CN106040167B - A kind of preparation method and its usage of magnetism multi-stage porous carbon material - Google Patents
A kind of preparation method and its usage of magnetism multi-stage porous carbon material Download PDFInfo
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- CN106040167B CN106040167B CN201610362527.8A CN201610362527A CN106040167B CN 106040167 B CN106040167 B CN 106040167B CN 201610362527 A CN201610362527 A CN 201610362527A CN 106040167 B CN106040167 B CN 106040167B
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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
- B01J20/02—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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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The present invention provides a kind of preparation method and its usages of magnetic multi-stage porous carbon material, it carries out as steps described below: weighing ferric nitrate and ethylenediamine tetra-acetic acid metal sylvite is put into mortar and mixes, grinding uniformly, then fills this blend into tube furnace, is passed through inert gas, it is calcined, after natural cooling, the product in tube furnace is taken out, the ethyl alcohol/distilled water washed product for being 1:1 with volume ratio, magnetism multi-stage porous carbon material is made in drying.Prepared magnetic multi-stage porous carbon material possesses higher specific surface area, big to the adsorption capacity of antibiotic, is applied to environmental wastewater and handles, and the rate of adsorption is fast, and performance is stablized, and has preferable Magnetic Isolation performance and reproducibility.
Description
Technical field
The invention belongs to technical field of environment function material preparation, refer specifically to a kind of preparation side of magnetic multi-stage porous carbon material
Method and application thereof.
Background technique
Chloramphenicol (Chloramphenicol, CAP) is the antibiotic generated by Venezuela Streptothrix, and it is wide to belong to biocidal property
Antibiotic is composed, has stronger inhibiting effect to Gram-negative bacteria and gram-positive bacteria, is widely used in for a long time
The prevention and treatment of human and animal's communicable disease and the growth promoter of animal.Taking in internal antibiotic cannot be biological
Body fully absorbs, most of to exclude in vitro, to finally flow into water body with original shape or metabolin, and culture fishery is then directly with original shape
Water body is put into, residue problem becomes increasingly conspicuous.Nowadays, many countries including China, CAP sewage treatment plant water outlet,
It is continually detected in surface water and groundwater.Since chloramphenicol has serious toxic side effect, long-term micro intake is not only
A variety of bacterial strains such as Escherichia coli, salmonella can be made to generate drug resistance, and the imbalance of animal body normal flora can be caused, resisted
Power reduction, the various diseases of easy infection.Therefore, the effective and economic and practical processing means of development are established selectively to remove in environment
Chloromycetin series antibiotics residual is extremely urgent.
Porous carbon materials are a kind of porous structure materials using carbon as skeleton main body, have large specific surface area, hole knot
Structure is flourishing, chemical stability high (acid and alkali-resistance), mechanical performance are strong and the excellent properties such as cellular structure and aperture size are adjustable, together
When have both electric conductivity, thermal conductivity and its preparation cost is cheap, process is easy, always by the blueness of domestic and international Technological research personnel
It looks at.But Recent study finds that single aperture structure carbon material is unable to satisfy the demand of performance application, therefore, multi-stage porous carbon materials
The exploitation of material is come into being.Multi-stage porous carbon material is that a kind of duct of two kinds (or a variety of) interconnects constructs that form multidimensional mutual
The novel structure carbon material of open network.Its research is concentrated on micro--mesoporous, big-mesoporous, big-bis- mesoporous, micro--Jie-is big at present
Hole and pore structure is built altogether with level-one, they have both the performance of single Porous materials and multistage pore structure is flourishing and cooperative ability,
The surface chemical property of high specific surface area, high surface and multiplicity, shows excellent bulk properties, is widely used as height
Imitate adsorbent.The raw material of production multi-stage porous carbon can be coal, sawdust, shell, Animal Bone head etc., Current resource is in short supply, the energy
Be critical, in the case where environmental degradation, the circulation of resource is more concerned by people with clean utilization, seek it is renewable, low at
This carbon matrix precursor, especially biomass sources, preparing the multi-stage porous carbon material haveing excellent performance is one of the target for continuing to pursue.
