CN108514863A - The method and its products therefrom that charcoal coats magnetic halloysite compound adsorbent are prepared using humic acid - Google Patents
The method and its products therefrom that charcoal coats magnetic halloysite compound adsorbent are prepared using humic acid Download PDFInfo
- Publication number
- CN108514863A CN108514863A CN201710752788.5A CN201710752788A CN108514863A CN 108514863 A CN108514863 A CN 108514863A CN 201710752788 A CN201710752788 A CN 201710752788A CN 108514863 A CN108514863 A CN 108514863A
- Authority
- CN
- China
- Prior art keywords
- powdered
- galapectite
- molysite
- humic acid
- charcoal
- 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
Classifications
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to sewage purification technologies, belong to the Waste water treatment medicament of absorption heavy metal ion and organic dyestuff, the method and its products therefrom that charcoal coats magnetic halloysite compound adsorbent are prepared in particular with humic acid, iron chloride or ferric nitrate and halloysite clay are sequentially added in ethyl alcohol polar solvent, and dispersion liquid is formed by stirring, it adds solid powdery ammonium hydrogen carbonate and is persistently stirred to react to obtain FeOOH galapectite mixtures, then by wet grinding by humic acid and FeOOH galapectite mixture mixings, then humic acid and FeOOH galapectite mixtures are further roasted in inert gas, then it obtains by Fe3O4The charcoal that halloysite composite material is constituted coats magnetic halloysite compound adsorbent.Raw material of the present invention is easy to get, and implementation condition is mild, easy to operate, be easy to industrialized production.
Description
Technical field
The invention belongs to sewage purification technologies, belong to the Waste water treatment medicament of absorption heavy metal ion and organic dyestuff, special
It is not to prepare the method and its products therefrom that charcoal coats magnetic halloysite compound adsorbent using humic acid.
Background technology
Nano magnetic composite materials are to utilize nanometer Fe3O4Etc. magnetic components coupled with other functional materials obtain more work(
Energy material, is with a wide range of applications in the fields such as catalysis, water process, energy storage and conversion, magnetic storage, magnetic imaging.Especially
It is in dye wastewater treatment field：On the one hand, magnetic component coupled with catalytic active component can prepare it is various for degrading
The efficient mangneto recycling catalyst or photochemical catalyst of organic dye pollutant；On the other hand, magnetic component and high absorption property base
The coupling of body ingredient can prepare magnetic adsorptive material for adsorbing organic pollution, meanwhile, matrix composition can also play point
Dissipate and fix nanometer Fe3O4Effect, prevent nanometer Fe3O4Reunite and slows down oxidation.Therefore, selection is cheap, performance is stable and comes
The abundant matrix composition in source is also the important option for preparing nano magnetic composite materials.
Angstrom trachelospermum jasminoide is a kind of alumino-silicate clays mineral with tubular structure, including 1 ︰, 1 type structural unit layers, belong to double
Octahedral build structure clay, but still with the presence of intermediary water between its structural unit layer.It has larger specific surface area, relatively strong
Ion-exchange capacity, higher thermally and chemically stability, especially unique one-dimensional tubular morphology feature becomes one kind
Ideal nano carrier material, meanwhile, galapectite has higher adsorption capacity, quilt to a variety of organic dyestuff and heavy metal ion
It is widely used in wastewater treatment.To make this kind of clay absorbent convenient for recycling, by magnetic nanoparticle it is immobilized on galapectite by
To extensive concern.
Xie Yanfang et al. then utilize galapectite-Fe3O4Compound adsorbs water Methylene Blue, dimethyl diaminophenazine chloride and methyl orange
（Chemical Engineering Journal, 2011,168 ︰ 959-963.）.Zhang bin et al. use chemical precipitation method
Prepare galapectite-Fe3O4Magnetic composite, and for dye methyl violet in Adsorption water（Desalination, 2012,
293 ︰ 46-52）.Mohammad Amjadi et al. are successfully prepared using chemical precipitation method for adsorbing heavy metal cadmium ion
Fe3O4/ galapectite compound（Microchimica Acta, 2015,182 ︰ 1627-1633）.
