CN103611494A - Amido modified attapulgite clay adsorbent and method for preparing and adsorbing humic acid - Google Patents
Amido modified attapulgite clay adsorbent and method for preparing and adsorbing humic acid Download PDFInfo
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Abstract
The invention discloses an amido modified attapulgite clay adsorbent. The adsorbent is prepared by reacting silane and acid modified attapulgite clay, wherein the mass to volume ratio of the acid modified attapulgite clay and the silane is 1:(1-2)g/mL. According the amido modified attapulgite clay adsorbent disclosed by the invention, the attapulgite clay is modified via the silane by using lots of silicon hydroxyls on the surface of the attapulgite clay, then the attapulgite clay adsorbent with high amino content is synthesized by fully combining the characteristics of the attapulgite clay and the silane; the chemical property of the attapulgite clay adsorbent is stable and free of the influence of external environmental factors; meanwhile, the preparation method of the adsorbent disclosed by the invention is simple, the cost is low, the adsorbent can be used for well adsorbing humic acid.
Description
Technical field
The invention belongs to adsorbent technical field, be specifically related to a kind of amino modified attapulgite adsorbent, the invention still further relates to the preparation method of this adsorbent and the method for absorption humic acid.
Background technology
Humic acid is through the decomposition of microorganism and a kind of dark color, acidity and the hydrophilic colloid type organic that complicated chemical process forms by vegeto-animal remains.Humic acid in natural water body is a kind of polymeric organic acid containing multiple functional groups such as carboxyls, phenolic hydroxyl group, alcoholic extract hydroxyl group, accounts for 50%～90% of total organic matter in water.The existence of humic acid has formed serious threat to the water quality safety of drinking water.Humic acid very easily reacts with chlorhexidine-containing disinfectant and produces the multiple toxic byproduct that has in disinfecting process, and these accessory substances have the effect of " carcinogenic, teratogenesis, mutagenesis " to people.Humic acid in water very easily ionization and electronegative, the functional groups such as the contained carboxyl of this anionic polymerisation bath surface, hydroxyl can or interact with other organic pollution with contained complexing of metal ion in water, formation has the polymer substance of labyrinth, affects heavy metal and the organic pollution migration and conversion in water.
The method of removing humic acid in water mainly contains absorption method, bioanalysis, flocculence, membrane filter technique and photoelectrochemical method etc.But because the biological species of degraded humic acid exists limitation, clearance is low, periodicity is long; The security of flocculant exists to be queried; Calcium in natural water body, magnesium plasma and humic acid generation complexing, cause film seriously polluted; Photoelectrochemical method operating cost is high, power consumption is large, treating capacity is limited.The advantage of absorption method is that removal efficiency is high, easy and simple to handle, and can not produce side reaction and affect water quality.
Absorption is a kind of interfacial phenomenon relevant with surface energy, is often divided into chemisorbed, physical absorption and ion-exchange absorption.In adsorption process, most of absorption is the result of three kinds of comprehensive absorption of suction type often.At present, active carbon, resinae material and inorganic mineral etc. are the widely used adsorbents of research.And the difficult life of active carbon and difficult absorption hydrophilic small molecules etc. become the subject matter that limits its extensive use; And anion exchange resin partial organic substances in adsorbed water body simultaneously limits its extensive use, non-ionic resin in solution to hydrophilic small molecules Adsorption of Organic poor effect.
Natural inorganic mineral is the focus of studying at present, and these natural minerals have higher surface-active and larger specific surface mostly, in water treatment procedure, can show good adsorptivity.Wherein, attapulgite is the special natural monodimension nanometer material of a kind of structure.Because the impurity that attapulgite self is contained is more, therefore restrict the scope of application of natural attapulgite, and had repulsion between natural attapulgite and humic acid, low to the clearance of humic acid.
Summary of the invention
The object of this invention is to provide a kind of amino modified attapulgite adsorbent, solved natural attapulgite impurities more and and humic acid between there is repulsion, the problem low to humic acid clearance.
