CN103566886A - Method for preparing magnetic activated carbon through DC cataphoresis deposition method - Google Patents
Method for preparing magnetic activated carbon through DC cataphoresis deposition method Download PDFInfo
- Publication number
- CN103566886A CN103566886A CN201310571607.0A CN201310571607A CN103566886A CN 103566886 A CN103566886 A CN 103566886A CN 201310571607 A CN201310571607 A CN 201310571607A CN 103566886 A CN103566886 A CN 103566886A
- Authority
- CN
- China
- Prior art keywords
- active carbon
- molysite
- colloidal sol
- magnetic
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method for preparing magnetic activated carbon through the DC cataphoresis deposition method. The method comprises the following steps: by utilizing the property that ferriferous colloidal particles in molysite collosol carry positive charge, and under the action of an additional pulse electric field, iron colloid particles are directionally electrophoresed into an activated carbon fine pores fixed near a negative pole; then the product obtained in the last step is impregnated in an alkali solution to be subjected to in-situ co-precipitation reaction so as to obtain the magnetic activated carbon. The method provided by the invention can realize green and efficient preparation of ferromagnetic magnetic activated carbon. Compared with a traditional method, the method provided by the invention has the advantages that the content of magnetic objects in the magnetic activated carbon is high, the magnetism is strong, the technology is simple, the cost is relatively low, and the method is suitable for industrial production after being modified.
Description
One, technical field
The present invention relates to a kind of preparation method of magnetic active carbon, specifically a kind of method of preparing magnetic active carbon by direct current electrophoretic deposition.
Two, background technology
Active carbon is widely used in fields such as catalytic reaction, bio-separation, cleaner productions as catalyst carrier and adsorbent.In application process, the recovery of active carbon adopts filtration method to realize conventionally, and the low weak effect of separative efficiency, has affected it and applied.The research and development main purpose of magnetic active carbon is to give active carbon with magnetic, makes it in use can realize quick, inexpensive, efficient separated recovery.At present, magnetic active carbon is applied more field and is comprised the industries such as sewage disposal and noble metal recovery.
The existing preparation method of magnetic active carbon comprises:
1, absorption method: magnetic nanoparticle is carried out to finishing, by adsorption and chemisorption, be attached to the inwall of activated carbon capillary.
2, sol impregnation method: prepare the precursor sol of magnetic material, make magnetic micelle enter activated carbon capillary road by infusion process, then obtain magnetic active carbon by processes such as subsequent chemical reaction, high-temperature process.
3, magnetic fluid infusion process: prepare magnetic fluid, make the magnetic nanoparticle in magnetic fluid enter activated carbon capillary road by normal pressure or impregnating by pressure method, then obtain magnetic active carbon by processes such as oven dry.
, there is the shortcoming of following several respects in the magnetic active carbon preparation method that these are traditional:
1, owing to lacking enough power, the microchannel of magnetic-particle or magnetic micelle active carbon more difficult to get access, so in magnetic active carbon, effectively magnetic material content is lower, magnetic is weak and unstable.
2, dipping or absorption method process is slow, efficiency is low, therefore by these methods, preparing magnetic active carbon is unwell to large-scale production.
3, magnetic fluid infusion process, prepares magnetic fluid complex process, and reagent consumption is large, easily produces and pollutes; Sol impregnation method, the treatment process after micelle dipping needs the conditions such as high temperature, vacuum, and preparation cost is high.
Three, summary of the invention
The present invention is for avoiding the existing weak point of above-mentioned existing magnetic active carbon technology of preparing, aim to provide a kind of method of preparing magnetic active carbon by direct current electrophoretic deposition, technical problem to be solved is to improve specific magnetization and the preparation efficiency of magnetic active carbon, reduce production costs, to be suitable for suitability for industrialized production.
The present invention utilizes the positively charged character of micelle in molysite colloidal sol, under the effect of external electric field, make the directed electrophoresis of iron content colloidal solid to being fixed in the micropore hole of active carbon of negative electrode, then by soaking in aqueous slkali, original position coprecipitation reaction occurs obtain magnetic active carbon.
The present invention prepares the method for magnetic active carbon by direct current electrophoretic deposition, comprise each unit process of preparation, electrophoretic deposition and post processing of molysite colloidal sol:
The preparation of described molysite colloidal sol is with FeCl
2and/or FeSO
4and FeCl
3for solute, take deionized water as solvent, according to Fe
3+and Fe
2+the ratio preparation molysite colloidal sol of mol ratio 2:1, the zeta potential that the concentration of adjusting molysite colloidal sol and pH value make iron content micelle is 10-30meV; Can regulate by hydrochloric acid solution or sodium hydroxide solution the pH value of molysite colloidal sol; The zeta potential of iron content micelle is by electrophoresis technique determining, to grasp the carrying capacity size of iron content micelle under variable concentrations and pH value condition.