To improve halloysite surface nano Fe3O4Oxidation resistance, and further improve compound performance, it is right
It is very necessary that composite particles carry out surface modification.Mu Bin et al. prepare chitosan Fe using spray drying process3O4/ Ai Luo
Stone/tetracycline multicomponent microballoon（RSC Advances, 2013,3 ︰ 23423-23431.）.Dai Jiangdong et al. will then gather
It closes object and is coated in magnetic halloysite nanotube surface for tetracycline in quick adsorption waste water（RSC Advances, 2014,4 ︰
7967-7978.）.The magnetic halloysite that Jiang Ling et al. prepare charcoal cladding using glucose as charcoal source using hydro-thermal method is received
Mitron simultaneously is used to adsorb methylene blue dye（Chemical Research in Chinese Universities, 2014,30 ︰
971–977.）
Using bentonite as carrier, by α-Fe2O3Nano particle is fixed on clay particle surface or interlayer will not only overcome it is respective
Disadvantage, but also because two kinds of surface charge property different materials it is compound due to generate synergistic effect.Therefore, using distinct methods system
Standby α-Fe2O3/ clay complex and its performance study cause extensive concern.According to pertinent literature, Chen etc.（Separation
And Purification Technology, 2009,67 ︰ 282-288）It is prepared containing ferrum collosol using sodium carbonate as precipitating reagent, with
Bentonite mixing prepares α-Fe using 350 DEG C of dryings2O3/ bentonite（bentonite）Compound.Du etc.（Catalysis
Communications, 2009,10 ︰ 1854-1858）Liquor ferri trichloridi is precipitated using solid sodium bicarbonate, it is outstanding with bentonite
Supernatant liquid mixes, and carries out burin-in process at 65 DEG C and 95 DEG C respectively, then obtain the α-of different component ratio after drying at 120 DEG C
Fe2O3/ bentonite compound.
There is potential use with water treatment field in catalysis in view of charcoal coated magnetic clay, establishes new preparation method and be used for
It is very necessary to develop high efficiency charcoal coated magnetic clay.
Invention content
The purpose of the present invention is to provide a kind of charcoal cladding magnetic halloysite compound adsorbent is prepared using humic acid
Method and its products therefrom, raw material are easy to get, and implementation condition is mild, easy to operate, be easy to industrialized production.
The object of the present invention is achieved like this：It is a kind of to prepare charcoal cladding magnetic halloysite compound absorption using humic acid
A-1, molysite is dissolved by carrier of liquid polar organic solvent in liquid polar organic solvent by the method for agent, make molysite with
Liquid polar organic solvent is mixed into uniform clear iron salt solutions；Liquid polar organic solvent be methanol and/or ethyl alcohol and/or
Propyl alcohol, propyl alcohol include normal propyl alcohol and/or isopropanol, and molysite is iron chloride and/or ferric nitrate, molysite and liquid in iron salt solutions
Molal quantity/volume ratio of polar organic solvent is：Volume=0.0025- of the Mo Er number ︰ liquid polar organic solvents of molysite
0.1mol/L；A-2, powdered galapectite is added in iron salt solutions, makes powdered galapectite in iron using ultrasonic agitation mode
The powdered galapectite mixed dispersion liquid of iron salt solutions-is fully blended together in salting liquid with molysite, ultrasonic agitation action time is 2-
15min；In the powdered galapectite mixed dispersion liquid of iron salt solutions-, molal quantity/mass ratio of molysite and powdered galapectite
For：Quality=0.5-5mol/kg of the powdered galapectites of Mo Er numbers ︰ of molysite, powdered galapectite and liquid polar organic solvent
Mass/volume ratio be：Volume=1-25g/L of the Zhi Liang ︰ liquid polar organic solvents of powdered galapectite；A-3, in molysite
Solid powdery ammonium hydrogen carbonate is added in solution-powder shape galapectite mixed liquor, solid powdery is made using magnetic agitation mode
Ammonium hydrogen carbonate mutually mixed well with the powdered galapectite mixed liquor of iron salt solutions-as precipitating reagent react then generate containing by
The brownish red suspension of brownish red suspended matter caused by solid powdery ammonium hydrogen carbonate, magnetic agitation action time are 3-24h；
In the powdered galapectite mixed liquor of iron salt solutions-, the mass/mass ratio of solid powdery ammonium hydrogen carbonate and molysite is：Solid powder