Another object of the present invention is to provide the preparation method of above-mentioned amino modified attapulgite adsorbent.
The 3rd object of the present invention is to provide the method for above-mentioned amino modified attapulgite adsorbent absorption humic acid.
The technical solution adopted in the present invention is, amino modified attapulgite adsorbent, take silane and acid attapulgite modified be raw material, by reaction, obtain, wherein sour attapulgite modified and mass volume ratio silane is 1:1～2g/mL.
Feature of the present invention is also,
Silane is γ-aminopropyltrimethoxysilane (APTES) and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (NAPTES).
The hydrochloric acid solution that during acid is attapulgite modified, acid used is 1～1.5mol/L.
Another technical scheme of the present invention is, the preparation method of amino modified attapulgite adsorbent specifically implements according to following steps:
Step 1, acid is attapulgite modified
The attapulgite that is 1:10 by mass ratio filters the large particulate matter of removing beaker bottom mix ultrasonic dispersion 10～30min with distilled water after; After the there-necked flask that the attapulgite of ultrasonic mistake is placed in to the hydrochloric acid solution that 1～1.5mol/L is housed reacts 8～12h at 60 ℃～90 ℃, filter, washing until neutral, is dried, and obtains acid attapulgite modified;
Step 2, the preparation of amino modified attapulgite
Acid that step 1 is obtained is attapulgite modified to be joined and in there-necked flask, adds toluene solution again; ultrasonic dispersion 10～30min; then under nitrogen protection, add silane; sour attapulgite modified and mass volume ratio silane is 1:1～2g/mL; react 10～12h at 100～120 ℃ after, filter; purify, finally, with vacuum drying at 100～105 ℃ after absolute ethyl alcohol purification 8～24h, obtain amino modified attapulgite.
Feature of the present invention is also,
In step 1, the attapulgite of ultrasonic mistake and the mass volume ratio of hydrochloric acid solution are 1:10g/mL.
In step 2, attapulgite modified and mass volume ratio toluene solution of acid is to be 1:30～60g/mL.
In step 2, silane is γ-aminopropyltrimethoxysilane (APTES) and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (NAPTES).
The 3rd technical scheme of the present invention is, adopt the method for above-mentioned amino modified attapulgite adsorbent absorption humic acid, the amino modified attapulgite adsorbent that adds 0.0005 times of its quality in the water body purifying in wish, humic acid in adsorbed water under the condition that 25 ℃, pH are 2.0～9.5, after absorption 1min～24h, collect amino modified attapulgite adsorbent, the humic acid in purifying water body.
Feature of the present invention is also,
In the water body that wish purifies, the concentration of humic acid is 15.8～252mg/L.
The invention has the beneficial effects as follows, amino modified attapulgite adsorbent of the present invention, utilize a large amount of silicon hydroxyl in attapulgite self surface, adopt silane to carry out modification to attapulgite, fully in conjunction with the feature of attapulgite and silane, the synthetic attapulgite adsorbent with high amino content, its stable chemical nature, not affected by external environment factor, and the preparation method of adsorbent of the present invention is simple, with low cost, absorption property is good.
The specific embodiment
Below in conjunction with the specific embodiment, the present invention is described in detail.
Amino modified attapulgite adsorbent of the present invention, the silane of take is attapulgite modified with acid is raw material, by reaction, obtain, wherein sour attapulgite modified and mass volume ratio silane are 1:1～2g/mL, silane is γ-aminopropyltrimethoxysilane (APTES) and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (NAPTES), the hydrochloric acid solution that during acid is attapulgite modified, acid used is 1～1.5mol/L.
Amino modified attapulgite adsorbent of the present invention, utilize a large amount of silicon hydroxyl in attapulgite self surface, adopt silane to carry out modification to attapulgite, the abundant feature in conjunction with attapulgite and silane, the synthetic attapulgite adsorbent with high amino content, its stable chemical nature, is not affected by external environment factor, and the preparation method of adsorbent of the present invention is simple, with low cost, absorption property is good.
