CN101785989B - Nanometer manganese dioxide/active aluminum oxide compound adsorbent and method for preparing same - Google Patents
Nanometer manganese dioxide/active aluminum oxide compound adsorbent and method for preparing same Download PDFInfo
- Publication number
- CN101785989B CN101785989B CN 201010142654 CN201010142654A CN101785989B CN 101785989 B CN101785989 B CN 101785989B CN 201010142654 CN201010142654 CN 201010142654 CN 201010142654 A CN201010142654 A CN 201010142654A CN 101785989 B CN101785989 B CN 101785989B
- Authority
- CN
- China
- Prior art keywords
- manganese dioxide
- compound adsorbent
- aluminum oxide
- oxide compound
- active aluminum
- 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.)
- Expired - Fee Related
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a nanometer manganese dioxide/active aluminum oxide compound adsorbent. The compound adsorbent is a granular material, the grain size is 4 to 6 meshes, the surface of the compound adsorbent has a nanometer pore structure, and the pore size is 5 to 10 nanometers. Compared with the conventional manganese dioxide/active aluminum oxide compound adsorbent, the nanometer manganese dioxide/active aluminum oxide compound adsorbent of the invention has the advantages that: in the grain size is large; the pore size is smaller as the surface has the nanometer pore structure; the adsorption rate is higher; the adsorption capacity is as high as to reach an adsorption equilibrium within 20 minutes in 20mg/L chromium-containing solution, the adsorption equilibrium can be achieved within 20 minutes; and the chromium adsorption capacity is as high as 12mg/g and reduces the chromium content of the solution to below 0.001mg/L, which is much lower than the national limit value which is 0.05mg/L. When the compound adsorbent of the invention is used for reducing heavy metal chromium content of a source of drinking water, the out-factory water is guaranteed to meet the standards; simultaneously, because a surface active agent is added when the compound adsorbent is prepared, the manganese dioxide content of active aluminum oxide spheres is higher and the manganese dioxide is dispersed more uniformly; and thus, the load manganese dioxide is insusceptible to falling off, and the secondary pollution is not caused to the water body.
Description
Technical field
The present invention relates to a kind ofly can effectively remove nanometer manganese dioxide/active aluminum oxide compound adsorbent of crome metal in the micropollutant water and preparation method thereof, belong to water-treatment technology field.
Background technology
In recent years, the heavy metal quantity that is discharged in the drinking water source water body owing to social production, life activity day by day accumulated, and human beings'health and life security in serious threat.Wherein chromium is the most common, the most serious pollutant of harm residents ' health.
Chromium is a kind of heavy metal element of many uses and bigger to human body harm.Chromium can pass through alimentary canal, respiratory tract, skin and mucous membrane and invade human body, brings out lung cancer and nasopharyngeal carcinoma.The compound of all chromium is all toxic, and chromic toxicity is almost bigger 100 times than trivalent chromium.
The carcinogenesis of chromium and compound thereof is affirmed to have long remote effect of latent phase by IARC.Chromium to the pollution of water body not only China and also in the whole world each state all quite serious.As the keypoint control object is generally classified pollution of chromium in countries in the world.
The improvement method that heavy metal chromium pollutes in the water body mainly contains physico-chemical process and biological restoration method two big classes at present, wherein based on the coagulant sedimentation in the physico-chemical process, ion-exchange and absorption method.Absorption method is to handle in the micropollutant water comparatively effective method of heavy metal chromium, and the selection of adsorbent is vital part in the absorption method.Usually adopt activated alumina as adsorbent in the routine techniques, because it has bigger specific area, and the dechromisation effect is more stable, but the adsorption capacity of activated alumina is not high, when the chromium content in the water is higher, effect is obvious inadequately, and what employing at present was more for this reason is manganese dioxide-active oxidation aluminium composite material.But in long-term the use, existing manganese dioxide-active oxidation aluminium composite material still exposes following shortcoming: because material particle size is less, surface void is bigger, the content that adds the manganese dioxide on the activated alumina bead lower (less than 5%), and disperse more inhomogeneous, cause the material adsorption capacity little, dechromisation efficient is low, and the manganese dioxide obscission easily takes place, and causes the secondary pollution of water body.