Quality=0.8-6kg/kg of the Zhi Liang ︰ iron salt solutions of last shape ammonium hydrogen carbonate；A-4, first to containing the reddish brown of brownish red suspended matter
Color suspension is filtered by vacuum to extract the brown-red solid deposit therein containing FeOOH- galapectite mixtures, then is adopted
It with ethyl alcohol washs brown-red solid deposit and is not belonging to brown-red solid deposit to remove in brown-red solid deposit
The brown-red solid deposit of washed mistake is then placed in 40-80 DEG C of physical environment dry 6-24h to go by solid impurity
Except the liquid impurity in brown-red solid deposit, then will be ground into powder by dried brown-red solid deposit
FeOOH- galapectite mixtures；B-1, it powdered humic acid is mixed into pure water phase is mixed as a paste of presoma
Then pasty mixture is ground 5-10min by object；The mass/volume of molysite and pure water in a pasty mixture
Than for：Volume=0.5-1g/ml of the matter amount ︰ pure water of molysite, B-2, first by be ground pasty mixture and powder
Last shape FeOOH- galapectites mixture is mutually mixed into secondary pasty mixture, then secondary pasty mixture is ground 0.5-1.0h,
Then the secondary pasty mixture being ground is dried, then continues to regrind by the secondary pasty mixture being oven-dried
5-10min and form powdered object；Powdered humic acid and powdered FeOOH- galapectites are mixed in secondary pasty mixture
Close object mass/mass ratio be：Quality=0.05- of the powdered FeOOH- galapectites mixtures of Zhi Liang ︰ of powdered humic acid
0.4kg/kg；B-3, powdered object is placed in the physics for being full of and having the inert gas not chemically reacted with powdered object
It is begun heat to from room temperature in environment after the fixed temperature value selected in 350-600 DEG C with baking modes in the fixed temperature value
Keep the temperature 3-6h；Heating rate since room temperature is 1-10 DEG C/min, and inert gas is argon gas and/or nitrogen；In powdered object
Body obtains after completing heat preservation in powdered by Fe3O4The charcoal cladding magnetic halloysite compound that halloysite composite material is constituted is inhaled
Attached dose.
The object of the present invention is achieved like this：It is a kind of to prepare charcoal cladding magnetic halloysite compound absorption using humic acid
The method products therefrom of agent, by using humic acid prepare charcoal coat magnetic halloysite compound adsorbent method obtain be in powder
Last shape is by Fe3O4The charcoal that halloysite composite material is constituted coats magnetic halloysite compound adsorbent.
The present invention makes full use of natural humic acid as charcoal source and reducing agent, develops humic acid answering in rich carbon composite
With products therefrom coats magnetic halloysite composite material as charcoal（Magnetic halloysite nano-complex）It can be used in waste water
Adsorb heavy metal ion and organic dyestuff.
The present invention is by FeOOH superfine nano particle reductions at Fe3O4It is fixed in rodlike galapectite surface and stick, then is stirring
Both iron chloride polycation is adsorbed on by electrostatic interaction on the electronegative galapectite barred body in surface under the effect of mixing, make
Stable soliquid is formed, after soliquid is then filtered drying, using humic acid as charcoal source, in inert gas
It roasts and is reduced by Fe3O4The charcoal that halloysite composite material is constituted coats magnetic halloysite compound adsorbent.
On the whole, brief implementation steps of the invention are：Iron chloride or nitric acid are sequentially added in ethyl alcohol polar solvent
Iron and halloysite clay form dispersion liquid by stirring, add solid powdery ammonium hydrogen carbonate and are persistently stirred to react to obtain
FeOOH- galapectite mixtures, then by wet grinding by humic acid and FeOOH- galapectite mixture mixings, then into
One step roasts humic acid and FeOOH- galapectite mixtures in inert gas, then obtains by Fe3O4Halloysite composite material
The charcoal of composition coats magnetic halloysite compound adsorbent.Brief implementation steps according to the present invention it can be seen that, raw material of the present invention
It is easy to get, implementation condition is mild, easy to operate, be easy to industrialized production.
Description of the drawings
The present invention will be further described with reference to the accompanying drawings.
