CN109364897A - A kind of cross-linked chitosan-charcoal micro-sphere absorption material and preparation method thereof - Google Patents
A kind of cross-linked chitosan-charcoal micro-sphere absorption material and preparation method thereof Download PDFInfo
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- CN109364897A CN109364897A CN201811642298.0A CN201811642298A CN109364897A CN 109364897 A CN109364897 A CN 109364897A CN 201811642298 A CN201811642298 A CN 201811642298A CN 109364897 A CN109364897 A CN 109364897A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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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
- B01J20/22—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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
Cross-linked chitosan of the invention-charcoal micro-sphere absorption material, including chitosan, charcoal powder and crosslinking agent, chitosan are uniformly mixed with charcoal powder.Preparation method are as follows: chitosan is added in dilute acid soln first, stirs into colloidal sol；Then charcoal powder is added in colloidal sol, stirring forms mixed sols；Then mixed sols is instilled in alkaline solution and forms microballoon；Microballoon is rinsed to neutrality, and microballoon is impregnated in crosslinking agent, is rinsed with deionized water to neutrality after immersion.Cross-linked chitosan of the invention-charcoal micro-sphere absorption material and preparation method thereof, prepared cross-linked chitosan, biological carbon microspheres have the characteristics that pore structure is flourishing, coarse, complicated, with biggish specific surface area, to in water body heavy metal ion and organic dyestuff have good adsorption capacity, it can completely be withdrawn after use, solve the problems, such as to be difficult to the secondary pollution caused by completely recycling when chitosan, charcoal adsorb in powder form.
Description
Technical field
The present invention relates to a kind of cross-linked chitosan-charcoal micro-sphere absorption materials and preparation method thereof, more specifically, especially
It is related to a kind of cross-linked chitosan-charcoal that can be used for adsorbing the pollutants such as heavy metal, organic dyestuff in water body
Micro-sphere absorption material and preparation method thereof.
Background technique
Due to serious exploitation industrialized fast-developing and to natural resources, water pollution is caused to become protection environment
One of maximum threat.If the content of polluter has been more than environment carrying limit in water body, the self-purification capacity of environment will subtract
It is weak, and then aquatic ecosystem balance is destroyed, huge threat is also resulted in the health of the mankind.Heavy metal wastewater thereby mainly comes
Derived from industrial and mining enterprises, have the characteristics that biological non-degradable, and can be acted on by food chain and enter human body, and is rich in human body
Collection, so as to cause various diseases and disorder, finally causes to seriously endanger to human health.For example hexavalent chromium is a kind of
Toxic heavy metal has the characteristics that dissolubility is high-leveled and difficult to be precipitated, and many detrimental effects is generated to animals and plants, into human body
After can become a kind of potent carcinogen.Waste water from dyestuff is mainly derived from weaving, rubber and dyeing, big with discharge amount,
The features such as organic pollutant content is high, change of water quality is big, it is standby because of its toxic action to animals and plants or even the mankind in environment
Concerned, wherein organic dyestuff is a kind of important organic compound, and chemical mechanical is stablized, and biodegradability is poor, therefore
Increase the processing difficulty of waste water from dyestuff.
The physical chemistry processing method of common at present processing heavy metal and organic dye waste water is chemical precipitation method, chemistry
Oxidation-reduction method, membrane separation process, ion-exchange, solvent extraction, electrolysis method, absorption method etc., these methods cost, effectively
Property and environment influence that aspect is different, and absorption method has many advantages, such as simple, effective, at low cost, obtained in water process at present
It is widely applied.However, finding the friendly adsorbent of efficient, low cost, ecology is the key that show absorption advantage.
The amino (- NH of chitosan2) and hydroxyl (- OH) can be used as coordination and reaction site, be removal waste water in it is organic
One of object and the most promising adsorbent of heavy metal, mainly by chitin, (nature is only second to the second of cellulose to chitosan
Biopolymer abundant) deacetylation forms, there is attraction economically, however, the mechanical strength of chitosan beads is low, acid
It is unstable, limit the application of its absorption.
Charcoal is a kind of porous carbon material newly developed, is to pass through biomass pyrolytic under conditions of hypoxemia or anaerobic
For the of generation compared with other kinds of adsorbent, useless biomass has many advantages, such as that cost-effectiveness is high, safe and reliable, answers extensively
It is produced for charcoal.Charcoal large specific surface area has the potentiality of absorption pollutant.The charcoal of report is in pollutant removal
In application be to be carried out in suspension system mostly, since charcoal is difficult to separate with purified solution, may cause secondary dirt
Dye problem.This problem limits overall application of the charcoal in water process.
