CN108176368A - A kind of charcoal Chitosan Composites and its preparation method and application - Google Patents
A kind of charcoal Chitosan Composites and its preparation method and application Download PDFInfo
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- CN108176368A CN108176368A CN201711260508.5A CN201711260508A CN108176368A CN 108176368 A CN108176368 A CN 108176368A CN 201711260508 A CN201711260508 A CN 201711260508A CN 108176368 A CN108176368 A CN 108176368A
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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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- 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
- B01J20/28—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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- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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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
- B01J20/28054—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 surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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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
- C02F1/283—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
- C02F1/28—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention discloses a kind of charcoal Chitosan Composites and its preparation method and application, preparation method to include the following steps：(a) biological material and soluble ferric iron salt, sulfuric acid solution are mixed to get mixed solution, mixed solution is ultrasonically treated, then filtered, is dry, obtaining biological carbon materials head product BC；(b) biological carbon materials L Fe are obtained by high temperature pyrolysis head product；(c) Chitosan powder of certain mass is dissolved in acetum and forms mixed solution, the biological carbon materials L Fe samples of certain mass is taken to be added in above-mentioned mixed liquor and heating stirring is carried out in water-bath, pH value to alkalinity and filtering drying is adjusted and charcoal Chitosan Composites LC Fe is made.The method of the present invention, manufacture craft is easy, and modified biological carbon materials are prepared to Cr in non-secondary pollution6+And Cu2+Adsorption capacity it is big, adsorption rate is high, has a wide range of applications in terms of wastewater treatment and purification.
Description
Technical field
The invention belongs to Materials Science and Engineering field, more particularly to a kind of preparation side of charcoal Chitosan Composites
Method and its in adsorbing heavy metal in water Cr6+And Cu2+Application.
Background technology
With the fast development of modern industrial and agricultural production, heavy metal passes through mining, metal smelt, intermetallic composite coating and change
The natural sources forms such as man-made pollution sources and geologic erosion, weathering such as work production waste water enter water body, and are endangered by food chain
The life and health of the mankind.More seriously heavy metal pollution has concealment, chronicity, irreversibility and consequence seriousness
The features such as.About the Treatment process of heavy metal pollution, at present, precipitation, UF membrane, ion exchange, absorption etc. are mostly taken.Absorption
Method mostly using add in adsorbent method, common adsorbent such as activated carbon, resin, ore etc., wherein charcoal due to
The features such as its source is wide, of low cost, porosity and the absorption for being widely used in heavy metal.Such as patent publication No. CN
105236507A discloses the side of Cr VI in the beta-cyclodextrin chitosan adsorbent removal waste water compound with walnut shell charcoal
Method, Wang Xufeng et al. (Treatment of Industrial Water .2017 in January the 1st phases of volume 37) uses KMnO4Modified corn core charcoal, and be used for
Adsorb the Cu in water2+And ammonia nitrogen, but these adsorbents are to the heavy metal Cu in waste water2+And Cr6+Adsorption capacity than relatively low, compared with
Hardly possible realizes efficient adsorption efficiency, therefore the adsorbent for preparing high adsorption capacity becomes a urgent problem to be solved.
Invention content
It is an object of the invention in view of the above-mentioned problems, by the modification to biological carbon material, provide a kind of charcoal shell
The preparation method of polysaccharide composite material, charcoal Chitosan Composites prepared by this method are big with adsorption capacity, adsorption rate
Height, can high-volume production, substantially increase the efficiency of sewage disposal.