Fig. 1 is obtained by embodiment 2-1 by Fe3O4The charcoal that halloysite composite material is constituted coats magnetic halloysite compound
The X ray diffracting spectrum of adsorbent；
Fig. 2 is obtained by embodiment 2-2 by Fe3O4The charcoal cladding magnetic halloysite compound that halloysite composite material is constituted is inhaled
Attached dose of X ray diffracting spectrum；
Fig. 3 is obtained by embodiment 2-3 by Fe3O4The charcoal cladding magnetic halloysite compound that halloysite composite material is constituted is inhaled
Attached dose of X ray diffracting spectrum；
Fig. 4 is the X ray diffracting spectrum of the existing powdered galapectite used in the present invention.
Specific implementation mode
A method of using humic acid prepare charcoal coat magnetic halloysite compound adsorbent, A-1, by molysite with liquid
Polar organic solvent is that carrier is dissolved into liquid polar organic solvent, and molysite is made to be mixed into uniformly with liquid polar organic solvent
Clear iron salt solutions；Liquid polar organic solvent is methanol and/or ethyl alcohol and/or propyl alcohol, and propyl alcohol includes normal propyl alcohol and/or different
Propyl alcohol, molysite are iron chloride and/or ferric nitrate, molal quantity/volume of molysite and liquid polar organic solvent in iron salt solutions
Than for：Volume=0.0025-0.1mol/L of the Mo Er number ︰ liquid polar organic solvents of molysite；A-2, it is added in iron salt solutions
Powdered galapectite makes powdered galapectite fully blend together molysite with molysite in iron salt solutions molten using ultrasonic agitation mode
The powdered galapectite mixed dispersion liquid of liquid-, ultrasonic agitation action time are 2-15min；It is mixed in the powdered galapectite of iron salt solutions-
It closes in dispersion liquid, molal quantity/mass ratio of molysite and powdered galapectite is：The matter of the powdered galapectites of Mo Er numbers ︰ of molysite
The mass/volume ratio of amount=0.5-5mol/kg, powdered galapectite and liquid polar organic solvent is：The matter of powdered galapectite
Volume=1-25g/L of Liang ︰ liquid polar organic solvents；A-3, solid is added in the powdered galapectite mixed liquor of iron salt solutions-
Powdered ammonium hydrogen carbonate makes solid powdery ammonium hydrogen carbonate as precipitating reagent and iron salt solutions-powder using magnetic agitation mode
Shape galapectite mixed liquor mutually mixes well reaction and then generates to be hanged containing the brownish red caused by solid powdery ammonium hydrogen carbonate
The brownish red suspension of float, magnetic agitation action time are 3-24h；In the powdered galapectite mixed liquor of iron salt solutions-, Gu
The mass/mass ratio of the powdered ammonium hydrogen carbonate of body and molysite is：The quality of the Zhi Liang ︰ iron salt solutions of solid powdery ammonium hydrogen carbonate
=0.8-6kg/kg；A-4, the brownish red suspension containing brownish red suspended matter is filtered by vacuum first it is therein to extract
Brown-red solid deposit containing FeOOH- galapectite mixtures, then ethyl alcohol is used to wash brown-red solid deposit to remove
The solid impurity for being not belonging to brown-red solid deposit in brown-red solid deposit, then consolidates the brownish red of washed mistake
Body deposit is placed in 40-80 DEG C of physical environment dry 6-24h to remove the liquid impurity in brown-red solid deposit, so
It will be ground into powder FeOOH- galapectite mixtures by dried brown-red solid deposit afterwards；B-1, powdered corruption is planted
It is sour to be mixed into a pasty mixture as presoma with pure water phase, then a pasty mixture is ground（Carry out
Wet grinding）5-10min；The mass/volume of molysite and pure water ratio is in a pasty mixture：The Zhi Liang ︰ of molysite are pure
Volume=0.5-1g/ml of water purification, B-2, be ground pasty mixture and powdered FeOOH- galapectites mixed first
It closes object and is mutually mixed into secondary pasty mixture, then secondary pasty mixture is ground into 0.5-1.0h, two will be then ground
Secondary pasty mixture drying, then continues regrinding 5-10min by the secondary pasty mixture being oven-dried and forms powder
Shape object；The mass/mass ratio of powdered humic acid and powdered FeOOH- galapectites mixture in secondary pasty mixture
For：Quality=0.05-0.4kg/kg of the powdered FeOOH- galapectites mixtures of Zhi Liang ︰ of powdered humic acid；B-3, by powder
Shape object is placed in the physical environment for being full of and having the inert gas not chemically reacted with powdered object to be added since room temperature
After heat to the fixed temperature value selected in 350-600 DEG C 3-6h is kept the temperature in the fixed temperature value with baking modes；It is opened from room temperature
The heating rate of beginning is 1-10 DEG C/min, and inert gas is argon gas and/or nitrogen；It is obtained after powdered object completes heat preservation
In powdered by Fe3O4The charcoal that halloysite composite material is constituted coats magnetic halloysite compound adsorbent.