Chitosan and charcoal are effectively assembled, chitosan mechanical strength is not only increased and acid is stablized, it is also easy
Avoid secondary pollution in being separated from water, have economically with technical feasibility.
Summary of the invention
The present invention in order to overcome the shortcomings of the above technical problems, provide it is a kind of can be used for in water body organic dyestuff,
The cross-linked chitosan that the pollutants such as heavy metal are adsorbed-charcoal micro-sphere absorption material and preparation method thereof.
Cross-linked chitosan of the invention-charcoal micro-sphere absorption material, including chitosan, charcoal powder and crosslinking agent,
Chitosan is uniformly mixed with charcoal powder.
Cross-linked chitosan of the invention-charcoal micro-sphere absorption material, the mass ratio of the chitosan and charcoal powder
For 1:0.3~0.8.
Cross-linked chitosan of the invention-charcoal micro-sphere absorption material, the crosslinking agent are glutaraldehyde, the biology powdered carbon
End is made by reed straw.
Cross-linked chitosan of the invention-charcoal micro-sphere absorption material preparation method, is prepared via a method which: first
Chitosan is added in dilute acid soln, colloidal sol is stirred into；Then charcoal powder is added in colloidal sol, it is molten that stirring forms mixing
Glue；Then mixed sols is instilled in alkaline solution and forms microballoon；Microballoon is rinsed to neutrality, and microballoon is soaked in crosslinking agent
Bubble, is rinsed to neutrality with deionized water after immersion, obtains cross-linked chitosan-biology carbon microspheres.
Cross-linked chitosan of the invention-charcoal micro-sphere absorption material preparation method is come real especially by following steps
It is existing:
M1g chitosan is added in the acetum that sufficient amount volume fraction is 2%, at 40 DEG C by a) dissolution of chitosan
Under the conditions of stir to forming uniform colloidal sol；M2g charcoal powder is slowly added to step a) and obtained by the b) addition of charcoal powder
In the colloidal sol taken, and continue to stir under the conditions of 40 DEG C of temperature, charcoal powder is made to be uniformly dispersed in colloidal sol；C) prepared by
The mixed sols obtained in step b) is added dropwise in the NaOH solution sedimentation basin of 2mol/L using needle tubing, is formed by microballoon
Microballoon of uniform size；After being added dropwise, the microballoon in solution is filtered out and is cleaned with deionized water to neutrality；D) is micro-
The microballoon obtained in step c) is placed in the glutaraldehyde water solution that volume fraction is 2% by the crosslinking of ball, impregnates certain period of time
Afterwards, it filters microballoon and is cleaned with deionized water to neutrality, obtain cross-linked chitosan-biology carbon microspheres.
Cross-linked chitosan of the invention-charcoal micro-sphere absorption material preparation method, charcoal described in step b)
The preparation process of powder is as follows:
B-1) reed dries and is crushed, and is first cleaned up reed straw with deionized water, then in 100 DEG C of temperature strip
Reed straw is dried under part, finally shreds reed straw；Reed after shredding is put into porcelain by the b-2) thermal activation of reed
It in crucible, is compacted and the sealing that closes the lid, is put into muffle furnace, 500 DEG C and constant temperature 2h are heated to, so that reed thermal activation；b-
3) is ground up, sieved, and is taken out after the carbonizing production after thermal activation is cooled to room temperature, and the sieve of 100 mesh numbers is crossed after grinding；b-4).
Cleaning and drying remove ash content, then use first with the carbonizing production obtained in the HCl solution cleaning step b-3 of 1mol/L)
Distilled water is cleaned to neutrality；Finally by carbonizing production, drying to constant weight, that is, has prepared charcoal powder.
Cross-linked chitosan of the invention-charcoal micro-sphere absorption material preparation method, in step a), M1g chitosan is mixed
Enter in 2% acetum that volume is 50*M1 ml；The ratio of the mass M 2 of the mass M 1 and charcoal powder of the chitosan
For 1:0.3~0.8；In step d), the period that microballoon impregnates in glutaraldehyde solution is 4h.