Summary of the invention
The present invention seeks to: provide that a kind of dispersiveness is better, adsorption capacity is bigger, and can not cause the nanometer manganese dioxide/active aluminum oxide compound adsorbent of secondary pollution to water body, heavy metal chromium content in can more efficiently reduction micropollutant water ensures that output water is up to standard.
Technical scheme of the present invention is: a kind of nanometer manganese dioxide/active aluminum oxide compound adsorbent, be particulate material, and particle diameter is 4～6 orders, the surface is nano-pore structure, aperture 5～10nm.
The BET specific area of above-mentioned nanometer manganese dioxide/active aluminum oxide compound adsorbent of the present invention is 250～320m
2/ g.
Manganese dioxide content in the adsorbent of the present invention on the unit mass activated alumina bead is 8～10%.
The present invention provides a kind of preparation method of above-mentioned nanometer manganese dioxide/active aluminum oxide compound adsorbent simultaneously, comprises the steps:
A. take by weighing 2～5g, particle diameter is 4～6 purpose activated alumina beads, washes 2-3 time repeatedly with deionized water, then drying for standby;
B. get 50～500ml, and concentration is the liquor potassic permanganate of 0.1mol/L～1mol/L, in described liquor potassic permanganate according to potassium permanganate: surfactant: the mass ratio of reducing agent=10: 1: 1, add surfactant and reducing agent respectively, it is stand-by to stir; Surfactant wherein is a kind of in sodium cetanesulfonate, dioctyl sodium sulfosuccinate, polyethylene glycol 800 or the cetomacrogol 1000; Reducing agent is: a kind of in ascorbic acid, glycerine or the n-butanol;
C. place step b to prepare gained solution the activated alumina bead that preliminary treatment is good among the step a, evenly stir 1.5～2h, mixing speed 50～70r/min, then the activated alumina bead is taken out, place baking oven to dry by the fire 2～3h down at 105 ℃, activated alumina bead after will drying at last is impregnated in the above-mentioned solution again, evenly stirs 1.5～2h;
D. the above-mentioned solution that contains the activated alumina bead that obtains is at last transferred in the autoclave that is lined with polytetrafluoroethylene (PTFE), under 150～160 ℃ of temperature conditions, react 10～12h, naturally cool to room temperature, handle through super-dry again, make nano-manganese dioxide-active aluminum oxide compound adsorbent.
Among above-mentioned preparation method's the step a: the activated alumina bead outward appearance that takes by weighing is white, and the surface is nano-pore structure, aperture 5～10nm, and the BET specific surface is between 250～330m
2/ g, particle diameter 4～6 orders.
Among the above-mentioned preparation method, the pH value of the solution that step b makes is controlled between 4～6, and the control of described pH value adopt to add the method for acid, and acid can be adopted a kind of in acetic acid, carbonic acid or the acetic acid.
Among above-mentioned preparation method's the step b, the surfactant of adding is in order to control manganese dioxide at activated alumina bead surface and inner decentralization.
The present invention also provides a kind of rapid filter filtering material that is applied to contain the water treatment plant of chromium at last, its by the aforementioned gained nanometer manganese dioxide/active aluminum oxide compound adsorbent of the present invention and quartz sand according to nanometer manganese dioxide/active aluminum oxide compound adsorbent: make behind the abundant mixing of the volume ratio of quartz sand=1: 100～200.
Advantage of the present invention is:
1. compare with traditional manganese dioxide/active aluminum oxide compound adsorbent, this nanometer manganese dioxide/active aluminum oxide compound adsorbent provided by the invention, particle diameter is bigger, and adding upper surface is nano-pore structure, the aperture is littler, so adsorption rate is faster, adsorption capacity is bigger, for the chromium-containing solution of 20mg/L, 20min can reach adsorption equilibrium, the adsorption capacity of chromium is up to 12mg/g, makes chromium content in the solution less than 0.001mg/L, is significantly less than national limit value 0.05mg/L.So adopt adsorbent provided by the invention to reduce heavy metal chromium content in the drinking water source water body, can the reliable guarantee output water up to standard.