Molal quantity/volume ratio of molysite and liquid polar organic solvent is preferably：0.005-0.05mol/L；Solid powder
The mass/mass of shape ammonium hydrogen carbonate and molysite ratio is preferably：2-3kg/kg；Powdered humic acid and powdered FeOOH- galapectites
The mass/mass ratio of mixture is preferably：0.1-0.2kg/kg；Heating rate is preferably 3-8 DEG C/min.
It is a kind of to prepare the method products therefrom that charcoal coats magnetic halloysite compound adsorbent using humic acid, by utilizing corruption
What the method that phytic acid prepares charcoal cladding magnetic halloysite compound adsorbent obtained is in powdered by Fe3O4Halloysite composite material
The charcoal of composition coats magnetic halloysite compound adsorbent.
The present invention verification embodiment be：
Embodiment 1：1.6g iron chloride is dispersed in 200mL absolute ethyl alcohols, 2g galapectites are then added, passes sequentially through ultrasound and stirs
It mixes and magnetic agitation mixing, adds 1.4g ammonium hydrogen carbonate, react 10h in stirring at normal temperature, be then filtered by vacuum, second is used in combination
Alcohol is washed, and then the precipitation through being filtered by vacuum is placed in baking oven or crucible in 80 DEG C of dry 6h, finally with by agate
Manufactured mortar grinder is at powdered FeOOH- galapectites mixture.
Embodiment 2-1：0.05g humic acids and 1.6ml pure water are sequentially added in the mortar made of agate, grinding is equal
It is even, it is subsequently added into the powdered FeOOH- galapectites mixture of 1 gained of 0.5g embodiments, 0.5h is ground successively, dries, is ground into
Powdered object, then drying, ground powdered object are placed in and are passed through in advance in the tube furnace of argon gas with 1-10 DEG C
Heating rate is heated to 500 DEG C and roasts 3h in argon gas, so far obtains by Fe3O4The charcoal that halloysite composite material is constituted coats magnetic
Property galapectite compound adsorbent.Using X-ray diffraction analysis instrument（Bruker D8 advance）Obtained by embodiment 2-1
Fe3O4Halloysite composite material carries out crystalline phase measurement, gained Fe3O4The XRD spectrum of halloysite composite material is as shown in Figure 1：Figure
1 XRD spectrum shows the Fe of charcoal cladding3O4Halloysite composite material is successfully acquired.
Embodiment 2-2：0.1g humic acids and 1.6ml pure water are sequentially added in the mortar made of agate, grinding is uniform,
It is subsequently added into the powdered FeOOH- galapectites mixture of 1 gained of 0.5g embodiments, 0.5h is ground successively, dries, pulverizes
Last shape object, then drying, ground powdered object are placed in and are passed through in advance in the tube furnace of argon gas with 1-10 DEG C of liter
Warm rate is heated to 500 DEG C and roasts 3h in argon gas, so far obtains by Fe3O4The charcoal coated magnetic that halloysite composite material is constituted
Galapectite compound adsorbent.Using X-ray diffraction analysis instrument（Bruker D8 advance）Obtained by embodiment 2-2
Fe3O4Halloysite composite material carries out crystalline phase measurement, gained Fe3O4The XRD spectrum of halloysite composite material is as shown in Figure 2：Figure
2 XRD spectrum shows the Fe of charcoal cladding3O4Halloysite composite material is successfully acquired.
Embodiment 2-3：0.2g humic acids and 1.6ml pure water are sequentially added in the mortar made of agate, grinding is uniform,
It is subsequently added into the powdered FeOOH- galapectites mixture of 1 gained of 0.5g embodiments, 0.5h is ground successively, dries, pulverizes
Last shape object, then drying, ground powdered object are placed in and are passed through in advance in the tube furnace of argon gas with 1-10 DEG C of liter
Warm rate is heated to 500 DEG C and roasts 3h in argon gas, so far obtains by Fe3O4The charcoal coated magnetic that halloysite composite material is constituted
Galapectite compound adsorbent.Using X-ray diffraction analysis instrument（Bruker D8 advance）Obtained by embodiment 2-3
Fe3O4Halloysite composite material carries out crystalline phase measurement, gained Fe3O4The XRD spectrum of halloysite composite material is as shown in Figure 3：Figure