The beneficial effects of the present invention are: cross-linked chitosan of the invention-charcoal micro-sphere absorption material and preparation method thereof,
Using will be added in dilute acid soln before and after chitosan, charcoal powder and stir into colloidal sol, alkaline solution is then instilled again
Microballoon is formed, finally microballoon is immersed in crosslinking agent and prepares cross-linked chitosan-biology carbon microspheres, prepared crosslinking shell is poly-
Sugar, biological carbon microspheres have the characteristics that pore structure is flourishing, coarse, complicated, have biggish specific surface area, aperture is mainly concentrated
Within the scope of 2~20nm；It can be used as effective adsorbent material in sewage disposal process, since it is inhaled in the form of microballoon
It is attached, can completely be withdrawn after use, solve chitosan, be difficult to when charcoal adsorbs in powder form completely to recycle caused by
Secondary pollution problem, beneficial effect is significant, is suitable for the application of popularization.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of chitosan microball in the present invention；
Fig. 2 is the scanning electron microscope diagram of biological carbon microspheres in the present invention；
Fig. 3 is cross-linked chitosan of the invention-biology carbon microspheres scanning electron microscope diagram；
Fig. 4 is chitosan microball CH, biological carbon microspheres C, cross-linked chitosan-biology carbon microspheres CSB infrared spectroscopy in the present invention
Figure；
Fig. 5 is chitosan microball CH in the present invention, biological carbon microspheres C, cross-linked chitosan-biology carbon microspheres CSB to Cr (VI) from
The comparison figure of sub- removal rate.
Specific embodiment
The invention will be further described with embodiment with reference to the accompanying drawing.
Cross-linked chitosan of the invention-biology carbon microspheres are made of chitosan, charcoal powder and crosslinking agent, chitosan with
Charcoal powder uniformly mixes, and for chitosan, charcoal and crosslinking agent is added, charcoal enhances the machine of chitosan
Tool performance, crosslinking agent enhance the acid resistance of chitosan, are to be conducive to recycling to avoid secondary pollution for charcoal.Chitosan
Mass ratio with charcoal powder is 1:0.3~0.8, and charcoal powder is prepared by biological straw, such as uses reed straw
Stalk preparation.Glutaraldehyde can be selected in crosslinking agent.Cross-linked chitosan of the invention-biology carbon microspheres preparation principle are as follows: by chitosan plus
Enter in dilute acid soln, stirs into colloidal sol；Then charcoal powder is added, stirring forms mixed sols；Then mixed sols is dripped
Enter and forms microballoon in alkaline solution；Finally, microballoon is impregnated in crosslinking agent, rinsed with deionized water to neutrality after immersion, i.e.,
Cross-linked chitosan-biology carbon microspheres are made.
Specific preparation process is as follows for biology carbon microspheres for cross-linked chitosan of the invention-:
M1g chitosan is added in the acetum that sufficient amount volume fraction is 2%, at 40 DEG C by a) dissolution of chitosan
Under the conditions of stir to forming uniform colloidal sol；
In the step, to guarantee that chitosan is uniformly mixed in acetum, M1g chitosan is mixed into 2% that volume is 50*M1 ml
Acetum in.
M2g charcoal powder is slowly added in the colloidal sol of step a) acquisition by the b) addition of charcoal powder, and 40
DEG C temperature under the conditions of continue to stir, so that charcoal powder is uniformly dispersed in colloidal sol；
In the step, the ratio of the mass M 2 of the mass M 1 and charcoal powder of chitosan is preferably 1:0.5~0.8.
In the step, the preparation process of charcoal powder is as follows:
B-1) reed dries and is crushed, and is first cleaned up reed straw with deionized water, then in 100 DEG C of temperature strip
Reed straw is dried under part, finally shreds reed straw；
Reed after shredding is put into porcelain crucible by the b-2) thermal activation of reed, is compacted and the sealing that closes the lid, and is put into horse boiling
In furnace, 500 DEG C and constant temperature 2h are heated to, so that reed thermal activation；
In the step, heating rate is chosen as 7 DEG C/min.
B-3) is ground up, sieved, and is taken out after the carbonizing production after thermal activation is cooled to room temperature, and 100 mesh numbers are crossed after grinding
Sieve；
B-4) cleaning and drying go ash disposal first with the carbonizing production obtained in the HCl solution cleaning step b-3 of 1mol/L)
Point, then wash with distilled water to neutral；Finally by carbonizing production, drying to constant weight, that is, has prepared charcoal powder.
In the step, drying temperature is chosen as 100 DEG C, drying time is chosen as 24 hours.
C) prepares microballoon, and the NaOH that the mixed sols obtained in step b) is added dropwise to 2mol/L using needle tubing is molten
In liquid precipitate pond, microballoon of uniform size is formed, is stirred continuously during being added dropwise, to prevent manufactured microballoon stick to each other；Drop
After adding, the microballoon in solution is filtered out and is cleaned with deionized water to neutrality；
The microballoon obtained in step c) is placed in the glutaraldehyde water solution that volume fraction is 2% by the d) crosslinking of microballoon, impregnates one
After section of fixing time, filters microballoon and cleaned with deionized water to neutrality, obtain cross-linked chitosan-biology carbon microspheres.
In the above preparation method, chitosan or charcoal powder are only added to the acetum that volume fraction is 2%
In, colloidal sol is then stirred into, in the NaOH solution sedimentation basin for instilling 2mol/L, in the micro-sphere crosslinked processing for passing through step d)
Afterwards, chitosan microball and biological carbon microspheres can be respectively formed.
As shown in Figure 1, Figure 2 and Figure 3, the chitosan microball (being indicated with CH) prepared in the present invention, biology is set forth
Carbon microspheres (being indicated with C), cross-linked chitosan-biology carbon microspheres (being indicated with CSB) scanning electron microscope diagram, it is seen then that shell is poly-
The structure of sugared microballoon is more mixed and disorderly, is a seed capsules skin shape structure without apparent pore structure.It is provided in the structure of charcoal
Apparent hole, but the structure in aperture is more single, and hole wall is more smooth.It is poly- by crosslinking shell made of two kinds of Material claddings
The characteristics of biological carbon microspheres of sugar-combine two kinds of materials, has flourishing pore structure, internal out-of-flatness and very coarse, hole
Gauge structure is complicated and irregular, and such a structure increases the adsorption sites of adsorbent, facilitate the attachment of pollutant, make adsorptivity
It can improve.
As shown in figure 4, it is micro- to give chitosan microball CH in the present invention, biological carbon microspheres C, cross-linked chitosan-charcoal
The infrared spectrogram of ball CSB, one of the top is the spectrum line of charcoal (C), in 1500-1690cm−1Occur one in range
A apparent absorption peak is formed by the stretching vibration of C=C and C=O.Bottom one spectrum line for CH, in 3398cm-1
Very strong absorption peak is the stretching vibration as O-H and N-H and between molecule and molecule caused by hydrogen bond；In 2921cm-1With
2876cm-1The absorption peak at place is that the C-H stretching vibration of the methyl and methine on residual sugar base is formed, 1599 cm-1Place corresponds to
The characteristic absorption peak of amide；In 1420 cm-1With 1382 cm-1Corresponding absorption peak is respectively the C-H of methylene and the C- of methyl
H stretching vibration absworption peak；In 1154 cm-1With 895 cm-1Place is polysaccharide structures absorption peak, especially in 895 cm-1Locate absorption peak
Appearance, illustrate be in chitosan beta comfiguration glycoside bond；1077cm-1The absorption peak at place is the C-O of hydroxyl in chitosan (CH)
Caused by stretching vibration.Intermediate one is chitosan-charcoal complex microsphere (CSB) spectrum line, it can be seen from the figure that shell
With the IR spectra of PVDC after charcoal is compound compared with the spectrum line of chitosan (CH), the position of absorption peak has occurred obviously glycan
Variation, internal chemical bond also change correspondingly, and illustrate that charcoal powder is successfully embedded in chitosan.
As shown in figure 5, it is micro- to give chitosan microball CH in the present invention, biological carbon microspheres C, cross-linked chitosan-charcoal
Ball CSB is to the comparison figure of Cr (VI) ion remaval rate, and in the identical situation of injected volume of adsorbent, CSB, CH and C are to Cr
(VI) ion remaval rate is respectively 92.34%, 69.95% and 7.06%, and CSB illustrates CSB to the removal rate highest of Cr (VI) ion
There is removal effect well to hexavalent chromium (Cr (VI)).
Claims (7)
1. a kind of cross-linked chitosan-charcoal micro-sphere absorption material, it is characterised in that: including chitosan, charcoal powder and friendship
Join agent, chitosan is uniformly mixed with charcoal powder.
2. cross-linked chitosan according to claim 1-charcoal micro-sphere absorption material, it is characterised in that: the chitosan
Mass ratio with charcoal powder is 1:0.3~0.8.
3. cross-linked chitosan according to claim 1 or 2-charcoal micro-sphere absorption material, it is characterised in that: the crosslinking
Agent is glutaraldehyde, and the charcoal powder is made by reed straw.
4. a kind of preparation method of cross-linked chitosan described in claim 1-charcoal micro-sphere absorption material, which is characterized in that
It is prepared via a method which: chitosan being added in dilute acid soln first, stirs into colloidal sol；Then charcoal is added in colloidal sol
Powder, stirring form mixed sols；Then mixed sols is instilled in alkaline solution and forms microballoon；Microballoon is rinsed to neutrality,
Microballoon is impregnated in crosslinking agent, is rinsed with deionized water to neutrality after immersion, cross-linked chitosan-biology carbon microspheres are obtained.
5. cross-linked chitosan according to claim 4-charcoal micro-sphere absorption material preparation method, which is characterized in that
It is realized especially by following steps:
M1g chitosan is added in the acetum that sufficient amount volume fraction is 2%, at 40 DEG C by a) dissolution of chitosan
Under the conditions of stir to forming uniform colloidal sol；
M2g charcoal powder is slowly added in the colloidal sol of step a) acquisition by the b) addition of charcoal powder, and at 40 DEG C
Continue to stir under the conditions of temperature, charcoal powder is made to be uniformly dispersed in colloidal sol；
C) prepares microballoon, and the NaOH solution that the mixed sols obtained in step b) is added dropwise to 2mol/L using needle tubing is heavy
In the pond of shallow lake, microballoon of uniform size is formed；After being added dropwise, by the microballoon in solution filter out and with deionized water clean to
It is neutral；
The microballoon obtained in step c) is placed in the glutaraldehyde water solution that volume fraction is 2% by the d) crosslinking of microballoon, impregnates one
After section of fixing time, filters microballoon and cleaned with deionized water to neutrality, obtain cross-linked chitosan-biology carbon microspheres.
6. cross-linked chitosan according to claim 5-charcoal micro-sphere absorption material preparation method, which is characterized in that
The preparation process of charcoal powder described in step b) is as follows:
B-1) reed dries and is crushed, and is first cleaned up reed straw with deionized water, then in 100 DEG C of temperature strip
Reed straw is dried under part, finally shreds reed straw；
Reed after shredding is put into porcelain crucible by the b-2) thermal activation of reed, is compacted and the sealing that closes the lid, and is put into horse boiling
In furnace, 500 DEG C and constant temperature 2h are heated to, so that reed thermal activation；
B-3) is ground up, sieved, and is taken out after the carbonizing production after thermal activation is cooled to room temperature, and the sieve of 100 mesh numbers is crossed after grinding；
B-4) cleaning and drying go ash disposal first with the carbonizing production obtained in the HCl solution cleaning step b-3 of 1mol/L)
Point, then wash with distilled water to neutral；Finally by carbonizing production, drying to constant weight, that is, has prepared charcoal powder.
7. cross-linked chitosan according to claim 5 or 6-charcoal micro-sphere absorption material preparation method, feature exist
In: in step a), M1g chitosan is mixed into 2% acetum that volume is 50*M1 ml；The mass M 1 of the chitosan with
The ratio of the mass M 2 of charcoal powder is 1:0.3~0.8；In step d), period that microballoon impregnates in glutaraldehyde solution
For 4h.
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| CN110142032A (en) * | 2019-06-11 | 2019-08-20 | 盐城工学院 | Chitosan biological carbon composite and its preparation method and application |
| CN110496605A (en) * | 2019-08-26 | 2019-11-26 | 南京大学 | A kind of chitosan-biology carbon composite and application method |
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| CN114797787A (en) * | 2022-03-24 | 2022-07-29 | 桂林理工大学 | Preparation and application of iron-loaded coconut shell activated carbon chitosan composite microspheres |
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| CN115337912A (en) * | 2022-08-03 | 2022-11-15 | 河池学院 | Magnetic cross-linked chitosan-polyethyleneimine/biochar composite gel particles and preparation method thereof |
| CN115465851A (en) * | 2022-06-01 | 2022-12-13 | 北京化工大学 | Synergistic application method for conditioning red soil by modified biomass carbon/humus/chemical fertilizer |
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