A kind of preparation method of charcoal Chitosan Composites, which is characterized in that include the following steps：
(1) luffa for take cleaning first, shredding is mixed with soluble ferric iron salt, then adds in H2SO4Solution, gained
It is filtered after mixture is sonicated, is finally dried in vacuo filtrate, obtain biological carbon materials head product；
(2) 2~4h is pyrolyzed to biological carbon materials head product under 700 DEG C~900 DEG C of temperature condition, and washing is straight repeatedly
To neutrality, biological carbon materials are obtained；
(3) Chitosan powder is taken to be dissolved in acetum and forms mixed solution, biological carbon materials are added to above-mentioned mixing
Heating stirring is carried out in solution and in water-bath；The mass ratio of biological carbon materials and chitosan is 1:0.25~1:1, it is added dropwise
Solution to the pH value that NaOH solution adjusts in water-bath is 8.5~9.5 and continues to stir, finally by the insoluble matter mistake in solution
Filter, washs, is dried to obtain charcoal Chitosan Composites.
Preferably, the soluble ferric iron salt described in step (1) is FeCl3﹒ 6H2O、Fe2(SO4)3With Fe (NO3)3In appoint
Meaning is one or more of, a concentration of 0.5mol/L~1.5mol/L of the soluble ferric iron salt.
Preferably, the quality proportioning of the luffa described in step (1) and soluble ferric iron salt is 1:4~1:8.
Preferably, step (1) soluble ferric iron salt and H2SO4Volume ratio be 2:1~3:1, H2SO4It is a concentration of
0.98mol/L。
Preferably, the time being ultrasonically treated in step (1) is 2h, frequency 100KHz, and the vacuum drying temperature is
50 DEG C~100 DEG C, the time is 8~12h.
Preferably, a concentration of 2mg/ml~6mg/ml of the chitosan in acetum, the mixed solution in step (3)
Heating temperature for 40 DEG C~70 DEG C, mixing time is 0.5h~2h.
Preferably, the drying condition described in step (3) is drying 12h~18h at a temperature of 90 DEG C~150 DEG C.
Preferably, all solution are with nitrogen air blowing 5-10 minutes in step (1) preparation process, and step (2) whole process is in nitrogen
It is carried out in gas atmosphere.
The present invention is had the following advantages and advantageous effect relative to the prior art：
(1) present invention is modified to obtain and has larger specific surface area (BET specific surface area is using natural biological carbon
134.68m2g-1), flourishing pore structure (total pore volume 0.069cm3/ g, Micropore volume 0.025cm3/ g) and a variety of surface functional groups,
Be conducive to adsorb heavy metal ion.
(2) pass through FeCl3The biological carbon surface of processing, forms a large amount of pore channels, makes life after negative magnetic is carried out to charcoal
The specific surface area increase of object charcoal, surface irregularity, number cells increase, and provide more adsorption sites.Biological carbon surface
With iron ion complexation reaction occurs for functional group, a kind of charcoal Chitosan Composites is formed, for heavy metal ion in solution
With preferable suction-operated.After absorption, used biological carbon Chitosan Composites are again due to its ferromagnetic characteristic
It can be attracted by magnetic force and be easily collected very much.
(3) the charcoal Chitosan Composites that the present invention obtains, remain the structure of charcoal, and be successfully introduced into shell
Glycan, compared with biological carbon materials, charcoal Chitosan Composites are to the Cu in water2+And Cr6+Adsorption effect it is more bright
It is aobvious, adsorption capacity bigger.
(4) preparation method of the invention is simple and easy to operate, and preparation process takes short, easy large-scale production.
Description of the drawings
Fig. 1 is the SEM figures of charcoal Chitosan Composites sample prepared by embodiment 1.
Fig. 2 is the SEM figures of charcoal Chitosan Composites sample prepared by embodiment 2.
Fig. 3 is the XRD diagram of charcoal Chitosan Composites sample prepared by embodiment 1,2,3.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the present invention is done and is further described in detail, but the present invention will
The protection domain asked is not limited to the range of embodiment expression.
