CN109317095A - A kind of composite material and preparation method for hexavalent chromium removal - Google Patents
A kind of composite material and preparation method for hexavalent chromium removal Download PDFInfo
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- CN109317095A CN109317095A CN201811185016.9A CN201811185016A CN109317095A CN 109317095 A CN109317095 A CN 109317095A CN 201811185016 A CN201811185016 A CN 201811185016A CN 109317095 A CN109317095 A CN 109317095A
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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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The present invention provides a kind of composite material and preparation method for hexavalent chromium removal, which includes charcoal, and carried magnetic ferriferrous sulfide on biological carbon matrix；The step of preparation method includes: that charcoal is made using rice husk as raw material by pyrolysis calcination method；Charcoal is soaked in sulfur acid ferrous iron solution, using L-cysteine as sulphur source, ethylene glycol is solvent, passes through solvent-thermal method one-step synthesis magnetic bio charcoal/ferriferrous sulfide composite material；The step of application, is: the composite material is added in containing the hexavalent chromium wastewater that concentration is 20mg/L, composite material usage amount is 0.2-1.0g/L, at 25 DEG C after oscillating reactions for a period of time, composite material is separated with magnet with solution, completes the removal to hexavalent chromium in waste water.The present invention has many advantages, such as that composite material and preparation method thereof is simple, at low cost, environmental-friendly and high to hexavalent chromium removal efficiency in waste water.
Description
Technical field
The present invention relates to functionalization material preparation process field and field of water pollution control, specifically a kind of to be used for six
Magnetic bio charcoal/ferriferrous sulfide composite material and preparation method of valence chromium removal.
Background technique
Chromium is widely used in the industries such as plating, the processing of metallurgy, leather tanning, timber, dyestuff manufacture.Due to Treatment process and
The limitation of supervision causes high-concentration chromium-containing wastewater to be thrown into natural water, or even directly polluted drinking water source.2012
In the big high poison pollution problem in the whole world ten that year is reported, pollution of chromium be ranked third.According to " Zhejiang Province's heavy metal pollution integrated control rule
Draw (- 2015 years 2010) ", the total emission volumn of chromium accounts for the 95.02% of Zhejiang Province's commercial metal total emission volumn.There are a variety of for chromium
Valence state and form, and the stability and bio-toxicity of different valence state and form chromium differ greatly.For example, Cr VI has acute poison
Property effect, lure distortion property and carcinogenesis, it is considered to be one of typical pollutant in heavy metal wastewater thereby.And trivalent chromium is often with oxidation
Chromium and chromium hydroxide exist, therefore have fewer environmental impacts.Therefore, the Cr VI gone in water removal becomes the emphasis of pollution of chromium reparation.
Currently, the method for removal Cr (VI) includes: physical treatment process (absorption method, ion-exchange, membrane separation process etc.), change
Learn facture (oxidation-reduction method, neutralization precipitation method, chemical precipitation method, flocculence, electrolysis method etc.) and biological treatment etc..
For example, there is the material of high-specific surface area to be usually used in for carbonaceous material, resin, polymer, agriculture and forestry organic waste material, microbial flocculant etc.
Cr (VI) absorption.Although these adsorbent materials are cheap, are easy to get, its absorption for being only able to achieve Cr VI cannot achieve Cr VI
Reduction.And the separation of reactant and product relatively difficult to achieve after reaction, lead to secondary pollution and increases subsequent treatment cost.
For this purpose, the iron-based material of reproducibility is often used as the reducing agent of Cr VI, to improve the reduction efficiency during hexavalent chromium removal.
For example, Zero-valent Iron, iron sulfide, (hydrogen) iron oxide etc. realize Cr VI by mechanism such as electronics transfer, electrostatic attraction and co-precipitation
Absorption and reduction.However, common iron-based material specific surface area is small, adsorption activated centre is single.It therefore, will be magnetic iron-based
Material is in conjunction with large specific surface area, surface functional group Carbon Materials abundant, and exploitation is efficiently for adsorbing-reduction coupling removal six
The new function material of valence chromium becomes the focus of growing interest.