Described electrophoretic deposition is to take described molysite colloidal sol as electrophoresis liquid, take carbon-point as anode, the copper sheet that surface is covered with active carbon of take is constructed electrophoretic apparatus as negative electrode, electrode spacing 5-12cm, it is DC pulse electric field that extra electric field is set, voltage 6-18v, pulse frequency 0.1-10Hz, effective pulsewidth occupation rate 60-80%, the electrophoretic deposition time is 240-720 second; The setting party of extra electric field is to being the direction that makes the moving direction sensing negative electrode place of iron content micelle, and iron content micelle is directed and is squeezed in activated carbon capillary hole under electrophoretic action.
Described post processing is that the alkali lye that active carbon prepared by electrophoretic deposition is under agitation placed in pH value 10-11 floods 5-10min, and 110-130 ℃ obtain magnetic active carbon after dry.
In the preparation process of molysite colloidal sol, the concentration of molysite colloidal sol is 0.5M left and right, and pH value is controlled at 3.5-5.5.
The copper sheet that described surface is covered with active carbon is that industrial activited carbon is ground and is sized to particle diameter≤0.15mm and is coated and fixed and obtained behind the surface of copper sheet by fine-structure mesh, control active carbon layer thickness≤2.0mm, so that the more equal even microchannel that enters fully active carbon of charged iron content micelle.
Described alkali lye is ammoniacal liquor or sodium hydroxide solution.
The present invention detects magnetic nanoparticle with the ferromagnetism of magnetic active carbon by instruments such as vibrating specimen magnetometers, electron microscope, the micro-structural of molysite nano particle/active carbon, to facilitate calculating magnetic material content and to estimate its magnetic adsorption effect.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the inventive method has obviously improved the magnetic of magnetic active carbon, specific magnetization is refined by the mono-state of 6-8emu/g(of negative pressure impregnation method, Zhang Guandong, Tian Qing, etc. the preparation of magnetic active carbon and sign, engineering and process journal, 2004,4 (2): 141-145) be increased to 34.1emu/g, and magnetic distributing homogeneity is protected, be conducive to the application of magnetic active carbon.
2, the inventive method has improved the preparation efficiency of magnetic active carbon greatly, can produce continuously, through amplifying transformation, can be used for large-scale industrial production.
3, the inventive method reagent consumption is few, pollutes little; Technique is simple, does not need high temperature, application of vacuum, can reduce the production cost of magnetic active carbon.
Four, accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is electrophoretic deposition principle schematic.
Number in the figure: 1 positive plate; 2 charged colloidal particles; 3 silk screens; 4 minus plates; 5 activated carbon granules
Fig. 2 is the scanning electron microscope image of magnetic active carbon in embodiment 2.As can be seen from Figure 2, magnetic active carbon keeps the original sheet of active carbon or block structure, and obvious clad is not found on surface, and this explanation magnetic components is mainly distributed in the inside of active carbon.
Fig. 3 is the images of transmissive electron microscope of magnetic active carbon in embodiment 1.As can be seen from Figure 3, in active carbon (translucent portion) dense distribution nano level magnetic-particle (stain that contrast is darker), illustrate larger proportion in the microchannel of active carbon filling magnetic-particle.
Fig. 4 is the hysteresis curve of magnetic active carbon sample, wherein magnetic active carbon sample in the corresponding embodiment 1,2,3 of curve 1,2,3 difference.As can be seen from Figure 4 the magnetic active carbon that prepared by embodiment 1-3 all shows the stronger room temperature superparamagnetism that goes out, wherein the specific magnetization of embodiment 1,2,3 products is respectively 34.1,30.0 and 22.6e mu/g, substantially exceeds the specific magnetization of the 6-8emu/g that negative pressure impregnation method obtains; Its coercivity is respectively 81.9,82.3 and 77.4Guass.Magnetic active carbon shows as superparamagnetism, is the characteristic feature of magnetic Nano material, and having confirmed the magnetic material in magnetic active carbon is atomic thin nano particle.
Five, the specific embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
1, the preparation of molysite colloidal sol
With FeCl
2and FeCl
3for solute, take deionized water as solvent, according to Fe
3+and Fe
2+the ratio compound concentration of mol ratio 2:1 is the molysite colloidal sol of 0.5M left and right, regulates the pH value of molysite colloidal sol to 3.5-4.0, controls the zeta potential 16-20meV of iron content micelle, and the zeta potential of iron content micelle passes through electrophoresis technique determining.
2, electrophoretic deposition
According to configuring electrophoretic deposition device shown in Fig. 1, take described molysite colloidal sol as electrophoresis liquid, take carbon-point as anode, the copper sheet that surface is covered with active carbon of take is constructed electrophoretic apparatus as negative electrode, electrode spacing 6cm, and it is DC pulse external electric field that extra electric field is set, voltage 6v, pulse frequency 5.0Hz, effective pulsewidth occupation rate 75%, the electrophoretic deposition time is 360 seconds; The setting party of extra electric field points to the direction at negative electrode place to the moving direction that is iron content micelle, iron content micelle is directed and is squeezed in activated carbon capillary hole under electrophoretic action.Wherein the surperficial copper sheet that is covered with active carbon is that industrial activited carbon (being produced by Chinese forest-science academy forest chemical research institute) is ground and is sized to particle diameter≤0.15mm and is coated and fixed and obtained behind the surface of copper sheet by fine-structure mesh, control active carbon layer thickness≤2.0mm, so that the more equal even microchannel that enters fully active carbon of charged iron content micelle.
3, post processing
It is that 10 NaOH solution floods 8min that the active carbon that electrophoretic deposition is obtained is placed in pH value under electric stirring, and 110-130 ℃ obtain magnetic active carbon after dry.
Embodiment 2:
1, the preparation of molysite colloidal sol
With FeCl
2and FeCl
3for solute, take deionized water as solvent, according to Fe
3+and Fe
2+the ratio compound concentration of mol ratio 2:1 is the molysite colloidal sol of 0.5M left and right, regulates the pH value of molysite colloidal sol to 4.0-4.5, controls the zeta potential 14-17meV of iron content micelle, and the zeta potential of iron content micelle passes through electrophoresis technique determining.
2, electrophoretic deposition
According to configuring electrophoretic deposition device shown in Fig. 1, take described molysite colloidal sol as electrophoresis liquid, take carbon-point as anode, the copper sheet that surface is covered with active carbon of take is constructed electrophoretic apparatus as negative electrode, electrode spacing 8cm, and it is DC pulse external electric field that extra electric field is set, voltage 12v, pulse frequency 2.5Hz, effective pulsewidth occupation rate 60%, the electrophoretic deposition time is 540 seconds; The setting party of extra electric field points to the direction at negative electrode place to the moving direction that is iron content micelle, iron content micelle is directed and is squeezed in activated carbon capillary hole under electrophoretic action.Wherein the surperficial copper sheet that is covered with active carbon is that industrial activited carbon is ground and is sized to particle diameter≤0.15mm and is coated and fixed and obtained behind the surface of copper sheet by fine-structure mesh, control active carbon layer thickness≤2.0mm, so that the more equal even microchannel that enters fully active carbon of charged iron content micelle.
3, post processing
The NaOH solution that active carbon after electrophoretic deposition is under agitation placed in to pH value 11 floods 6min, and 110-130 ℃ obtain magnetic active carbon after dry.
Embodiment 3:
1, the preparation of molysite colloidal sol
With FeSO
4and FeCl
3for solute, take deionized water as solvent, according to Fe
3+and Fe
2+the molysite colloidal sol that the ratio compound concentration of mol ratio 2:1 is 0.5M, regulates the pH value of molysite colloidal sol to 4.5-5.0, controls the zeta potential 12-15meV of iron content micelle, and the zeta potential of iron content micelle passes through electrophoresis technique determining.
2, electrophoretic deposition
According to configuring electrophoretic deposition device shown in Fig. 1, take described molysite colloidal sol as electrophoresis liquid, take carbon-point as anode, the copper sheet that surface is covered with active carbon of take is constructed electrophoretic apparatus as negative electrode, electrode spacing 8cm, and it is DC pulse external electric field that extra electric field is set, voltage 15v, pulse frequency 2.0Hz, effective pulsewidth occupation rate 60%, the electrophoretic deposition time is 600 seconds; The setting party of extra electric field points to the direction at negative electrode place to the moving direction that is iron content micelle, iron content micelle is directed and is squeezed in activated carbon capillary hole under electrophoretic action.Wherein the surperficial copper sheet that is covered with active carbon is that industrial activited carbon is ground and is sized to particle diameter≤0.15mm and is coated and fixed and obtained behind the surface of copper sheet by fine-structure mesh, control active carbon layer thickness≤2.0mm, so that the more equal even microchannel that enters fully active carbon of charged iron content micelle.
3, post processing
The NaOH solution that active carbon after electrophoretic deposition is under agitation placed in to pH value 11 floods 6min, and 110-130 ℃ obtain magnetic active carbon after dry.
Claims (4)
1. by direct current electrophoretic deposition, prepare a method for magnetic active carbon, comprise each unit process of preparation, electrophoretic deposition and post processing of molysite colloidal sol, it is characterized in that:
The preparation of described molysite colloidal sol is according to Fe
3+and Fe
2+the ratio preparation molysite colloidal sol of mol ratio 2:1, the zeta potential that the concentration of adjusting molysite colloidal sol and pH value make iron content micelle is 10-30meV;
Described electrophoretic deposition is to take described molysite colloidal sol as electrophoresis liquid, take carbon-point as anode, the copper sheet that surface is covered with active carbon of take is constructed electrophoretic apparatus as negative electrode, electrode spacing 5-12cm, it is DC pulse electric field that extra electric field is set, the direction that extra electric field is set is the direction that makes the moving direction sensing negative electrode place of iron content micelle, voltage 6-18v, ripple frequency 0.1-10Hz, effective pulsewidth occupation rate 60-80%, the electrophoretic deposition time is 240-720 second;
Described post processing is that the alkali lye that active carbon prepared by electrophoretic deposition is under agitation placed in pH value 10-11 floods 5-10min, and 110-130 ℃ obtain magnetic active carbon after dry.
2. preparation method according to claim 1, is characterized in that:
In the preparation process of molysite colloidal sol, the concentration of molysite colloidal sol is 0.5M, and pH value is controlled at 3.5-5.5.
3. preparation method according to claim 1, is characterized in that:
The copper sheet that described surface is covered with active carbon is that industrial activited carbon is ground and is sized to particle diameter≤0.15mm and is coated and fixed and obtained behind the surface of copper sheet by fine-structure mesh, controls active carbon layer thickness≤2.0mm.
4. preparation method according to claim 1, is characterized in that:
Described alkali lye is ammoniacal liquor or sodium hydroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310571607.0A CN103566886B (en) | 2013-11-15 | 2013-11-15 | Method for preparing magnetic activated carbon through DC cataphoresis deposition method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310571607.0A CN103566886B (en) | 2013-11-15 | 2013-11-15 | Method for preparing magnetic activated carbon through DC cataphoresis deposition method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103566886A true CN103566886A (en) | 2014-02-12 |
| CN103566886B CN103566886B (en) | 2015-04-29 |
Family
ID=50040114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310571607.0A Expired - Fee Related CN103566886B (en) | 2013-11-15 | 2013-11-15 | Method for preparing magnetic activated carbon through DC cataphoresis deposition method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103566886B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103991871A (en) * | 2014-06-05 | 2014-08-20 | 上海理工大学 | Method for preparing magnetic activated carbon from municipal sludge |
| CN109574090A (en) * | 2017-09-28 | 2019-04-05 | 比亚迪股份有限公司 | Hydroxide nickel cobalt manganese and positive electrode and preparation method thereof and lithium ion battery |
| CN112295724A (en) * | 2020-09-14 | 2021-02-02 | 杭州电子科技大学 | Flotation method and flotation device for powdered activated carbon with different regeneration degrees |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004024428A1 (en) * | 2002-09-10 | 2004-03-25 | The Trustees Of The University Pennsylvania | Carbon nanotubes: high solids dispersions and nematic gels thereof |
| CN101538711A (en) * | 2009-03-20 | 2009-09-23 | 同济大学 | Method for preparing ferroelectricicity-ferromagnetic composite thick film by combination of electrophoretic deposition and sol-gel |
| CN103329221A (en) * | 2011-01-26 | 2013-09-25 | 罗伯特·博世有限公司 | Synthesis of magnetic composites |
-
2013
- 2013-11-15 CN CN201310571607.0A patent/CN103566886B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004024428A1 (en) * | 2002-09-10 | 2004-03-25 | The Trustees Of The University Pennsylvania | Carbon nanotubes: high solids dispersions and nematic gels thereof |
| CN101538711A (en) * | 2009-03-20 | 2009-09-23 | 同济大学 | Method for preparing ferroelectricicity-ferromagnetic composite thick film by combination of electrophoretic deposition and sol-gel |
| CN103329221A (en) * | 2011-01-26 | 2013-09-25 | 罗伯特·博世有限公司 | Synthesis of magnetic composites |
Non-Patent Citations (2)
| Title |
|---|
| ZHENGYONG ZHANG ET AL.: "Novel magnetic Fe3O4@C nanoparticles as adsorbents for removal of organic dyes from aqueous solution", 《JOURNAL OF HAZARDOUS MATERIALS》, vol. 193, 2 August 2011 (2011-08-02) * |
| 周海佳 等: "电泳沉积制备功能薄膜材料研究进展", 《材料导报》, vol. 22, 31 August 2008 (2008-08-31) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103991871A (en) * | 2014-06-05 | 2014-08-20 | 上海理工大学 | Method for preparing magnetic activated carbon from municipal sludge |
| CN103991871B (en) * | 2014-06-05 | 2015-09-30 | 上海理工大学 | A kind of method utilizing municipal sludge to prepare magnetic active carbon |
| CN109574090A (en) * | 2017-09-28 | 2019-04-05 | 比亚迪股份有限公司 | Hydroxide nickel cobalt manganese and positive electrode and preparation method thereof and lithium ion battery |
| CN109574090B (en) * | 2017-09-28 | 2020-09-15 | 比亚迪股份有限公司 | Nickel cobalt manganese hydroxide, positive electrode material, preparation method of positive electrode material and lithium ion battery |
| CN112295724A (en) * | 2020-09-14 | 2021-02-02 | 杭州电子科技大学 | Flotation method and flotation device for powdered activated carbon with different regeneration degrees |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103566886B (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fayazi et al. | Fe3O4 and MnO2 assembled on halloysite nanotubes: a highly efficient solid-phase extractant for electrochemical detection of mercury (II) ions | |
| Pradhan et al. | Fabrication, growth mechanism, and characterization of α-Fe2O3 nanorods | |
| Kim et al. | Improvement of desalination efficiency in capacitive deionization using a carbon electrode coated with an ion-exchange polymer | |
| Chi et al. | Highly efficient recovery of uranium from seawater using an electrochemical approach | |
| Choi | Fabrication of a carbon electrode using activated carbon powder and application to the capacitive deionization process | |
| Liu et al. | Surfactant-free electrochemical synthesis of hierarchical platinum particle electrocatalysts for oxidation of ammonia | |
| Zhang et al. | A highly selective photoelectrochemical biosensor for uric acid based on core–shell Fe3O4@ C nanoparticle and molecularly imprinted TiO2 | |
| Laxman et al. | Improved desalination by zinc oxide nanorod induced electric field enhancement in capacitive deionization of brackish water | |
| Chen et al. | Fast catalytic reduction of an azo dye by recoverable and reusable Fe 3 O 4@ PANI@ Au magnetic composites | |
| Bazrafshan et al. | Synthesis of novel α-Fe2O3 nanorods without surfactant and its electrochemical performance | |
| Huang et al. | Desalination by capacitive deionization with carbon-based materials as electrode: a review | |
| CN103566886B (en) | Method for preparing magnetic activated carbon through DC cataphoresis deposition method | |
| Xu et al. | Enhancing brackish water desalination using magnetic flow-electrode capacitive deionization | |
| Guo et al. | Controlled synthesis, magnetic and sensing properties of hematite nanorods and microcapsules | |
| CN105417524A (en) | Preparation method of highly-ordered mesoporous graphene with thick controllable layer | |
| Riva et al. | Catalytic properties of FePd ferromagnetic nanowires at liquid/liquid interfaces | |
| Wang et al. | Electrocatalytic oxidation and detection of N-acetylcysteine based on magnetite/reduced graphene oxide composite-modified glassy carbon electrode | |
| CN104575658A (en) | Magnetic field and application of magnetic nanowires in transparent conductive film as well as transparent conductive film and preparation method | |
| Wang et al. | Recovery of rare earth by electro-sorption with sodium diphenylamine sulfonate modified activated carbon electrode | |
| CN104120481A (en) | Pure iron based surface Fe3O4 nano-column array and preparation method thereof | |
| Tao et al. | Highly efficient Li+/Mg2+ separation of monovalent cation permselective membrane enhanced by 2D metal organic framework nanosheets | |
| CN105565293A (en) | Preparation method of two-dimensional ordered mesoporous carbon framework film material | |
| Wang et al. | Reactivation of Fenton catalytic performance for Fe3O4 catalyst: optimizing the cyclic performance by low voltage electric field | |
| Xu et al. | Magnetic array for efficient and stable flow-electrode capacitive deionization | |
| Wang et al. | A smart potential-responsive ion exchange nanomaterial with superparamagnetism for cesium ion separation and recovery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150429 Termination date: 20151115 |
|
| EXPY | Termination of patent right or utility model |