3 XRD spectrum shows the Fe of charcoal cladding3O4Halloysite composite material is successfully acquired.
Claims (3)
1. a kind of preparing the method that charcoal coats magnetic halloysite compound adsorbent using humic acid, it is characterised in that：A-1, general
Molysite is dissolved by carrier of liquid polar organic solvent in liquid polar organic solvent, makes molysite and liquid polar organic solvent
It is mixed into uniform clear iron salt solutions；Liquid polar organic solvent is methanol and/or ethyl alcohol and/or propyl alcohol, and propyl alcohol includes just
Propyl alcohol and/or isopropanol, molysite are iron chloride and/or ferric nitrate, molysite and liquid polar organic solvent in iron salt solutions
Mole/volume ratio is：Volume=0.0025-0.1mol/L of the Mo Er number ︰ liquid polar organic solvents of molysite；A-2, in molysite
Powdered galapectite is added in solution, keeps powdered galapectite fully equal with molysite in iron salt solutions using ultrasonic agitation mode
The powdered galapectite mixed dispersion liquid of iron salt solutions-is blended together, ultrasonic agitation action time is 2-15min；In iron salt solutions-powder
In shape galapectite mixed dispersion liquid, molysite and powdered galapectite mole/mass/mass ratio is：The Mo Er number ︰ powder of molysite
The mass/volume ratio of quality=0.5-5mol/kg of shape galapectite, powdered galapectite and liquid polar organic solvent is：Powder
Volume=1-25g/L of the Zhi Liang ︰ liquid polar organic solvents of shape galapectite；A-3, it is mixed in the powdered galapectite of iron salt solutions-
Solid powdery ammonium hydrogen carbonate is added in liquid, makes solid powdery ammonium hydrogen carbonate as precipitating reagent and iron using magnetic agitation mode
The powdered galapectite mixed liquor of salting liquid-mutually mixes well reaction and then generates to contain to be caused by solid powdery ammonium hydrogen carbonate
Brownish red suspended matter brownish red suspension, magnetic agitation action time be 3-24h；In the powdered galapectite of iron salt solutions-
In mixed liquor, the mass/mass ratio of solid powdery ammonium hydrogen carbonate and molysite is：The Zhi Liang ︰ iron of solid powdery ammonium hydrogen carbonate
Quality=0.8-6kg/kg of salting liquid；A-4, the brownish red suspension containing brownish red suspended matter is filtered by vacuum first
To extract the brown-red solid deposit therein for having generated FeOOH- galapectite mixtures, then it is solid using ethyl alcohol washing brownish red
Body deposit will then be washed with removing the solid impurity for being not belonging to brown-red solid deposit in brown-red solid deposit
The brown-red solid deposit washed is placed in 40-80 DEG C of physical environment dry 6-24h to remove brown-red solid deposit
In liquid impurity, then will be ground into powder FeOOH- galapectite mixtures by dried brown-red solid deposit；
B-1, powdered humic acid and pure water phase are mixed into a pasty mixture as presoma, then mix a paste
It closes object and grinds 5-10min；The mass/volume of molysite and pure water ratio is in a pasty mixture：The Zhi Liang ︰ of molysite are pure
Volume=0.5-1g/ml of water, B-2, be ground pasty mixture mixed with powdered FeOOH- galapectites first
Object is mutually mixed into secondary pasty mixture, then secondary pasty mixture is ground 0.5-1.0h, then secondary by what is be ground
Pasty mixture is dried, and the secondary pasty mixture being oven-dried then is continued regrinding 5-10min and is formed powdered
Object；The mass/mass ratio of powdered humic acid and powdered FeOOH- galapectites mixture is in secondary pasty mixture：
Quality=0.05-0.4kg/kg of the powdered FeOOH- galapectites mixtures of Zhi Liang ︰ of powdered humic acid；B-3, will be powdered
Object is placed in the physical environment for being full of and having the inert gas not chemically reacted with powdered object and is begun to warm up from room temperature
After to the fixed temperature value selected in 350-600 DEG C 3-6h is kept the temperature in the fixed temperature value with baking modes；Since room temperature
Heating rate be 1-10 DEG C/min, inert gas be argon gas and/or nitrogen；It is in after powdered object completes heat preservation
It is powdered by Fe3O4The charcoal that halloysite composite material is constituted coats magnetic halloysite compound adsorbent.