Summary of the invention
The shortcomings that the purpose of the invention is to overcome the prior art and deficiency provide a kind of magnetic for hexavalent chromium removal
Property charcoal/ferriferrous sulfide composite material and preparation method.This method is biological carbon feedstock with rice husk, using solvent-thermal method
One-step synthesis magnetic bio charcoal/ferriferrous sulfide composite material.By charcoal in conjunction with magnetic ferriferrous sulfide, life is not only realized
The magnetization of object charcoal, also increases the adsorption capacity of composite material, to provide, one kind is low in cost, preparation process is simple, easily divides
Material from Cr VI in, environmental-friendly removal waste water.
The present invention is realized by the following technical programs:
A kind of composite material for hexavalent chromium removal, it is characterised in that the composite material be using charcoal as carrier,
With solvent heat legal load magnetism ferriferrous sulfide, wherein the mass ratio of magnetic ferriferrous sulfide is 5-30%.
A kind of preparation method of the composite material for hexavalent chromium removal, it is characterised in that the preparation method by with
Lower step composition:
1) using rice husk as raw material, the thermal cracking 2-4h under 400-600 DEG C of limited oxygen condition obtains black bio charcoal solid；
2) black bio charcoal solid made from step 1) is crushed into 5min through the pulverizer that power is 1000W, gained powder crosses 100
Mesh；
3) it takes powder made from step 2 through 0.1mol/L hydrochloric acid washing by soaking, removes the impurity such as ash content, residue in charcoal；
4) it will be placed in air dry oven by the charcoal powder of step 3) processing, 90 DEG C of set temperature, dry 6h, gained is solid
Body is clean charcoal, for use；
5) green vitriol is dissolved in 25mL ethylene glycol；
6) 1.0g charcoal is sufficiently mixed with iron-containing liquor in step 5) by ultrasound；
7) L-cysteine is dissolved in 25 milliliters of ethylene glycol；
8) solution in step 7) is added to dropwise in the mixed liquor of step 6), control time for adding is 10-15min, and mixing is made
Liquid；
9) mixed liquor made from step 8) is transferred to 100mL polytetrafluoroethylliner liner, and in reaction cartridge kettle；
10) above-mentioned stainless steel cauldron is placed in air dry oven and is reacted；
11) after reaction to step 10), cooled to room temperature takes out liner from reaction kettle, and it is solid to collect liner at the bottom
Body；
12) step 11) obtained solid is respectively washed 2-3 times through water and ethyl alcohol, 4-6h, gained is dried in vacuo under the conditions of 50-60 DEG C
Solid is magnetic bio charcoal/ferriferrous sulfide composite material.
A kind of preparation method of composite material for hexavalent chromium removal, it is characterised in that seven hydration in step 5)
The dosage of ferrous sulfate is 0.189-1.132g.
A kind of preparation method of composite material for hexavalent chromium removal, it is characterised in that half Guang of L- in step 7)
The dosage of propylhomoserin is 0.082-0.493g.
A kind of preparation method of composite material for hexavalent chromium removal, it is characterised in that air blast in step 10)
The drying temperature of drying box is 160-200 DEG C, reaction time 12-24h.
Magnetic bio charcoal/ferriferrous sulfide composite material of above-mentioned preparation is applied to the processing of the waste water containing hexavalent chromium,
It is characterized in that mainly comprising the steps that
1) 0.2-1.0g/L magnetic bio charcoal/ferriferrous sulfide composite wood is added into the hexavalent chromium wastewater that concentration is 20mg/L
Material, adjusting pH value are 3.2-11.2, and mixed liquor is made；
2) mixed liquor is placed in constant temperature oscillator, 1h is shaken with 200r/min revolving speed, after the reaction was completed with magnet by composite wood
Material is separated with waste water, completes the removal of hexavalent chromium.
Compared with prior art, the invention has the following advantages:
1) preparation method of magnetic bio charcoal/ferriferrous sulfide composite material provided by the invention uses rice husk for raw material preparation
Charcoal and iron content, sulphur presoma mixed liquor be made through solvent thermal reaction, it is easy to operate, at low cost, and preparation method and work
Skill is simple, can effectively realize industrialized production.In addition, the rice husk in agriculture and forestry organic waste material exists as raw material for the composite material
Hexavalent chromium wastewater, which is administered, provides application guarantee；
2) charcoal in magnetic bio of the invention charcoal/ferriferrous sulfide composite material has large specific surface area, surface function
Group's characteristic abundant, while ferriferrous sulfide can provide a large amount of reduction row ferrous irons and sulphion, be the absorption of hexavalent chromium
Diversified approach is provided with reduction.Meanwhile the material has magnetism, it is easy to from separating in treated waste water, for containing six
The improvement of valence chromium waste water provides technical support；
3) magnetic bio of the invention charcoal/ferriferrous sulfide composite material has the characteristics that environmental-friendly, practicability is high.
Detailed description of the invention
Fig. 1 is that magnetic bio charcoal/ferriferrous sulfide composite material x-ray powder prepared by the embodiment of the present invention 1 spreads out
Penetrate figure.
Specific embodiment
Below in conjunction with Figure of description, the present invention will be further described, and provides specific embodiment, but of the invention
Protection scope is not limited to that.
Embodiment 1
A kind of magnetic bio charcoal/ferriferrous sulfide composite material for hexavalent chromium removal, is made by following steps:
1) using rice husk as raw material, the thermal cracking 2h under 600 DEG C of limited oxygen condition obtains black bio charcoal solid；
2) 1) middle gained charcoal is crushed into 5min through the pulverizer that power is 1000W, gained powder sieves with 100 mesh sieve；
3) gained charcoal powder in 2) is taken to remove the impurity such as ash content, residue in charcoal through 0.1mol/L hydrochloric acid washing by soaking；
4) 3) middle gained charcoal powder is placed in air dry oven, 90 DEG C of set temperature, dry 6h, obtained solid is as clean
Net charcoal；
5) green vitriol is dissolved in 25mL ethylene glycol；
6) 1.0 g charcoals are sufficiently mixed with iron-containing liquor in step 5) by ultrasound；
7) L-cysteine is dissolved in 25 milliliters of ethylene glycol, step 5) and 7) in L-cysteine used and seven hydrated sulfuric acids it is sub-
Iron dosage is as shown in table 1；
8) solution in step 7) is added to dropwise in the mixed liquor of step 6), control time for adding is 10min；
9) 8) mixed liquor in is transferred to 100mL polytetrafluoroethylliner liner, and in reaction cartridge kettle；
10) above-mentioned stainless steel cauldron is placed in air dry oven, is arranged 180 DEG C of reaction temperature, reaction time 12h；
11) to after reaction, cooled to room temperature takes out liner from reaction kettle in 10), it is solid to collect liner at the bottom
Body；
12) 11) obtained solid is respectively washed 3 times through water and ethyl alcohol, 6h is dried in vacuo under the conditions of 60 DEG C, obtained solid is magnetism
Magnetic bio charcoal/ferriferrous sulfide composite material.
13) according to Fe in composite material obtained by ratio in table 13S4/ charcoal ratio is 5%, 10%, 20%, 30%, therefore is numbered
For FC-5, FC-10, FC-20, FC-30.
Table 1
By above-mentioned resulting magnetic bio charcoal/ferriferrous sulfide composite material as being scanned under x-ray powder diffraction instrument, result
As shown in Figure 1, crystallinity gradually increases with the raising of ferriferrous sulfide ratio, while retaining charcoal characteristic diffraction peak,
Illustrate that synthesized material is magnetic bio charcoal/ferriferrous sulfide composite material.
Embodiment 2
Four kinds of magnetic bio charcoal/ferriferrous sulfide composite materials prepared by embodiment 1 are applied to the waste water containing hexavalent chromium
Processing comprising the steps of:
1) it weighs appropriate potassium bichromate to be dissolved in ultrapure water, is made into the hexavalent chromium stock solution of 20mg/L；
2) take above-mentioned Cr VI stock solution 50mL in 100mL conical flask, respectively weigh 0.04g FC-5, FC-10, FC-20,
FC-30 composite material is immediately transferred into constant temperature oscillator in the solution, and revolving speed 200r/min is arranged, and temperature is 25 DEG C；
3) respectively with to take 1mL sample to mix with two hydrazine color developing agent of 2mL diphenyl phosphinylidyne aobvious after reacting 5,10,20,30,40,60min
Color, and mixed liquor absorbance is measured using ultraviolet-uisible spectrophotometer；
Gained absorbance after reaction solution colour developing after above-mentioned reaction is analyzed and processed, the results are shown in Table 2, can therefrom see
Out with the increase of ferriferrous sulfide ratio in composite material, the efficiency for removing Cr VI is gradually increased.
Table 2
Embodiment 3
Magnetic bio charcoal/ferriferrous sulfide composite material prepared by embodiment 1 is applied to the processing of the waste water containing hexavalent chromium,
It comprises the steps of:
1) it weighs appropriate potassium bichromate to be dissolved in ultrapure water, is made into the hexavalent chromium stock solution of 20mg/L；
2) it takes above-mentioned Cr VI stock solution 50mL in 100mL conical flask, weighs 0.01,0.02,0.03,0.04,0.05g respectively
FC-30 composite material is immediately transferred into constant temperature oscillator in the solution, and revolving speed 200r/min is arranged, and temperature is 25 DEG C；
3) respectively with to take 1mL sample to mix with two hydrazine color developing agent of 2mL diphenyl phosphinylidyne aobvious after reacting 5,10,20,30,40,60min
Color, and mixed liquor absorbance is measured using ultraviolet-uisible spectrophotometer；
Gained absorbance after reaction solution colour developing after above-mentioned reaction is analyzed and processed, result such as table 3, it can be seen that with
The increase of composite material concentration in reaction solution, removal efficiency of chrome gradually rise, when composite material concentration is 0.04, Cr VI
Removal effect highest.
Table 3
Embodiment 4
Magnetic bio charcoal/ferriferrous sulfide composite material prepared by embodiment 1 be applied to different initial pH values Cr VI from
The processing of sub- waste water comprising the steps of:
1) it weighs appropriate potassium bichromate to be dissolved in ultrapure water, is made into the hexavalent chromium stock solution of 20mg/L；
2) take above-mentioned Cr VI stock solution 50mL in 100mL conical flask, with the dilute hydrochloric acid and sodium hydroxide solution tune of 1mmol/L
The initial pH for saving Cr VI stock solution is respectively 3.2,5.2,7.2,9.2,11.2, weighs 0.04g FC-30 composite material in this
It in solution, and is immediately transferred into constant temperature oscillator, revolving speed 200r/min is set, temperature is 25 DEG C；
3) respectively with to take 1mL sample to mix with two hydrazine color developing agent of 2mL diphenyl phosphinylidyne aobvious after reacting 5,10,20,30,40,60min
Color, and mixed liquor absorbance is measured using ultraviolet-uisible spectrophotometer；
Gained absorbance after reaction solution colour developing after above-mentioned reaction is analyzed and processed, result such as table 4, it can be seen that with
The increase of the initial pH of reaction solution, removal efficiency of chrome first increase and reduce afterwards, when the initial pH of reaction solution be 5.2 when, Cr VI is gone
Except effect highest.
Table 4
Claims (6)
1. a kind of composite material for hexavalent chromium removal, it is characterised in that the composite material is using charcoal as carrier, with molten
Agent thermal method carried magnetic ferriferrous sulfide, wherein the mass ratio of magnetic ferriferrous sulfide is 5-30%.
2. a kind of preparation method of the composite material for hexavalent chromium removal, it is characterised in that the preparation method is by following steps group
At:
1) using rice husk as raw material, the thermal cracking 2-4h under 400-600 DEG C of limited oxygen condition obtains black bio charcoal solid；
2) black bio charcoal solid made from step 1) is crushed into 5min through the pulverizer that power is 1000W, gained powder crosses 100
Mesh；
3) it takes powder made from step 2 through 0.1mol/L hydrochloric acid washing by soaking, removes the impurity such as ash content, residue in charcoal；
4) it will be placed in air dry oven by the charcoal powder of step 3) processing, 90 DEG C of set temperature, dry 6h, gained is solid
Body is clean charcoal, for use；
5) green vitriol is dissolved in 25mL ethylene glycol；
6) 1.0g charcoal is sufficiently mixed with iron-containing liquor in step 5) by ultrasound；
7) L-cysteine is dissolved in 25 milliliters of ethylene glycol；
8) solution in step 7) is added to dropwise in the mixed liquor of step 6), control time for adding is 10-15min, and mixing is made
Liquid；
9) mixed liquor made from step 8) is transferred to 100mL polytetrafluoroethylliner liner, and in reaction cartridge kettle；
10) above-mentioned stainless steel cauldron is placed in air dry oven and is reacted；
11) after reaction to step 10), cooled to room temperature takes out liner from reaction kettle, and it is solid to collect liner at the bottom
Body；
12) step 11) obtained solid is respectively washed 2-3 times through water and ethyl alcohol, 4-6h, gained is dried in vacuo under the conditions of 50-60 DEG C
Solid is magnetic bio charcoal/ferriferrous sulfide composite material.
3. a kind of preparation method of the composite material for hexavalent chromium removal as claimed in claim 2, it is characterised in that step
5) dosage of green vitriol is 0.189-1.132g in.
4. a kind of preparation method of the composite material for hexavalent chromium removal as claimed in claim 2, it is characterised in that step
7) dosage of L-cysteine is 0.082-0.493g in.
5. a kind of preparation method of the composite material for hexavalent chromium removal as claimed in claim 2, it is characterised in that step
10) drying temperature of air dry oven is 160-200 DEG C in, reaction time 12-24h.
6. the place that magnetic bio charcoal/ferriferrous sulfide composite material prepared by claim 2 is applied to the waste water containing hexavalent chromium
Reason, it is characterised in that mainly comprise the steps that
1) 0.2-1.0g/L magnetic bio charcoal/tetra- fluidisation three-iron composite woods are added into the hexavalent chromium wastewater that concentration is 20mg/L
Material, adjusting pH value are 3.2-11.2, and mixed liquor is made；
2) mixed liquor is placed in constant temperature oscillator, 1h is shaken with 200r/min revolving speed, after the reaction was completed with magnet by composite wood
Material is separated with waste water, completes the removal of hexavalent chromium.
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Cited By (8)
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| CN109939643A (en) * | 2019-04-09 | 2019-06-28 | 西安工业大学 | α-Fe2O3Adulterate the preparation method and applications of charcoal |
| CN110340132A (en) * | 2019-06-28 | 2019-10-18 | 广东自华科技有限公司 | A kind of method that charcoal base Zero-valent Iron cooperates with reparation chromium-polluted soil with microorganism |
| CN110652964A (en) * | 2019-11-06 | 2020-01-07 | 北京高能时代环境技术股份有限公司 | Magnetic iron-based biochar composite material, preparation method and application |
| CN110980858A (en) * | 2019-11-25 | 2020-04-10 | 中国科学技术大学 | Preparation method and application of biochar-loaded nano zero-valent iron sulfide material |
| CN111925806A (en) * | 2020-07-20 | 2020-11-13 | 华东理工大学 | Sulfur-doped nano ferroferric oxide/biochar composite material as well as preparation method and application thereof |
| CN113788523A (en) * | 2021-10-08 | 2021-12-14 | 长春工业大学 | Preparation of modified activated carbon composite material |
| CN115608321A (en) * | 2022-10-27 | 2023-01-17 | 广东工业大学 | Composite material for efficiently treating hexavalent chromium pollution in environment and preparation method and application thereof |
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