The preparation method of above-mentioned amino modified attapulgite adsorbent, specifically implements according to following steps:
Step 1, acid is attapulgite modified
The attapulgite that is 1:10 by mass ratio filters the large particulate matter of removing beaker bottom mix ultrasonic dispersion 10～30min with distilled water after; After reacting 8～12h at 60 ℃～90 ℃, filters the there-necked flask that the attapulgite of ultrasonic mistake is placed in to the hydrochloric acid solution that 1～1.5mol/L is housed, the attapulgite of ultrasonic mistake and the mass volume ratio of hydrochloric acid solution are 1:10g/mL, washing is until neutral, and oven dry, obtains acid attapulgite modified;
Step 2, the preparation of amino modified attapulgite
Attapulgite modified the joining in there-necked flask of acid that step 1 is obtained, add again toluene solution (sour attapulgite modified and mass volume ratio toluene solution is to be 1:30～60g/mL), ultrasonic dispersion 10～30min, then under nitrogen protection, add silane, sour attapulgite modified and mass volume ratio silane is that 1:1～2g/mL(silane is γ-aminopropyltrimethoxysilane (APTES) and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (NAPTES)), react 10～12h at 100～120 ℃ after, filter, purify, finally with vacuum drying at 100～105 ℃ after absolute ethyl alcohol purification 8～24h, obtain amino modified attapulgite.
Attapulgite is natural minerals, and utilizing its Main Ingredients and Appearance of x-ray fluorescence analysis is SiO
2(mass content 64.5%), therefore abundant silicon hydroxyl is contained on surface, is easy to surface modification.By amino containing silane reagent, its surface is carried out obtaining amino modified attapulgite.Amino modified attapulgite is nanometer materials, has higher specific area and active amine, aspect separated from contaminants removal, has potential application foreground.
Adopt the method for above-mentioned amino modified attapulgite adsorbent absorption humic acid, in the water body that wish purifies, the concentration of humic acid is 15.8～252mg/L, the amino modified attapulgite adsorbent that adds 0.0005 times of its quality in the water body purifying in wish, humic acid in adsorbed water under the condition that 25 ℃, pH are 2.0～9.5, after absorption 1min～24h, collect amino modified attapulgite adsorbent, the humic acid in purifying water body.
In research, find, natural attapulgite is limited to humic acid adsorption capacity in water.For improving its adsorbance, be necessary its modifying surface.The synthetic amino modified attapulgite adsorbent surface of the present invention contains abundant active amino, it is easy to protonated and positively charged in water, and humic acid is electronegative because carboxyl, phenolic hydroxyl group dissociate in water body, therefore, pass through electrostatic interaction, humic acid is easy to be adsorbed onto the surface of amino modified attapulgite, and the compound forming with surface amino groups effect, thereby reaches the separated object of removing humic acid in water.
The preparation of amino modified attapulgite adsorbent
Embodiment 1
Step 1, acid is attapulgite modified
20g attapulgite is placed in to 200mL distilled water, after ultrasonic dispersion 30min, filters the large particulate matter of removing beaker bottom; After the there-necked flask that the attapulgite of ultrasonic mistake is placed in to the hydrochloric acid solution that 200mL, 1mol/L are housed reacts 8.5h at 80 ℃, filter, washing until neutral, is dried, and obtains acid attapulgite modified;
Step 2, the preparation of amino modified attapulgite
The attapulgite modified 4.0g of acid that step 1 is obtained joins in there-necked flask; the toluene solution that adds again 160mL; ultrasonic dispersion 30min; then under nitrogen protection, add N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (NAPTES) 6mL; react 12h at 110 ℃ after, filter, purify, finally with the absolute ethyl alcohol 12h that purifies; finally dry 12h under 100 ℃ of vacuum, obtains amino modified attapulgite.
Embodiment 2
Step 1, acid is attapulgite modified
20g attapulgite is placed in to 200mL distilled water, after ultrasonic dispersion 10min, filters the large particulate matter of removing beaker bottom; After the there-necked flask that the attapulgite of ultrasonic mistake is placed in to the hydrochloric acid solution that 200mL, 1.5mol/L are housed reacts 8h at 90 ℃, filter, washing until neutral, is dried, and obtains acid attapulgite modified;
Step 2, the preparation of amino modified attapulgite
The attapulgite modified 4.0g of acid that step 1 is obtained joins in there-necked flask; the toluene solution that adds again 120mL; ultrasonic dispersion 20min; then under nitrogen protection, add N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (NAPTES) 4mL; react 10h at 100 ℃ after, filter, purify, finally with the absolute ethyl alcohol 8h that purifies; finally dry 12h under 105 ℃ of vacuum, obtains amino modified attapulgite.
Embodiment 3
Step 1, acid is attapulgite modified
20g attapulgite is placed in to 200mL distilled water, after ultrasonic dispersion 20min, filters the large particulate matter of removing beaker bottom; After the there-necked flask that the attapulgite of ultrasonic mistake is placed in to the hydrochloric acid solution that 200mL, 1.2mol/L are housed reacts 12h at 60 ℃, filter, washing until neutral, is dried, and obtains acid attapulgite modified;
Step 2, the preparation of amino modified attapulgite
The attapulgite modified 4.0g of acid that step 1 is obtained joins in there-necked flask; the toluene solution that adds again 200mL; ultrasonic dispersion 10min; then under nitrogen protection, add N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (NAPTES) 8mL; react 11h at 120 ℃ after, filter, purify, finally with the absolute ethyl alcohol 24h that purifies; finally dry 12h under 102 ℃ of vacuum, obtains amino modified attapulgite.
Embodiment 4
Step 1, acid is attapulgite modified
20g attapulgite is placed in to 200mL distilled water, after ultrasonic dispersion 30min, filters the large particulate matter of removing beaker bottom; After the there-necked flask that the attapulgite of ultrasonic mistake is placed in to the hydrochloric acid solution that 200mL, 1mol/L are housed reacts 8.5h at 80 ℃, filter, washing until neutral, is dried, and obtains acid attapulgite modified;
Step 2, the preparation of amino modified attapulgite
The attapulgite modified 4.0g of acid that step 1 is obtained joins in there-necked flask; the toluene solution that adds again 240mL; ultrasonic dispersion 30min; then under nitrogen protection, add γ-aminopropyltrimethoxysilane (APTES) 6mL; react 12h at 110 ℃ after, filter, purify, finally with the absolute ethyl alcohol 12h that purifies; finally dry 12h under 100 ℃ of vacuum, obtains amino modified attapulgite.
Adopt the humic acid in this adsorbent adsorbed water body
Embodiment 5
With the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 1 preparation.The initial concentration of humic acid is 252mg/L, the amino modified attapulgite that adds 0.0005 times of contaminant water quality, humic acid under the condition that 25 ℃, pH are 6.9 in adsorbed water, after absorption 24h, collect amino modified attapulgite adsorbent, humic acid in purifying water body, adsorbance is 245.1mg/g, adsorbance is apparently higher than conventional adsorbent (bibliographical information: the maximal absorptive capacity 78mg/g of modified zeolite to humic acid, active carbon is 74mg/g to the maximal absorptive capacity of humic acid, and the maximal absorptive capacity of Humic Acid Using Polymeric Adsorbent Modified By Amin is 30.7mg/g).Adsorbance refers to the quality of the humic acid that every gram of adsorbent adsorbs.
Embodiment 6
With the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 1 preparation.The initial concentration of humic acid is 31.5mg/L, the amino modified attapulgite that adds 0.0005 times of contaminant water quality, humic acid under the condition that 25 ℃, pH are 6.7 in adsorbed water, after absorption 24h, collect amino modified attapulgite adsorbent, humic acid in purifying water body, recording humic acid adsorbance is 61.6mg/g, and clearance is 98.7%.
Embodiment 7
With reference to embodiment 6, with the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 1 preparation.When humic acid initial concentration is 63mg/L, other conditions are constant, and the adsorbance that records humic acid is 119.1mg/g, and clearance is 93.1%.
Visible, amino modified attapulgite adsorbent has compared with high adsorption capacity humic acid in water.
Embodiment 8
With the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.The initial concentration of humic acid is 63mg/L, the amino modified attapulgite that adds 0.0005 times of contaminant water quality, humic acid under the condition that 25 ℃, pH are 6.9 in adsorbed water, after absorption 24h, collect amino modified attapulgite adsorbent, humic acid in purifying water body, recording humic acid adsorbance is 55.1mg/g, and clearance is 43.5%.
Embodiment 9
With reference to embodiment 8, with the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.The Ca that adds 0.25mmol/L in absorption forward direction contaminant water
2+ion (CaCl
2solution), other conditions are constant, and the adsorbance that records humic acid is 84.0mg/g, and the clearance of humic acid is 67.7%.
Embodiment 10
With reference to embodiment 8, with the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.The Ca that adds 2mmol/L in absorption forward direction contaminant water
2+ion (CaCl
2solution), other conditions are constant, and the adsorbance that records humic acid is 109.7mg/g, and the clearance of humic acid is 88.0%.
As can be seen here, Ca in water
2+the existence of ion can improve the clearance of amino modified attapulgite adsorbent to humic acid.
Embodiment 11
With reference to embodiment 8, with the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.The initial concentration of humic acid is 15.8mg/L, and other conditions are constant, and recording humic acid adsorbance is 23.7mg/g, and clearance is 29.7%.
Embodiment 12
With reference to embodiment 8, with the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.The initial concentration of humic acid is 157.5mg/L, and other conditions are constant, and recording humic acid adsorbance is 77.3mg/g, and clearance is 24.7%.
As can be seen here, along with the increase of humic acid initial concentration, amino modified attapulgite increases gradually to the adsorbance of humic acid.
Embodiment 13
With the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.The initial concentration of humic acid is 63mg/L, the amino modified attapulgite that adds 0.0005 times of contaminant water quality, at 25 ℃, pH, be that 2.0(is acid) condition under humic acid in adsorbed water, after absorption 24h, collect amino modified attapulgite adsorbent, humic acid in purifying water body, the adsorbance that records humic acid is 123.8mg/g, and the clearance of humic acid is 98.7%.
Embodiment 14
With reference to embodiment 13, with the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.PH is adjusted to 4.9, and other conditions are constant, and the adsorbance that records humic acid is 107.5mg/g, and the clearance of humic acid is 85.8%.
Embodiment 15
With reference to embodiment 13, with the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.PH is adjusted to 8.3, and other conditions are constant, and the adsorbance that records humic acid is 23.0mg/g, and the clearance of humic acid is 18.3%.
Embodiment 16
With reference to embodiment 13, with the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.PH is adjusted to 9.5, and other conditions are constant, and the adsorbance that records humic acid is 13.5mg/g, and the clearance of humic acid is 10.6%.
As can be seen here, amino modified attapulgite adsorbent reduces along with the rising of pH the adsorbance of humic acid in water, and low pH is conducive to the removal of humic acid in water.
Embodiment 17
With the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.The initial concentration of humic acid is 94.5mg/L, the amino modified attapulgite that adds 0.0005 times of contaminant water quality, at 25 ℃, pH, be that 6.9(is acid) condition under humic acid in adsorbed water, after absorption 1min, collect amino modified attapulgite adsorbent, humic acid in purifying water body, the adsorbance that records humic acid is 16.8mg/g, and the clearance of humic acid is 8.9%.
Embodiment 18
With reference to embodiment 17, with the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.Adsorption time is 50min, and other conditions are constant, and the adsorbance that records humic acid is 48.5mg/g, and the clearance of humic acid is 25.7%.
Embodiment 19
With reference to embodiment 17, with the humic acid in the amino modified attapulgite adsorbent adsorbed water of embodiment 4 preparations.Adsorption time is 590min, and other conditions are constant, and the adsorbance that records humic acid is 66.2mg/g, and the clearance of humic acid is 35.1%.
As can be seen here, with the prolongation of adsorption time, adsorbance increases gradually, and absorption 10h reaches balance substantially.
Comparative example 1
Take attapulgite original soil as adsorbent, and adsorption conditions is with embodiment 6, and recording attapulgite is 27.3% to the clearance of humic acid.Be starkly lower than amino modified attapulgite adsorbent in invention.
Claims (9)
1. amino modified attapulgite adsorbent, is characterized in that, take silane and acid attapulgite modified be raw material, by reaction, obtain, wherein sour attapulgite modified and mass volume ratio silane is 1:1～2g/mL.
2. amino modified attapulgite adsorbent according to claim 1, is characterized in that, silane is γ-aminopropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.
3. amino modified attapulgite adsorbent according to claim 1 and 2, is characterized in that, the hydrochloric acid solution that during acid is attapulgite modified, acid used is 1～1.5mol/L.
4. the preparation method of amino modified attapulgite adsorbent according to claim 1, is characterized in that, specifically according to following steps, implements:
Step 1, acid is attapulgite modified
The attapulgite that is 1:10 by mass ratio filters the large particulate matter of removing beaker bottom mix ultrasonic dispersion 10～30min with distilled water after; After the there-necked flask that the attapulgite of ultrasonic mistake is placed in to the hydrochloric acid solution that 1～1.5mol/L is housed reacts 8～12h at 60 ℃～90 ℃, filter, washing until neutral, is dried, and obtains acid attapulgite modified;
Step 2, the preparation of amino modified attapulgite
Acid that step 1 is obtained is attapulgite modified to be joined and in there-necked flask, adds toluene solution again; ultrasonic dispersion 10～30min; then under nitrogen protection, add silane; sour attapulgite modified and mass volume ratio silane is 1:1～2g/mL; react 10～12h at 100～120 ℃ after, filter; purify, finally, with vacuum drying at 100～105 ℃ after absolute ethyl alcohol purification 8～24h, obtain amino modified attapulgite.
5. the preparation method of amino modified attapulgite adsorbent according to claim 4, is characterized in that, in step 1, the attapulgite of ultrasonic mistake and the mass volume ratio of hydrochloric acid solution are 1:10g/mL.
6. the preparation method of amino modified attapulgite adsorbent according to claim 4, is characterized in that, in step 2, attapulgite modified and mass volume ratio toluene solution of acid is to be 1:30～60g/mL.
7. the preparation method of amino modified attapulgite adsorbent according to claim 4, is characterized in that, in step 2, silane is γ-aminopropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.
8. adopt the method for amino modified attapulgite adsorbent absorption humic acid claimed in claim 1, it is characterized in that, the amino modified attapulgite adsorbent that adds 0.0005 times of its quality in the water body purifying in wish, humic acid in adsorbed water under the condition that 25 ℃, pH are 2.0～9.5, after absorption 1min～24h, collect amino modified attapulgite adsorbent, the humic acid in purifying water body.
9. the method for amino modified attapulgite adsorbent absorption humic acid according to claim 8, is characterized in that, in the water body that wish purifies, the concentration of humic acid is 15.8～252mg/L.
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| CN108704617A (en) * | 2018-05-16 | 2018-10-26 | 西安科技大学 | The preparation method and applications of humic acid/attapulgite magnetic composite material |
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| CN106975454A (en) * | 2017-04-28 | 2017-07-25 | 明光市飞洲新材料有限公司 | A kind of silane coupler modified method of attapulgite |
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| CN110918059A (en) * | 2019-12-10 | 2020-03-27 | 辽宁大学 | Porous carbon ceramic and preparation method and application thereof |
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| CN111659344A (en) * | 2020-06-16 | 2020-09-15 | 明光春计高分子材料有限公司 | Modified attapulgite adsorbent and production process thereof |
| CN113070047A (en) * | 2021-03-30 | 2021-07-06 | 江西理工大学 | Functionalized mineral material and preparation method and application thereof |
| CN114643048A (en) * | 2022-03-29 | 2022-06-21 | 东南大学 | Composite adsorption material and preparation method and application thereof |
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