2. according to claim 1 prepare the method that charcoal coats magnetic halloysite compound adsorbent using humic acid,
It is characterized in：Molysite and liquid polar organic solvent mole/volume ratio is preferably：0.005-0.05mol/L；Solid powdery carbon
The mass/mass ratio of sour hydrogen ammonium and molysite is preferably：2-3kg/kg；Powdered humic acid is mixed with powdered FeOOH- galapectites
The mass/mass ratio of object is preferably：0.1-0.2kg/kg；Heating rate is preferably 3-8 DEG C/min.
3. a kind of side as claimed in claim 1 or 2 preparing charcoal cladding magnetic halloysite compound adsorbent using humic acid
Method products therefrom, it is characterised in that：It is obtained by preparing the method that charcoal coats magnetic halloysite compound adsorbent using humic acid
In powdered by Fe3O4The charcoal that halloysite composite material is constituted coats magnetic halloysite compound adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710752788.5A CN108514863B (en) | 2017-08-29 | 2017-08-29 | Method for preparing carbon-coated magnetic halloysite compound adsorbent by using humic acid and product obtained by method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710752788.5A CN108514863B (en) | 2017-08-29 | 2017-08-29 | Method for preparing carbon-coated magnetic halloysite compound adsorbent by using humic acid and product obtained by method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108514863A true CN108514863A (en) | 2018-09-11 |
| CN108514863B CN108514863B (en) | 2021-04-09 |
Family
ID=63432696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710752788.5A Active CN108514863B (en) | 2017-08-29 | 2017-08-29 | Method for preparing carbon-coated magnetic halloysite compound adsorbent by using humic acid and product obtained by method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108514863B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198508A (en) * | 2021-04-30 | 2021-08-03 | 浙江工业大学 | Load type iron-nitrogen-carbon composite material and application thereof in treatment of dye wastewater |
| CN113351173A (en) * | 2021-06-03 | 2021-09-07 | 华南理工大学 | Humic acid-containing magnetic adsorption material and preparation method and application thereof |
| CN114307943A (en) * | 2021-12-31 | 2022-04-12 | 西藏大学 | Magnetic MgO adsorbent and preparation method and application thereof |
| CN114505054A (en) * | 2022-02-17 | 2022-05-17 | 江西省水利科学院 | Preparation method and application of high-content zero-valent ferromagnetic loaded biochar |
| CN117960123A (en) * | 2024-04-02 | 2024-05-03 | 清华大学 | Composite microsphere adsorbent of halloysite nanotube and cellulose derived carbon, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004068510A2 (en) * | 2003-01-27 | 2004-08-12 | Dalton Robert C | Field concentrators for artificial dielectric systems and devices |
| CN106964350A (en) * | 2017-03-15 | 2017-07-21 | 武汉理工大学 | A kind of Fe3O4@C@TiO2The simple method for preparing of Magneto separate photochemical catalyst |
-
2017
- 2017-08-29 CN CN201710752788.5A patent/CN108514863B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004068510A2 (en) * | 2003-01-27 | 2004-08-12 | Dalton Robert C | Field concentrators for artificial dielectric systems and devices |
| CN106964350A (en) * | 2017-03-15 | 2017-07-21 | 武汉理工大学 | A kind of Fe3O4@C@TiO2The simple method for preparing of Magneto separate photochemical catalyst |
Non-Patent Citations (3)
| Title |
|---|
| JIANG LING ETAL.: "Surface Modifications of Halloysite Nanotubes with Superparamagnetic Fe3O4 Nanoparticles and Carbonaceous Layers for Efficient Adsorption of Dyes in Water Treatment", 《CHEM. RES. CHIN. UNIV.》 * |
| JIANXIN CHEN ETAL.: "Comparative study of catalytic activity of different Fe-pillared bentonites in the presence of UV light and H2O2", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
| S. A. BASKAKOV ETAL.: "High Temperature Carbonization of Humic Acids and a Composite of Humic Acids with Graphene Oxide", 《NANOSTRUCTURED SYSTEMS AND MATERIALS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198508A (en) * | 2021-04-30 | 2021-08-03 | 浙江工业大学 | Load type iron-nitrogen-carbon composite material and application thereof in treatment of dye wastewater |