Using ethylenediamine tetra-acetic acid tripotassium salt as carbon source, ferric nitrate is handled the present invention as magnetic precursor, one step of high temperature, from
Carbonization self-activation prepares the magnetic multi-stage porous carbon material of high-specific surface area, has good adsorption effect to chloramphenicol, is one
Kind has promising adsorbent.
Summary of the invention
The present invention is using EDTAP dipotassium ethylene diamine tetraacetate or ethylenediamine tetra-acetic acid tripotassium salt as carbon source, and ferric nitrate is body before magnetic
Body prepares a kind of magnetic multi-stage porous carbon material, for quickly removing the chloramphenicol in water environment.
Using EDTAP dipotassium ethylene diamine tetraacetate or ethylenediamine tetra-acetic acid tripotassium salt as carbon source, ferric nitrate is magnetic presoma for this experiment,
Uniform using direct ground and mixed, high temperature cabonization processing is realized that synchronous magnetizing and activation prepare magnetic multi-stage porous carbon material, is ground
Raw material proportioning is studied carefully to the affecting laws of magnetic multi-stage porous carbon material, establishes control methods.Using chloramphenicol as research object, hole is established
Structure-activity relationship and adsorbing separation mechanism between gap structure and absorption property.Magnetic multi-stage porous carbon material is realized rapidly and efficiently
While absorption, recycling problem is solved.
The technical solution adopted by the present invention is that:
A kind of preparation method of magnetism multi-stage porous carbon material, carries out as steps described below:
It weighs ferric nitrate and ethylenediamine tetra-acetic acid metal sylvite is put into mortar and mixes, grinding is uniform, then by mixture
It is fitted into tube furnace, is passed through inert gas, calcined, after natural cooling, the product in tube furnace is taken out, volume ratio is used
For ethyl alcohol/distilled water washed product of 1:1, magnetism multi-stage porous carbon material (Magnetic Hierarchical is made in drying
Porous Carbon, MHPC).
The mass ratio of used ferric nitrate and ethylenediamine tetra-acetic acid metal sylvite is 1~4:20.
The ethylenediamine tetra-acetic acid metal sylvite is EDTA Dipotassium salt or ethylenediamine tetra-acetic acid tripotassium salt.
The inert gas is nitrogen or argon gas.
The calcining manners are as follows: heating rate is 3.0~10 DEG C of min-1, rise to 750~850 DEG C and 750~850
DEG C maintain 1.0~2.0h.
Prepared magnetic multi-stage porous carbon is used to adsorb the chloramphenicol in water.
Technological merit of the invention:
(1) the multi-stage porous carbon material is using EDTAP dipotassium ethylene diamine tetraacetate or ethylenediamine tetra-acetic acid tripotassium salt as carbon source, nitric acid
Iron is magnetic precursor, and abundance is cheap, economic and environment-friendly.
(2) the magnetism multi-stage porous carbon possesses higher specific surface area, big to the adsorption capacity of antibiotic, and it is dirty to be applied to environment
Water process, and the rate of adsorption is fast, and performance is stablized, and has preferable Magnetic Isolation performance and reproducibility.
(3) porous carbon materials are because of its own excellent property, such as high porosity, physico-chemical property stabilization can be used extensively
In fields such as environment, chemical industry, material, energy storage.
(4) operating method of the invention is simple and easy, process is shorter, easy controlled operation, is suitable for promoting the use of.
Detailed description of the invention
Fig. 1 is the electron microscope of the material prepared in embodiment 1, wherein (a) is scanning electron microscope (SEM) photograph, it (b) is transmission electron microscope picture；
Fig. 2 is the N of the material prepared in embodiment 12The attached thermoisopleth of absorption-desorption；
Fig. 3 is the adsorption isotherm map of the material for preparing in embodiment 1 to chloramphenicol in water environment；
Fig. 4 is the adsorption dynamics adsorption kinetics figure of the material for preparing in embodiment 1 to chloramphenicol in water environment.
Specific embodiment
In order to clarify the technical solutions and technical objectives of the present invention, with reference to the accompanying drawing and specific embodiment is the present invention
It is further to introduce.
Embodiment 1:
4.0g ferric nitrate and 20g ethylenediamine tetra-acetic acid tripotassium salt are fully ground, 15g sample synchronous carbon in tube furnace is taken
Change and activation, temperature are 750 DEG C, heating rate is 3 DEG C of min-1, maintain 1.0h；By product ethyl alcohol obtained and distilled water
Repeatedly, vacuum filtration is washed to neutrality, is dried to obtain magnetic multi-stage porous carbon material for mixed liquor washing.
It is completed using Staticadsorption experiment；The chloromycetin solution of 10mL various concentration is added in centrifuge tube, respectively to
2.0mg magnetism multi-stage porous carbon material is wherein added, is stood in water bath with thermostatic control, when having investigated solution ph, adsorbent amount, contact
Between, temperature influence that chloramphenicol is adsorbed；Absorption reach saturation after, 0.45um membrane filtration collect supernatant liquor, with it is ultraviolet can
Light-exposed photometer measures chloramphenicol molecular concentration unadsorbed in test solution in 278nm, and adsorption capacity (Q is calculatede)。
Wherein C0(mg L-1) and Ce(mg L-1) it is initial and equilibrium concentration respectively, m (mg) is adsorbent amount, V (mL)
For liquor capacity.
Taking 10mL initial concentration is respectively 30~300mg L-1Chloromycetin solution be added in centrifuge tube, be separately added into
2.0mg magnetism multi-stage porous carbon material, is placed on test fluid after standing for 24 hours in 298K water-bath, collects supernatant liquor, unadsorbed
Chloramphenicol molecular concentration is measured with ultraviolet-uisible spectrophotometer, and calculates adsorption capacity, last equilibrium adsorption according to result
Amount is 398.0mg g-1。
Taking 10mL initial concentration is 300mg L-1Chloromycetin solution be added in centrifuge tube, be separately added into 2.0mg magnetism
Multi-stage porous carbon material, test fluid is placed in the water-bath of 298K and stands 5.0~420min respectively.After the completion of standing, upper layer is collected
Clear liquid, unadsorbed chloramphenicol molecular concentration are measured with ultraviolet-uisible spectrophotometer, and are calculated absorption according to result and held
Amount；The result shows that: it is 300mg L in initial concentration-1, when temperature is 298K, 420min or so reaches adsorption equilibrium.
Fig. 1 is the electron microscope of the material prepared in embodiment 1, wherein (a) is scanning electron microscope (SEM) photograph, it (b) is transmission electron microscope picture；
From it can be seen that MHPC is laminated structure, and there are a large amount of discrete nanoparticles in (a), tight agglomeration together, surface compared with
For the coarse attachment for being conducive to pollutant.(b) it will be clear that the surface of laminated structure carbon material is attached with particle in, and
Content is relatively more, and the size of particle is about 85nm, and sheet carbon surface is dispersed with relatively large number of nano-pore, is conducive to as pollution
Object provides adsorption site；The result of TEM figure illustrates EDTA-3K and ferric nitrate mixed calcining, is successfully attached to iron conjunction object more
The surface of hole carbon.
Fig. 2 is the N of the material prepared in embodiment 12The attached thermoisopleth of absorption-desorption.It can be observed that carbon material from Fig. 2
Adsorpting type belong to I type (classifying according to IUPAC), show in sample containing a large amount of micropore, and in P/Po=0.4 starts
There is lesser hysteresis phenomenon, this is that have mesoporous adsorpting characteristic.
Fig. 3 is the adsorption isotherm map of the material for preparing in embodiment 1 to chloramphenicol in water environment, as shown in Figure 3: with
The raising of concentration, adsorbance increase therewith, this may be to provide more chances since temperature raises for CAP molecule to touch suction
Attached dose of surface improves the probability that CAP molecule and imprinted sites combine, while concentration increases the enough concentration diffusion drives of offer
Power, therefore adsorbance increases.When 298K, equilibrium adsorption capacity is 398.0mg g-1。
Fig. 4 is the adsorption dynamics adsorption kinetics figure of the material for preparing in embodiment 1 to chloramphenicol in water environment, as shown in Figure 4, with
The increase of time of contact, adsorbance increase sharply, and in preceding 100min, adsorbance increases comparatively fast, and 420min slowly tends to be flat later
Weighing apparatus, shows adsorption equilibrium faster.
Embodiment 2:
2.0g ferric nitrate and 20g EDTA Dipotassium salt are fully ground, 15g sample synchronous carbon in tube furnace is taken
Change and activation, temperature are 800 DEG C, heating rate is 5 DEG C of min-1, maintain 1.0h；By product ethyl alcohol obtained and distilled water
Repeatedly, vacuum filtration is washed to neutrality, is dried to obtain magnetic multi-stage porous carbon material for mixed liquor washing.It is grasped by 1 step of embodiment
Make, gained equilibrium adsorption capacity is 407.7mg g-1.It is 300mg L in initial concentration-1, when temperature is 298K, 400min or so reaches
To adsorption equilibrium.
Embodiment 3:
1.0g ferric nitrate and 20g ethylenediamine tetra-acetic acid tripotassium salt are fully ground, 15g sample synchronous carbon in tube furnace is taken
Change and activation, temperature are 850 DEG C, heating rate is 10 DEG C of min-1, maintain 2.0h；By product ethyl alcohol obtained and distilled water
Repeatedly, vacuum filtration is washed to neutrality, is dried to obtain magnetic multi-stage porous carbon material for mixed liquor washing.It is grasped by 1 step of embodiment
Make, gained equilibrium adsorption capacity is 444.2mg g-1.It is 300mg L in initial concentration-1, when temperature is 298K, 350min or so reaches
To adsorption equilibrium.
Claims (4)
1. a kind of preparation method of magnetism multi-stage porous carbon material, which is characterized in that carry out as steps described below:
It weighs ferric nitrate and ethylenediamine tetra-acetic acid metal sylvite is put into mortar and mixes, ferric nitrate and ethylenediamine tetra-acetic acid metallic potassium
The mass ratio of salt is 1~4:20, and grinding uniformly, then fills this blend into tube furnace, is passed through inert gas, calcined,
After natural cooling, the product in tube furnace is taken out, the ethyl alcohol/distilled water washed product for being 1:1 with volume ratio, is dried, system
Obtain magnetic multi-stage porous carbon material；The ethylenediamine tetra-acetic acid metal sylvite is EDTA Dipotassium salt or ethylenediamine tetrem
Sour tripotassium salt.
2. a kind of preparation method of magnetic multi-stage porous carbon material according to claim 1, which is characterized in that the inertia
Gas is nitrogen or argon gas.
3. a kind of preparation method of magnetic multi-stage porous carbon material according to claim 1, which is characterized in that the calcining
Mode is as follows: heating rate is 3.0~10 DEG C of min-1, rise to 750~850 DEG C and in 750~850 DEG C of 1.0~2.0h of maintenance.
4. the purposes of the magnetic multi-stage porous carbon material of the preparation of method described in claims 1 to 3 any one, which is characterized in that
The magnetism multi-stage porous carbon is used to adsorb the chloramphenicol in water.
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| CN107519874A (en) * | 2017-08-22 | 2017-12-29 | 江苏大学 | A kind of preparation method and applications of cobalt doped carboxylic acid potassium salt base combined multi-stage hole carbon material |
| CN109107596A (en) * | 2018-08-20 | 2019-01-01 | 河南师范大学 | The preparation method of the carbon nano enzyme of active metal and nitrogen codope and its application that hydrogen peroxide is detected as nanometer bio probe |
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| CN110182800A (en) * | 2019-07-15 | 2019-08-30 | 天津工业大学 | A kind of method for preparation of active carbon based on ethylene diamine tetraacetic acid sylvite |
| CN113398945B (en) * | 2021-05-19 | 2022-09-23 | 杭州师范大学 | Spherical C/FeMo nano composite photocatalyst and preparation method thereof |
| CN114334475A (en) * | 2021-10-01 | 2022-04-12 | 中国科学院宁波材料技术与工程研究所 | One-step synthesized high-specific-surface-area hierarchical pore carbon electrode material and preparation method and application thereof |
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