Embodiment 1：
Take the FeCl of the 1.0mol/L of luffa and 200ml after 10g crushing3﹒ 6H2O is mixed, and then adds in 50ml
0.98mol/L sulfuric acid.Gained mixture is ultrasonically treated 2h, and frequency 100KHz is filtered after mixing, then in vacuum
Dry 12h (70 DEG C), obtains biological carbon materials head product BC in drying box.Head product is heated to 700 DEG C under nitrogen atmosphere,
2h is pyrolyzed, and is washed repeatedly to neutrality, obtains biological carbon materials L-Fe.It is (pure that the Chitosan powder of 2g is first dissolved in 1.75mol/L
It in degree acetic acid 98%), adds in 2g biological carbon materials L-Fe samples to above-mentioned acetic acid, chitosan mixed liquor, and by compound
Heating stirring (60 DEG C, 2h) is carried out in water-bath, until being sufficiently mixed.Later, NaOH solution is added drop-wise in mixture directly
To PH=9, compound is continued to stir.Finally the insoluble matter in solution to be filtered, washing, drying (80 DEG C, 8h) is spare, just
To final product charcoal Chitosan Composites sample LC-Fe-1.
Embodiment 2：
Take the FeCl of the 1.0mol/L of luffa and 300ml after 10g crushing3﹒ 6H2O is mixed, and then adds in 100ml
0.98mol/L sulfuric acid.Gained mixture is ultrasonically treated 2h, and frequency 100KHz is filtered after mixing, then in vacuum
Dry 12h (100 DEG C), obtains biological carbon materials head product BC in drying box.Head product is heated to 700 under nitrogen atmosphere
DEG C, 2h is pyrolyzed, and washed repeatedly to neutrality and obtain biological carbon materials L-Fe.The Chitosan powder of 1g is first dissolved in 1.75mol/L
In the acetic acid of (purity 98%), add in 2g biological carbon materials L-Fe samples to above-mentioned acetic acid, chitosan mixed liquor, and by chemical combination
Object carries out heating stirring (60 DEG C, 2h) in water-bath, until being sufficiently mixed.Later, NaOH solution is added drop-wise in mixture
Until PH=9, compound is continued to stir.Finally the insoluble matter in solution is filtered, washing, drying (80 DEG C, 8h) is spare, just
Obtain final product charcoal Chitosan Composites sample LC-Fe-2.
Embodiment 3：
Take the FeCl of the 1.0mol/L of luffa and 200ml after 10g crushing3﹒ 6H2O is mixed, and then adds in 100ml
0.98mol/L sulfuric acid.Gained mixture is ultrasonically treated, and frequency 100KHz, time 2h are filtered, so after mixing
The dry 12h (50 DEG C) in vacuum drying chamber afterwards, obtains biological carbon materials head product BC.Head product is heated under nitrogen atmosphere
To 700 DEG C, 2h is pyrolyzed, and washed repeatedly to neutrality and obtain biological carbon materials L-Fe.First the Chitosan powder of 0.75g is dissolved in
In the acetic acid of 1.75mol/L (purity 98%), 1g biological carbon materials L-Fe samples are added in above-mentioned acetic acid, chitosan mixed liquor
In, and compound is carried out to heating stirring (60 DEG C, 2h) in water-bath, until being sufficiently mixed.Later, NaOH solution is added dropwise
Into mixture until PH=9, compound is continued to stir.Finally the insoluble matter in solution is filtered, washing, drying (80 DEG C,
It is 8h) spare, just obtain final product charcoal Chitosan Composites sample LC-Fe-3.
Instance analysis：
SEM electron-microscope scannings are carried out to the charcoal Chitosan Composites of gained, as a result as shown in Figure 1 and Figure 2.It can by Fig. 1
To find out, LC-Fe-1 samples prepared by embodiment 1 are in granular form and crystal is stacked with, from figure 2 it can be seen that implementing
It can significantly observe that particle is reduced in LC-Fe-2 composite materials prepared by example 2, show that chitosan is combined to the degree on material more
It is smaller.
Surface area of sample prepared by embodiment 1 is carried out using ASAP2020 specific surface areas and distribution of pores structural test machines
Characterization, design parameter are as shown in table 1.Modified charcoal has larger specific surface area, and the physical absorption for heavy metal provides
Site, meanwhile, it is also beneficial to the compound of chitosan.
1 porous material structural parameters of table
XRD diffraction analysis is carried out to the charcoal Chitosan Composites obtained in embodiment 1,2,3, as shown in figure 3, real
Charcoal-the Chitosan Composites for applying the preparation of example 2,3 show characteristic peak similar to Example 1, but peak intensity is different, shows
Composite material assigns magnetic.
Adsorption experiment is carried out to the charcoal Chitosan Composites obtained in embodiment 1,2,3, method is as follows：
The Cu that 100mL is prepared is added in 250mL conical flasks2+Or Cr6+Solution, then add respectively a certain amount of adsorbent (LC-Fe-1,
LC-Fe-2, LC-Fe-3), constant-temperature table is placed in, 30 DEG C, adsorption experiment is carried out under the conditions of 150r/min, timing sampling is divided
Analysis.Obtained analysis data such as table 2, shown in table 3：
Table 2Cu2+Desorption balance data in Examples 1 to 3 on prepared specimen material
Table 3Cr6+Desorption balance data in Examples 1 to 3 on prepared specimen material
It, should under conditions of initial concentration is 100mg/L by table 2, table 3 it is found that the adsorption effect of LC-Fe-1 is relatively preferable
Composite material is 149.79mg/g to the adsorbance of copper, and Cu is removed for 82.8mg/g. to the adsorbance of Cr VI2+With Cr6+Change
Patent disclosed in learning adsorbent has the adsorbent of biological carbon materials, as patent publication No. 201510585777.3 discloses β-ring paste
The adsorbance of smart chitosan and the adsorbent of the compound preparation of walnut shell charcoal is to Cr (VI) in 47.4mg/g, Wang Xufeng et al.
(Treatment of Industrial Water the 1st phase of volume 37) uses KMnO4Modified corn core charcoal, and for adsorbing the Cu in water2+And ammonia nitrogen, it is right
Cu2+Maximal absorptive capacity can reach 88.50mg/g.In contrast, more than biological carbon materials are to Cu2+And Cr6+Adsorption capacity compared with
Low, biological carbon materials effect prepared by luffa is more preferable.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of preparation method of charcoal Chitosan Composites, which is characterized in that include the following steps：
(1) luffa for take cleaning first, shredding is mixed with soluble ferric iron salt, then adds in H2SO4Solution, gained mixing
It is filtered after object is sonicated, is finally dried in vacuo filtrate, obtain biological carbon materials head product；
(2) 2~4h is pyrolyzed to biological carbon materials head product under 700 DEG C~900 DEG C of temperature condition, and is washed in repeatedly
Property, obtain biological carbon materials；
(3) Chitosan powder is taken to be dissolved in acetum and forms mixed solution, biological carbon materials are added to above-mentioned mixed solution
In and carry out in water-bath heating stirring；The mass ratio of biological carbon materials and chitosan is 1:0.25~1:1, it is molten that NaOH is added dropwise
Solution to the pH value that liquid adjusts in water-bath is 8.5~9.5 and continues to stir, and finally filters the insoluble matter in solution, washing,
It is dried to obtain charcoal Chitosan Composites.
2. preparation method according to claim 1, which is characterized in that the soluble ferric iron salt described in step (1) is FeCl3﹒
6H2O、Fe2(SO4)3With Fe (NO3)3In any one or a few, a concentration of 0.5mol/L of the soluble ferric iron salt~
1.5mol/L。
3. preparation method according to claim 2, which is characterized in that luffa and soluble iron described in step (1)
The quality proportioning of salt is 1:4~1:8.
4. according to the preparation method described in claims 1 or 2 or 3, which is characterized in that soluble ferric iron salt described in step (1) with
H2SO4Volume ratio be 2:1~3:1, H2SO4A concentration of 0.98mol/L.
5. preparation method according to claim 4, which is characterized in that the time being ultrasonically treated in step (1) is 2h, frequency
For 100KHz, the vacuum drying temperature is 50 DEG C~100 DEG C, and the time is 8~12h.
6. according to the preparation method described in claims 1 or 2 or 3, which is characterized in that chitosan is in acetum in step (3)
In a concentration of 2mg/ml~6mg/ml, the heating temperature of the mixed solution is 40 DEG C~70 DEG C, mixing time for 0.5h~
2h。
7. according to the preparation method described in claims 1 or 2 or 3, which is characterized in that drying condition is 90 described in step (3)
DEG C~150 DEG C at a temperature of dry 12h~18h.
8. according to the preparation method described in claims 1 or 2 or 3, which is characterized in that all solution in step (1) preparation process
With nitrogen air blowing 5-10 minutes, step (2) is whole to be carried out in nitrogen atmosphere.
9. charcoal Chitosan Composites prepared by claim 1~8 any one the method.
10. the application of charcoal Chitosan Composites described in claim 9, which is characterized in that the material is used to adsorb in water
Heavy metal ion Cr6+And Cu2+。
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| CN108905982A (en) * | 2018-07-18 | 2018-11-30 | 广西南宁荣威德新能源科技有限公司 | It is a kind of for removing the preparation method of the adsorbent of aflatoxin in peanut oil |
| CN109364897A (en) * | 2018-12-29 | 2019-02-22 | 山东省分析测试中心 | A kind of cross-linked chitosan-charcoal micro-sphere absorption material and preparation method thereof |
| CN109589941A (en) * | 2018-12-26 | 2019-04-09 | 农业部环境保护科研监测所 | Preparation method, magnetic composite and its application of magnetic composite |
| CN110124638A (en) * | 2019-06-05 | 2019-08-16 | 清华大学深圳研究生院 | The chitosan of grafted by quaternary ammonium group and biological carbon composite and its preparation method and application |
| CN110124639A (en) * | 2019-06-05 | 2019-08-16 | 清华大学深圳研究生院 | The chitosan of carboxyl grafting and biological carbon composite and its preparation method and application |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108905982A (en) * | 2018-07-18 | 2018-11-30 | 广西南宁荣威德新能源科技有限公司 | It is a kind of for removing the preparation method of the adsorbent of aflatoxin in peanut oil |
| CN109589941A (en) * | 2018-12-26 | 2019-04-09 | 农业部环境保护科研监测所 | Preparation method, magnetic composite and its application of magnetic composite |
| CN109364897A (en) * | 2018-12-29 | 2019-02-22 | 山东省分析测试中心 | A kind of cross-linked chitosan-charcoal micro-sphere absorption material and preparation method thereof |
| CN110124638A (en) * | 2019-06-05 | 2019-08-16 | 清华大学深圳研究生院 | The chitosan of grafted by quaternary ammonium group and biological carbon composite and its preparation method and application |
| CN110124639A (en) * | 2019-06-05 | 2019-08-16 | 清华大学深圳研究生院 | The chitosan of carboxyl grafting and biological carbon composite and its preparation method and application |
| CN110354804A (en) * | 2019-07-29 | 2019-10-22 | 江西省科学院 | A kind of its application of the preparation method of wetland plant and pig manure compound bio charcoal |
| CN110496605A (en) * | 2019-08-26 | 2019-11-26 | 南京大学 | A kind of chitosan-biology carbon composite and application method |
| CN110586046A (en) * | 2019-09-27 | 2019-12-20 | 常州大学 | Preparation method of organic modified biochar for treating heavy metal cadmium in wastewater |
| CN110975835A (en) * | 2019-12-19 | 2020-04-10 | 东北农业大学 | Preparation method of biochar-ferroferric oxide-chitosan composite material |
| CN110975835B (en) * | 2019-12-19 | 2024-04-16 | 东北农业大学 | Preparation method of biochar-ferroferric oxide-chitosan composite material |
| CN113617337A (en) * | 2021-08-25 | 2021-11-09 | 齐齐哈尔大学 | Preparation method and application of adsorbent based on garden waste |
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