| CN113351173A (en) * | 2021-06-03 | 2021-09-07 | 华南理工大学 | Humic acid-containing magnetic adsorption material and preparation method and application thereof |
| CN114307943A (en) * | 2021-12-31 | 2022-04-12 | 西藏大学 | Magnetic MgO adsorbent and preparation method and application thereof |
| CN114307943B (en) * | 2021-12-31 | 2024-03-22 | 西藏大学 | Magnetic MgO adsorbent and preparation method and application thereof |
| CN114505054A (en) * | 2022-02-17 | 2022-05-17 | 江西省水利科学院 | Preparation method and application of high-content zero-valent ferromagnetic loaded biochar |
| CN114505054B (en) * | 2022-02-17 | 2023-03-10 | 江西省水利科学院 | Preparation method and application of high-content zero-valent ferromagnetic loaded biochar |
| CN117960123A (en) * | 2024-04-02 | 2024-05-03 | 清华大学 | Composite microsphere adsorbent of halloysite nanotube and cellulose derived carbon, and preparation method and application thereof |
| CN117960123B (en) * | 2024-04-02 | 2024-06-11 | 清华大学 | Composite microsphere adsorbent of halloysite nanotube and cellulose derived carbon, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108514863B (en) | 2021-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108514863A (en) | The method and its products therefrom that charcoal coats magnetic halloysite compound adsorbent are prepared using humic acid | |
| Xiong et al. | Highly enhanced adsorption performance to uranium (VI) by facile synthesized hydroxyapatite aerogel | |
| Xia et al. | A facile synthesis of hydroxyapatite for effective removal strontium ion | |
| CN111203180B (en) | Magnetic biochar composite adsorbent and preparation method and application thereof | |
| CN106916314B (en) | The preparation method of metal-organic framework materials MIL 88B (Fe) | |
| CN106975443B (en) | A kind of preparation method and application of magnetic modified bentonite adsorbent | |
| Ma et al. | Facile and scalable synthesis of magnetite/carbon adsorbents by recycling discarded fruit peels and their potential usage in water treatment | |
| Wang et al. | A novel magnetic Cd (II) ion-imprinted polymer as a selective sorbent for the removal of cadmium ions from aqueous solution | |
| CN102250347B (en) | Preparation method of chelating type ion exchange resin with natural halloysite nanotube (HNT) as matrix | |
| CN106475066B (en) | Preparation method, product and the application of Magnaglo acticarbon | |
| CN106423051A (en) | Preparation method and application of magnetic activated hydrothermal biochar microspheres | |
| CN111686694B (en) | MIL-101 material preparation method and application | |
| CN108579664A (en) | Magnetic nanometer composite material and its preparation method and application based on two-dimensional layer material magadiite | |
| Amin et al. | LDH of NiZnFe and its composites with carbon nanotubes and data-palm biochar with efficient adsorption capacity for RB5 dye from aqueous solutions: Isotherm, kinetic, and thermodynamics studies | |
| CN106964311A (en) | A kind of magnetic Nano Yi Meng clays for loading nano zero valence iron and preparation method thereof, application | |
| CN108940217B (en) | Aluminum-based metal organic framework @ gamma-alumina composite material and preparation and application thereof | |
| CN107961764A (en) | A kind of preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon | |
| CN108393073A (en) | A kind of preparation method of general magnetic adsorbent and application | |
| CN111111612A (en) | Preparation and use method of magnetic porous biochar for removing chromium in water | |
| CN105148835B (en) | Granular pattern 13X molecular sieves/attapulgite loaded Nanoscale Iron nickel material and preparation method thereof | |
| CN110090618A (en) | Prussian blue/classifying porous charcoal compound adsorbent of one kind and its preparation method and application | |
| CN104891513B (en) | A kind of preparation method of Magnetic Bentonite | |
| CN107930670B (en) | A kind of heterogeneous catalysis material and its preparation method and application that self-cradling type is homogeneously changed | |
| CN103769082B (en) | The charcoal load activity preparation method of MnOx, product and application | |
| Yang et al. | A critical review on the development of lanthanum-engineered biochar for environmental applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |