, alkali resistance is strong, it is removing
It is not eluted during harmful substance in water.Adsorbent material containing cerium ion is because of its inexpensive, pollution-free, good stability
And adsorption and dephosphorization effect it is good the advantages that be concerned.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of cerium modified chitosan dephosphorization granule adsorbent, not only dephosphorization
Rate is high, large amount of adsorption, and tp removal rate influenced by temperature and pH it is smaller.
The present invention is implemented as follows:
A kind of preparation method of cerium modified chitosan dephosphorization granule adsorbent, includes the following steps:
Step 1: weighing Chitosan powder and be dissolved in acetum, stirring forms chitosan solution to being completely dissolved；
Step 2: cerous nitrate aqueous solution being added in chitosan solution, constant speed stirring forms six nitric hydrate cerium solution；
Step 3: standing six nitric hydrate cerium solution and take six uniform nitric hydrate cerium solution in culture dish after bubble eliminates
It forms a film after middle curtain coating in baking oven inner gel；
Step 4: culture dish is impregnated with sodium hydroxide solution, diaphragm takes off film after heaving, is washed diaphragm to neutrality with distilled water, and
In drying in oven；
Step 5: the diaphragm of drying being added in crosslinking agent, is crosslinked in thermostat water bath, crosslinker solution diaphragm is formed；
Step 6: being washed with distilled water crosslinking agent extra on crosslinker solution diaphragm and drying, grinding and sieving；
Step 7: the particle after sieving is protonated at room temperature with hydrochloric acid solution, and is dried after being washed with distilled water to neutrality,
Obtain the cerium modified chitosan dephosphorization granule adsorbent.
In the step 1, the volumetric concentration of acetum is 1.9%-2.1%, the quality of the chitosan solution of formation
Volumetric concentration is 2%.
In the step 2, the concentration of cerous nitrate aqueous solution is 0.5mol/L, six nitric hydrate cerium solution of formation
Volumetric concentration is 9%-11%.
In the step 4, the volumetric concentration of sodium hydroxide solution is 10%.
In the step 5, crosslinking agent is epoxychloropropane ethanol solution, and the concentration of epoxychloropropane ethanol solution is
2.5%, the mass-volume concentration of the crosslinker solution diaphragm of formation is 4%.
In the step 5, the temperature of thermostat water bath is 55-65 DEG C, and the time of crosslinking is 6-8 hours.
In the step 6, the mesh density of sieving is 100 mesh or 200 mesh.
In the step 7, the concentration of hydrochloric acid solution is 6-8mol/L, the mass-volume concentration of particle in hydrochloric acid solution
It is 10%.
In the step 7, the time of protonation is 0.5-1 hours.
In the preparation method of cerium modified chitosan dephosphorization granule adsorbent, the temperature of drying is 55-65 DEG C.
Compared with prior art, the present invention having the following beneficial effects:
1, the present invention is modified, with sodium hydroxide using chitosan as adsorbent skeleton with six nitric hydrate ceriums, epoxychloropropane
For forming agent, it is prepared with hydrochloric acid protonation, there is porous structure, preferable dephosphorization function can be played.
2, the present invention has many advantages, such as that cheap, pollution-free, excellent adsorption, stability are high.
Not only dephosphorizing rate is high by the present invention, large amount of adsorption, and tp removal rate influenced by temperature and pH it is smaller.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of the cerium modified chitosan dephosphorization granule adsorbent of the present invention.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples.
Attached drawing 1 is referred to, a kind of preparation method of cerium modified chitosan dephosphorization granule adsorbent includes the following steps:
Step 1: weighing Chitosan powder and be dissolved in acetum, stirring forms shell to (until solution is uniformly mixed) is completely dissolved
Glycan solution.
Step 2: the CeNO of 0.5mol/L being added in chitosan solution3•6H2O(cerous nitrate) aqueous solution, it is small that constant speed stirs 2
When, form six nitric hydrate cerium solution.