2. compare with the manganese dioxide/active aluminum oxide compound adsorbent that did not add the surfactant preparation in the past, manganese dioxide content among the present invention on every gram activated alumina bead is higher, can reach 8～10%, and the decentralization on activated alumina bead surface is better, so make and manganese dioxide difficult drop-off after the load can not cause secondary pollution to water body.
3. this nanometer manganese dioxide/active aluminum oxide compound adsorbent provided by the invention, its cost of manufacture is low and preparation method is easy, stable.
The specific embodiment
Embodiment 1:
This nanometer manganese dioxide/active aluminum oxide compound adsorbent that present embodiment provides, outward appearance are the spherical particulate material of black, particle diameter 4 orders, and the surface is nano-pore structure by field emission electron microscopy observation, aperture 5nm, the BET specific area is 300.52m
2/ g.Its preparation methods steps is as follows:
A, take by weighing 4.0g, particle diameter 4 purpose activated alumina beads wash 2 times repeatedly with deionized water, and dry back is standby; The activated alumina bead outward appearance that takes by weighing is white, and the surface is nano-pore structure, aperture 5nm, BET specific area 325.43m
2/ g.
B, at 200mL, concentration is in the 0.5mol/L liquor potassic permanganate, according to potassium permanganate: sodium cetanesulfonate: the mass ratio of ascorbic acid=10: 1: 1, add sodium cetanesulfonate and ascorbic acid respectively, add suitable acetic acid, adjusting the pH value of solution value is 5, and it is stand-by to stir;
C. the activated alumina bead that preliminary treatment is good among the step a is placed above-mentioned solution, evenly stir 2h, mixing speed 50r/min, then the activated alumina bead is taken out, place baking oven to dry by the fire 2h down at 105 ℃, alumina globule after will drying at last is impregnated in the above-mentioned solution again, evenly stirs 2h;
D. the above-mentioned solution that contains the activated alumina bead that obtains is at last transferred in the autoclave that is lined with polytetrafluoroethylene (PTFE), reacted 12h down at 150 ℃, naturally cool to room temperature, handle through super-dry again, make nanometer manganese dioxide/active aluminum oxide compound adsorbent.
Get the nanometer manganese dioxide/active aluminum oxide compound adsorbent 0.1g of above-mentioned preparation, place 100ml, in the chromium-containing solution of 12.5mg/L, stir 20min fast after, take out adsorbent, record residue chromium content in the chromium-containing solution less than 0.001mg/L.
Embodiment 2:
This nanometer manganese dioxide/active aluminum oxide compound adsorbent that present embodiment provides, outward appearance are the spherical particulate material of black, particle diameter 6 orders, and the surface is nano-pore structure by field emission electron microscopy observation, aperture 8nm, the BET specific area is 295.78m
2/ g, its preparation methods steps is as follows:
A. take by weighing 2.0g, particle diameter 6 purpose activated alumina beads are used deionized water rinsing 2 times, and dry back is standby; The activated alumina bead outward appearance that takes by weighing is white, and the surface is nano-pore structure, aperture 8nm, BET specific surface 315.21m
2/ g.
B. at 50mL, concentration is in the 1.0mol/L liquor potassic permanganate, according to potassium permanganate: polyethylene glycol 800: the mass ratio of n-butanol=10: 1: 1, add polyethylene glycol 800 and n-butanol respectively, add suitable carbonic acid, adjusting the pH value of solution value is 4.5, and it is stand-by to stir;
C. the activated alumina bead that preliminary treatment is good among the step a is placed above-mentioned solution, evenly stir 2h, mixing speed 60r/min, then the activated alumina bead is taken out, place baking oven to dry by the fire 2h down at 105 ℃, alumina globule after will drying at last is impregnated in the above-mentioned solution again, evenly stirs 2h;
D. the above-mentioned solution that contains the activated alumina bead that obtains is at last transferred in the autoclave of polytetrafluoroethylcontainer container, reacted 10h down at 160 ℃, naturally cool to room temperature, handle through super-dry again, make nanometer manganese dioxide/active aluminum oxide compound adsorbent.
Get the nanometer manganese dioxide/active aluminum oxide compound adsorbent 0.2g of above-mentioned preparation, place 150mL, in the chromium-containing solution of 20mg/L, stir 20min fast after, take out adsorbent, record residue chromium content in the chromium-containing solution less than 0.005mg/L.
Embodiment 3:
A kind of rapid filter filtering material that is applied to contain the water treatment plant of chromium is provided, its by embodiment 1 gained nanometer manganese dioxide/active aluminum oxide compound adsorbent and quartz sand according to nanometer manganese dioxide/active aluminum oxide compound adsorbent: make behind the abundant mixing of volume ratio of quartz sand=1: 150.
Claims (4)
1. the preparation method of a nanometer manganese dioxide/active aluminum oxide compound adsorbent, described nanometer manganese dioxide/active aluminum oxide compound adsorbent is particulate material, and particle diameter is 4～6 orders, and the surface is nano-pore structure, aperture 5～10nm; It is characterized in that comprising the steps:
A. take by weighing 2～5g, particle diameter is 4～6 purpose activated alumina beads, washes 2-3 time repeatedly with deionized water, then drying for standby;
B. get 50～500ml, and concentration is the liquor potassic permanganate of 0.1mol/L～1mol/L, in described liquor potassic permanganate according to potassium permanganate: surfactant: the mass ratio of reducing agent=10: 1: 1, add surfactant and reducing agent respectively, it is stand-by to stir; Surfactant wherein is a kind of in sodium cetanesulfonate, dioctyl sodium sulfosuccinate, polyethylene glycol 800 or the cetomacrogol 1000; Reducing agent is: a kind of in ascorbic acid, glycerine or the n-butanol;
C. place step b to prepare gained solution the activated alumina bead that preliminary treatment is good among the step a, evenly stir 1.5～2h, mixing speed 50～70r/min, then the activated alumina bead is taken out, place baking oven to dry by the fire 2～3h down at 105 ℃, activated alumina bead after will drying at last is impregnated in the above-mentioned solution again, evenly stirs 1.5～2h;
D. the above-mentioned solution that contains the activated alumina bead that obtains is at last transferred in the autoclave that is lined with polytetrafluoroethylene (PTFE), under 150～160 ℃ of temperature conditions, react 10～12h, naturally cool to room temperature, handle through super-dry again, make nano-manganese dioxide-active aluminum oxide compound adsorbent.
2. the preparation method of nanometer manganese dioxide/active aluminum oxide compound adsorbent according to claim 1, it is characterized in that among the described step a: the activated alumina bead outward appearance that takes by weighing is white, the surface is nano-pore structure, aperture 5～10nm, and the BET specific area is between 250～330m
2/ g, particle diameter 4～6 orders.
3. the preparation method of nanometer manganese dioxide/active aluminum oxide compound adsorbent according to claim 1, it is characterized in that the pH value control of the solution that described step b makes is between 4～6, the method that adds acid is adopted in the control of described pH value, and a kind of in acetic acid, carbonic acid and the acetic acid adopted in acid.
4. the preparation method of nanometer manganese dioxide/active aluminum oxide compound adsorbent according to claim 1 is characterized in that among the described step b, and the surfactant of adding is in order to control manganese dioxide at activated alumina bead surface and inner decentralization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010142654 CN101785989B (en) | 2010-04-06 | 2010-04-06 | Nanometer manganese dioxide/active aluminum oxide compound adsorbent and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010142654 CN101785989B (en) | 2010-04-06 | 2010-04-06 | Nanometer manganese dioxide/active aluminum oxide compound adsorbent and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101785989A CN101785989A (en) | 2010-07-28 |
| CN101785989B true CN101785989B (en) | 2013-07-10 |
Family
ID=42529451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010142654 Expired - Fee Related CN101785989B (en) | 2010-04-06 | 2010-04-06 | Nanometer manganese dioxide/active aluminum oxide compound adsorbent and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101785989B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102773070B (en) * | 2012-08-26 | 2014-03-12 | 西安科技大学 | Preparation method of magnetic nanometer particle with activated aluminium oxide shell |
| CN103566876A (en) * | 2013-09-26 | 2014-02-12 | 蚌埠华纺滤材有限公司 | Hydrogen-sulfide-removed modified active carbon and preparation method thereof |
| CN107774235B (en) * | 2017-10-31 | 2023-06-23 | 华南师范大学 | Composite metal oxide loaded corncob fiber adsorption material and preparation method and application thereof |
| CN113426471B (en) * | 2021-06-28 | 2022-10-04 | 哈尔滨工业大学 | Dynamic preparation method and enhanced oxidation filtration application of nascent-state nano-layered manganese catalyst |
| CN115554446B (en) * | 2022-08-01 | 2024-03-08 | 盐城工学院 | Multifunctional air freshener and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3027219B2 (en) * | 1991-05-14 | 2000-03-27 | 株式会社日本触媒 | How to remove nitrogen oxides |
| CN101058069A (en) * | 2007-06-01 | 2007-10-24 | 山东大学 | Manganese dioxide/active aluminum oxide composite adsorbing material and its preparation method |
-
2010
- 2010-04-06 CN CN 201010142654 patent/CN101785989B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3027219B2 (en) * | 1991-05-14 | 2000-03-27 | 株式会社日本触媒 | How to remove nitrogen oxides |
| CN101058069A (en) * | 2007-06-01 | 2007-10-24 | 山东大学 | Manganese dioxide/active aluminum oxide composite adsorbing material and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| JP特许第3027219B2 2000.01.28 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101785989A (en) | 2010-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101785989B (en) | Nanometer manganese dioxide/active aluminum oxide compound adsorbent and method for preparing same | |
| CN110102260A (en) | A kind of iron and manganese oxides-charcoal composite material and preparation method and application | |
| CN103521174B (en) | Indoor air purification material and preparation method thereof | |
| CN104667916B (en) | Method for preparing catalytic wet oxidation catalyst | |
| CN100460056C (en) | Method for preparing sulfate akaganeite adsorbent for de-arsenation | |
| US10933406B2 (en) | Method of preparing large-size high-porosity Fe-doped photocatalytic porous magnetic microspheres and uses thereof | |
| CN110787790B (en) | Sea urchin-shaped metal oxide porous photocatalytic material and preparation method and application thereof | |
| CN107469834A (en) | A kind of ZnS/CuS nanometer sheets composite photo-catalyst preparation method | |
| CN102764659A (en) | Cobalt-modified bismuth tungstate composite photocatalyst, its preparation method and application thereof | |
| Cai et al. | Self-enhanced and efficient removal of As (III) from water using Fe–Cu–Mn composite oxide under visible-light irradiation: synergistic oxidation and mechanisms | |
| CN110624534A (en) | Biological genetic WO3Photocatalyst and preparation method and application thereof | |
| CN104667985B (en) | A kind of catalytic wet oxidation catalyst and preparation method thereof | |
| CN105080588A (en) | Preparation method for adsorption catalyst for removing indoor formaldehyde | |
| CN206229202U (en) | A kind of absorption bag based on Graphene | |
| CN110237702A (en) | A kind of material for air purification and preparation method thereof | |
| CN107335422A (en) | A kind of preparation method of carbon functionalization cerium oxide | |
| CN101905103A (en) | Method for manufacturing composite millipore filter element for efficiently removing arsenic and fluoride in drinking water | |
| CN105709737B (en) | Catalytic wet oxidation catalyst and its preparation method | |
| Liu et al. | Constructing a novel type-Ⅱ ZnO/BiOCOOH heterojunction microspheres for the degradation of tetracycline and bacterial inactivation | |
| CN104667936B (en) | Method for preparing catalytic wet oxidation catalyst | |
| Sahu et al. | As (III) removal from aqueous solutions using simultaneous oxidation and adsorption process by hierarchically magnetic flower-like Fe3O4@ C-dot@ MnO2 nanocomposite | |
| CN108912887B (en) | Diatom ooze coating capable of degrading formaldehyde and used for interior decoration | |
| CN104667922A (en) | Method for preparing noble metal catalyst for catalytic wet oxidation | |
| CN110773145A (en) | Ce-doped TiO based on modified diatomite 2Preparation method and application of floating type photocatalytic composite material | |
| CN115069208B (en) | Porous fiber bundle-shaped titanium-based lithium adsorbent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130710 Termination date: 20140406 |