Step 3: standing six nitric hydrate cerium solution, after bubble eliminates, the solution for taking 10mL uniform is 90mm in diameter
Culture dish in be cast after 55-65 DEG C baking oven inner gel form a film.
Step 4: impregnating culture dish with sodium hydroxide solution, diaphragm with tweezers takes off film after heaving, washed diaphragm with distilled water
It washs to neutrality, and in 55-65 DEG C of drying in oven.
Step 5: the diaphragm of the drying of weakly acidic pH being added in crosslinking agent, is handed in 55 DEG C -65 DEG C of thermostat water bath
Connection 6-8 hours forms crosslinker solution diaphragm.
Step 6: being washed with distilled water crosslinking agent extra on crosslinker solution diaphragm, and dried at 55-65 DEG C, pulverizer
It crushes, sieves with 100 mesh sieve or 200 meshes, it is ensured that partial size is unified.
Step 7: the particle after sieving being protonated 0.5-1 hours at room temperature with hydrochloric acid solution, and is washed with distilled water
It is dried at 55-65 DEG C after to neutrality, obtains the cerium modified chitosan dephosphorization granule adsorbent.
In the step 1, the volumetric concentration of acetum is 1.9%-2.1%, it is preferred that the volume of acetum is dense
Degree is 2%；The mass-volume concentration of the chitosan solution of formation is 2%.
In the step 2, the volumetric concentration of six nitric hydrate cerium solution is 9%-11%, it is preferred that six nitric hydrates
The volumetric concentration of cerium solution is 10%.
In the step 4, the volumetric concentration of sodium hydroxide solution is 10%, easily takes off film under this solubility, and will not destroy
Other structures.
In the step 5, crosslinking agent is epoxychloropropane ethanol solution, and the concentration of epoxychloropropane ethanol solution is
2.5%, the mass-volume concentration of the crosslinker solution diaphragm of formation is 4%, it is preferred that crosslinking temperature is 60 DEG C, crosslinking time 6-8
Hour.
In the step 7, the concentration of hydrochloric acid solution is 6-8mol/L, the mass-volume concentration of particle in hydrochloric acid solution
It is 10%.
Embodiment 1:
2g chitosan is added in beaker, 100mL 2%(v/v is added) acetum, the chitosan of stirring and dissolving, formation is molten
The mass-volume concentration of liquid is 2%.Add the CeNO that volumetric concentration is 10%, 0.5mol/L3•6H2O aqueous solution, 2h is to complete for stirring
After fully dissolved, stand.The solution for taking 10mL uniform diameter be 90mm culture dish in be cast, under 60 DEG C of baking ovens gel at
Film.Be to take off film after 10% sodium hydroxide solution impregnates culture dish with volumetric concentration, diaphragm, which distills, is washed to neutrality, at 60 DEG C
It is dry in baking oven.Diaphragm after 2g drying is added in conical flask, is added the ethanol solution of 2.5% epoxychloropropane of 50mL, in
8h is stirred in 60 DEG C of thermostat water bath.Diaphragm after being washed with distilled water crosslinking sieves with 100 mesh sieve after dry at 60 DEG C.Taper
Particle after 1g sieving is added in bottle, is added the hydrochloric acid of 10mL 6mol/L, stirs 1h at room temperature, be washed with distilled water to neutrality,
Drying is at 60 DEG C to get cerium modified chitosan dephosphorization granule adsorbent.
50mL 20mg/L phosphorus solution is added in 100mL conical flask, weighs the cerium modified chitosan of the above-mentioned preparation of 0.12g
Dephosphorization granule adsorbent vibrates 40min in gas bath constant temperature oscillator under the conditions of 25 DEG C, 200rpm and uses molybdenum after filter paper filtering
The anti-spectrophotometry of antimony measures phosphorus content, and for removal rate up to 92.0%, adsorption capacity reaches 7.6660mg/g.
50mL 20mg/L phosphorus solution is added in 100mL conical flask, weighs the cerium modified chitosan of the above-mentioned preparation of 0.12g
Dephosphorization granule adsorbent changes 30 DEG C of adsorption temp, 40 DEG C, 50 DEG C, 60 DEG C respectively, shakes under the conditions of 200rpm in gas bath constant temperature
It swings after vibrating filter paper filtering in device, measuring tp removal rate is respectively 95.7%, 98.4%, 99.2% and 99.9%, it is seen that temperature is to this
Adsorption process influence is smaller, but temperature increases the removal for being conducive to phosphorus.
50mL 20mg/L phosphorus solution is added in 100mL conical flask, weighs the cerium modified chitosan of the above-mentioned preparation of 0.12g
Dephosphorization granule adsorbent, with 0.1mol/L HCl or 0.1mol/L NaOH adjust respectively pH value of solution be 1,3,5,7,9,25 DEG C,
Vibrate 40min under the conditions of 200rpm in gas bath constant temperature oscillator, after filter paper filtering, measure removal rate be respectively 79.8%,
96.6%, 91.1%, 85.7% and 81.4%, it is seen that it is smaller on adsorption process influence, but removal rate highest under mildly acidic conditions,
PH value of solution after absorption is kept at 5 or so.
Embodiment 2:
2g chitosan is added in beaker, 100mL 2%(v/v is added) acetum, the chitosan of stirring and dissolving, formation is molten
The mass-volume concentration of liquid is 2%.Add the CeNO that volumetric concentration is 10%, 0.5mol/L3•6H2O aqueous solution, 2h is to complete for stirring
After fully dissolved, stand.The solution for taking 10mL uniform diameter be 90mm culture dish in be cast, under 60 DEG C of baking ovens gel at
Film.Be to take off film after 10% sodium hydroxide solution impregnates culture dish with volumetric concentration, diaphragm, which distills, is washed to neutrality, at 60 DEG C
It is dry in baking oven.Diaphragm after 2g drying is added in conical flask, is added the ethanol solution of 2.5% epoxychloropropane of 50mL, in
8h is stirred in 60 DEG C of thermostat water bath.Diaphragm after being washed with distilled water crosslinking sieves with 100 mesh sieve after dry at 60 DEG C.Taper
Particle after 1g sieving is added in bottle, is added the hydrochloric acid of 10mL 8mol/L, stirs 1h at room temperature, be washed with distilled water to neutrality,
Drying is at 60 DEG C to get cerium modified chitosan dephosphorization granule adsorbent.
50mL 20mg/L phosphorus solution is added in 100mL conical flask, weighs the cerium modified chitosan of the above-mentioned preparation of 0.12g
Dephosphorization granule adsorbent vibrates 40min in gas bath constant temperature oscillator under the conditions of 25 DEG C, 200rpm and uses molybdenum after filter paper filtering
The anti-spectrophotometry of antimony measures phosphorus content, and for removal rate up to 96.4%, adsorption capacity reaches 8.0299mg/g.
50mL 20mg/L phosphorus solution is added in 100mL conical flask, weighs the cerium modified chitosan of the above-mentioned preparation of 0.12g
Dephosphorization granule adsorbent changes 30 DEG C of adsorption temp, 40 DEG C, 50 DEG C, 60 DEG C respectively, shakes under the conditions of 200rpm in gas bath constant temperature
It swings after vibrating filter paper filtering in device, measuring tp removal rate is respectively 96.8%, 99.1%, 99.9% and 100%, it is seen that temperature is to the suction
Attached process influence is smaller, but temperature increases the removal for being conducive to phosphorus.
50mL 20mg/L phosphorus solution is added in 100mL conical flask, weighs the cerium modified chitosan of the above-mentioned preparation of 0.12g
Dephosphorization granule adsorbent, with 0.1mol/L HCl or 0.1mol/L NaOH adjust respectively pH value of solution be 1,3,5,7,9,25 DEG C,
Vibrate 40min under the conditions of 200rpm in gas bath constant temperature oscillator, after filter paper filtering, measure removal rate be respectively 80.3%,
98.2%, 94.4%, 89.7% and 82.5%, it is seen that it is smaller on adsorption process influence, but removal rate highest under mildly acidic conditions,
PH value of solution after absorption is kept at 5 or so.
Embodiment 3:
2g chitosan is added in beaker, 100mL 2%(v/v is added) acetum, the chitosan of stirring and dissolving, formation is molten
The mass-volume concentration of liquid is 2%.Add the CeNO that volumetric concentration is 10%, 0.5mol/L3•6H2O aqueous solution, 2h is to complete for stirring
After fully dissolved, stand.The solution for taking 10mL uniform diameter be 90mm culture dish in be cast, under 60 DEG C of baking ovens gel at
Film.Be to take off film after 10% sodium hydroxide solution impregnates culture dish with volumetric concentration, diaphragm, which distills, is washed to neutrality, at 60 DEG C
It is dry in baking oven.Diaphragm after 2g drying is added in conical flask, is added the ethanol solution of 2.5% epoxychloropropane of 50mL, in
6h is stirred in 60 DEG C of thermostat water bath.Diaphragm after being washed with distilled water crosslinking sieves with 100 mesh sieve after dry at 60 DEG C.Taper
Particle after 1g sieving is added in bottle, is added the hydrochloric acid of 10mL 6mol/L, stirs 1h at room temperature, be washed with distilled water to neutrality,
Drying is at 60 DEG C to get cerium modified chitosan dephosphorization granule adsorbent.
50mL 50mg/L phosphorus solution is added in 100mL conical flask, weighs the cerium modified chitosan of the above-mentioned preparation of 0.12g
Dephosphorization granule adsorbent vibrates 40min in gas bath constant temperature oscillator under the conditions of 25 DEG C, 200rpm and uses molybdenum after filter paper filtering
The anti-spectrophotometry of antimony measures phosphorus content, and for removal rate up to 90.8%, adsorption capacity reaches 7.5649mg/g.
50mL 50mg/L phosphorus solution is added in 100mL conical flask, weighs the cerium modified chitosan of the above-mentioned preparation of 0.12g
Dephosphorization granule adsorbent changes 30 DEG C of adsorption temp, 40 DEG C, 50 DEG C, 60 DEG C respectively, shakes under the conditions of 200rpm in gas bath constant temperature
It swings after vibrating filter paper filtering in device, measuring tp removal rate is respectively 92.6%, 95.0%, 97.6% and 99.3%, it is seen that temperature is to this
Adsorption process influence is smaller, but temperature increases the removal for being conducive to phosphorus.
50mL 50mg/L phosphorus solution is added in 100mL conical flask, weighs the cerium modified chitosan of the above-mentioned preparation of 0.12g
Dephosphorization granule adsorbent, with 0.1mol/L HCl or 0.1mol/L NaOH adjust respectively pH value of solution be 1,3,5,7,9,25 DEG C,
Vibrate 40min under the conditions of 200rpm in gas bath constant temperature oscillator, after filter paper filtering, measure removal rate be respectively 77.4%,
95.8%, 90.3%, 85.3% and 80.7%, it is seen that it is smaller on adsorption process influence, but removal rate highest under mildly acidic conditions,
PH value of solution after absorption is kept at 5 or so.
The above is merely preferred embodiments of the present invention, it is not intended to limit the protection scope of invention, it is therefore, all at this
Any modification, equivalent replacement, improvement and so within the spirit and principle of invention, should be included in protection scope of the present invention
Within.
Claims (10)
1. a kind of preparation method of cerium modified chitosan dephosphorization granule adsorbent, it is characterized in that: including the following steps:
Step 1: weighing Chitosan powder and be dissolved in acetum, stirring forms chitosan solution to being completely dissolved；
Step 2: cerous nitrate aqueous solution being added in chitosan solution, constant speed stirring forms six nitric hydrate cerium solution；
Step 3: standing six nitric hydrate cerium solution and take six uniform nitric hydrate cerium solution in culture dish after bubble eliminates
It forms a film after middle curtain coating in baking oven inner gel；
Step 4: culture dish is impregnated with sodium hydroxide solution, diaphragm takes off film after heaving, is washed diaphragm to neutrality with distilled water, and
In drying in oven；
Step 5: the diaphragm of drying being added in crosslinking agent, is crosslinked in thermostat water bath, crosslinker solution diaphragm is formed；
Step 6: being washed with distilled water crosslinking agent extra on crosslinker solution diaphragm and drying, grinding and sieving；
Step 7: the particle after sieving is protonated at room temperature with hydrochloric acid solution, and is dried after being washed with distilled water to neutrality,
Obtain the cerium modified chitosan dephosphorization granule adsorbent.
2. the preparation method of cerium modified chitosan dephosphorization granule adsorbent according to claim 1, it is characterized in that: described
Step 1 in, the volumetric concentration of acetum is 1.9%-2.1%, and the mass-volume concentration of the chitosan solution of formation is 2%.
3. the preparation method of cerium modified chitosan dephosphorization granule adsorbent according to claim 1, it is characterized in that: described
Step 2 in, the concentration of cerous nitrate aqueous solution is 0.5mol/L, and the volumetric concentration of six nitric hydrate cerium solution of formation is 9%-
11%。
4. the preparation method of cerium modified chitosan dephosphorization granule adsorbent according to claim 1, it is characterized in that: described
Step 4 in, the volumetric concentration of sodium hydroxide solution is 10%.
5. the preparation method of cerium modified chitosan dephosphorization granule adsorbent according to claim 1, it is characterized in that: described
Step 5 in, crosslinking agent is epoxychloropropane ethanol solution, and the concentration of epoxychloropropane ethanol solution is 2.5%, the friendship of formation
The mass-volume concentration for joining solution diaphragm is 4%.
6. the preparation method of cerium modified chitosan dephosphorization granule adsorbent according to claim 1, it is characterized in that: described
Step 5 in, the temperature of thermostat water bath is 55-65 DEG C, and the time of crosslinking is 6-8 hours.
7. the preparation method of cerium modified chitosan dephosphorization granule adsorbent according to claim 1, it is characterized in that: described
Step 6 in, the mesh density of sieving is 100 mesh or 200 mesh.
8. the preparation method of cerium modified chitosan dephosphorization granule adsorbent according to claim 1, it is characterized in that: described
Step 7 in, the concentration of hydrochloric acid solution is 6-8mol/L, and the mass-volume concentration of particle is 10% in hydrochloric acid solution.
9. the preparation method of cerium modified chitosan dephosphorization granule adsorbent according to claim 1, it is characterized in that: described
Step 7 in, time of protonation is 0.5-1 hours.
10. the preparation method of cerium modified chitosan dephosphorization granule adsorbent according to claim 1, it is characterized in that: in institute
In the preparation method for the cerium modified chitosan dephosphorization granule adsorbent stated, the temperature of drying is 55-65 DEG C.
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| CN113477226A (en) * | 2021-07-28 | 2021-10-08 | 佛山科学技术学院 | Method for removing trivalent antimony in aqueous solution by using chitosan modified charcoal |
| CN115738997A (en) * | 2022-11-23 | 2023-03-07 | 东北农业大学 | Preparation method and application of cerium-iron co-modified hydrophilic porous biochar |
| CN116809034A (en) * | 2023-08-31 | 2023-09-29 | 天津包钢稀土研究院有限责任公司 | Preparation method of dephosphorizing agent based on rare earth modified gangue |
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