CN103480267A - Air cleaning material, and preparation method and application thereof - Google Patents
Air cleaning material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an air cleaning material, and a preparation method and an application thereof, and belongs to the technical field of chemical catalytic decomposition. The air cleaning material comprise a base material and a manganese oxide loaded on the base material; the manganese oxide is a birnessite type manganese oxide prepared by performing in-situ reduction on a permanganate and a reducing agent; and the base material is filter cotton, non-woven fabrics, cotton cloth, gauze, or fiber with particle filtering function. The preparation method comprises the following steps: step 1, dissolving a quaternary ammonium salt and the permanganate in water, adding the base material; step 2, adding the reducing agent into the solution obtained in the step 1, mixing uniformly; step 3, heating the solution obtained in the step 2 at a constant temperature; and step 4, taking out the base material and drying to obtain the finished product. According to the technical scheme, the manganese oxide is simple loaded on the fiber material base material such as filter cotton and the like, so that the obtained low-wind-resistance cleaning material is capable of continuously rapid degrading formaldehyde and ozone in the air at room temperature; and the preparation method of the air cleaning material is simple and low in cost, and no other pollutions are introduced.
Description
Technical field
The invention belongs to chemical catalysis decomposition technique field, particularly pollutant decomposition technique field in surrounding air.
Background technology
Contain a large amount of particles in air, as dust, dust, flue dust, mine dust, sand dust, powder etc., the filter-type fiber base material purify to remove aspect airborne particle play a part indispensable, but also there are inorganic pollution thing and the volatile organic contaminant of a lot of gaseous states in the interior space of people's work, life, as nitrogen oxide, ozone, formaldehyde, toluene, dimethylbenzene etc.Wherein formaldehyde has stimulation toxicity, is a kind of carcinogen, can be via suction and skin contact and affect health.It is a kind of common indoor air pollutants, mainly from indoor construction material and ornament, discharges, and has slow release, the lasting characteristics of polluting.2002, there is the researcher to investigate Multimetal oxide, removal effect (Atmospheric Environment 2002 as PARA FORMALDEHYDE PRILLS(91,95)s such as silver oxide, cupric oxide, cobalt oxide, zinc oxide, titanium dioxide, di-iron trioxide and manganese dioxide, 36,5543 – 5547), find that under normal temperature, the manganese dioxide PARA FORMALDEHYDE PRILLS(91,95) has the highest removal activity.There is in recent years report that Mn oxide is carried on to (Applied Catalysis B:Environmental 2004,51,83 – 91 on aluminium oxide, titanium dioxide and granular activated carbon; CN102294237; Top Catal 2008,47,109 – 115; ACTA Scientiae Circumstantiae 2008,28,337-341), but these base material of granular pattern for Supported Manganese oxide windages are large, be difficult to actual the use while being applied to the active ventilation cleaning mode of air gas, moreover, the removal effect of PARA FORMALDEHYDE PRILLS(91,95) is poor, under room temperature, is difficult to practical requirement.2011, the American Studies person sticks on glass fibre at room temperature PARA FORMALDEHYDE PRILLS(91,95) by the Mn oxide of preparation by organic gel good removal effect (Applied Catalysis B:Environmental 2011,107,34 – 41), but this kind of manufacture of materials long, complex process consuming time and introduce organic gel and easily produce new pollution.Also there is the researcher that Mn oxide is carried on to Nano Lett. 2010,10 on the porous spinning fabric, 708-714; Nano Lett. 2011,11,2905 – 2911), its process need first is applied to material surface by prepared Chinese ink or Graphene, and step is more complicated, and Mn oxide is not strong for load solid, easily comes off.Therefore invent the scavenging material of being convenient to practical application that a kind of preparation technology is simple, cost is low, windage is low, the formaldehyde pollution of removing in room air for economical and effective has important practical value.
Summary of the invention
The present invention is directed to deficiency of the prior art and provide that a kind of to take the fiber that filter cotton, nonwoven, cotton, gauze etc. have a filtration of particulate matters function be base material material for air purification and preparation and renovation process, the problem solved is how permanganate to be loaded on the air filting material of low windage easily, make the scavenging material of the Supported Manganese oxide that obtains can at room temperature continue, degrade rapidly airborne formaldehyde, ozone, and the preparation method of this scavenging material is simple, cost is low, do not introduce other pollutants.
A kind of material for air purification of the present invention, comprise base material and Mn oxide, Mn oxide loads on base material, it is characterized in that, described base material is filter cotton, nonwoven, cotton, gauze and fiber with filtration of particulate matters function, birnessite type Mn oxide prepared by permanganate and reducing agent local reduction way by described Mn oxide.
The preparation method of a kind of material for air purification of the present invention, is characterized in that, the method comprises the following steps:
(1) quaternary ammonium salt and permanganate are dissolved in water, add base material;
(2) add reducing agent to arrive in step (1) gained solution, fully stir evenly;
(3) solution of step (2) gained is carried out to heated at constant temperature;
(4) take out base material and carry out drying, obtain finished product.
The mixture that described quaternary ammonium salt is a kind of or arbitrary proportion in softex kw and hexadecyltrimethylammonium chloride.The mass ratio of described permanganate and base material is 1:0.2 ~ 1:2.Described permanganate is water miscible permanganate.Described water miscible permanganate is a kind of in sodium permanganate, potassium permanganate and ammonium permanganate or their any combination.Described reducing agent is a kind of in methyl alcohol, ethanol and ethylene glycol or their any combination.Described heating-up temperature is room temperature ~ 50 ℃, and the time is 0.5 ~ 12 hour; Described baking temperature is room temperature ~ 200 ℃.The concentration of described quaternary ammonium salt is 0.1 ~ 10g/L, and permanganate is 1:10 ~ 1:300 with the amount of substance ratio of reducing agent.
The material for air purification prepared according to above-mentioned material for air purification or above-mentioned preparation method is as in arbitrary purifier that needs purifying formaldehyde and/or ozone or directly described scavenging material is positioned over to the application of scavenging material in the space that needs purifying formaldehyde and/or ozone.
Particle and the dust of the present invention's base material used in not only can filtered air at room temperature decomposes airborne formaldehyde and ozone after the Mn oxide of local reduction way load.
Advantage of the present invention is mainly reflected in:
(1) adopt the Mn oxide of local reduction way one-step synthesis support type, preparation technology is simple, cost is low, is easy to large-scale production.
(2) active component load on filter cotton is firm, and load capacity is with the concentration adjustment by adjusting presoma permanganate.
(3) the scavenging material windage prepared is low, and has good pliability, is convenient to be prepared into various shape, and the air cleaning that is suitable for various ways is processed.
(4) scavenging material of inventing is the airborne formaldehyde of fast decoupled at room temperature, purifies cost low, and can fast and conveniently regenerate.
The accompanying drawing explanation
Fig. 1 is the photo after filter cotton Supported Manganese oxide of the present invention.
Fig. 2 is the electron micrograph before and after filter cotton Supported Manganese oxide.
Fig. 2 a is filter cotton low power electromicroscopic photograph.
Fig. 2 b, Fig. 2 c are the low power electromicroscopic photograph after filter cotton Supported Manganese oxide of the present invention;
Fig. 2 d is filter cotton high power electromicroscopic photograph.
Fig. 2 e, Fig. 2 f are the high power electromicroscopic photograph after filter cotton Supported Manganese oxide of the present invention.
Fig. 3 is the Raman spectrum that the present invention loads on Mn oxide on filter cotton.
Fig. 4 is the removal effect figure of filter cotton Supported Manganese oxide of the present invention to formaldehyde in air.
Fig. 5 is the regeneration effect figure of filter cotton Supported Manganese oxide of the present invention to formaldehyde in air.
The following specific embodiment further illustrates the present invention in connection with above-mentioned accompanying drawing.
The specific embodiment
Material for air purification of the present invention, comprise base material and Mn oxide, and Mn oxide loads on base material, and base material is filter cotton, nonwoven, cotton, gauze and fiber with filtration of particulate matters function, and wherein Mn oxide can be the birnessite type Mn oxide.
Below in conjunction with drawings and Examples, the present invention is described in more detail.
Embodiment 1:
Take 0.04 gram softex kw and be dissolved in 20 milliliters of ultra-pure waters, ultrasonic dissolution is to forming uniform solution.The softex kw solution of 0.25 gram filter cotton after cutting being put into to configuration soaks.Take 0.25 gram potassium permanganate, potassium permanganate is joined in the softex kw solution that is placed with filter cotton.Ultrasonicly dissolve fully to potassium permanganate, add subsequently 15 ml methanol, the solution of gained is positioned under 45 ℃ of water-baths to reaction 6 hours.Take out filter cotton and dry under 105 ℃, obtain the filter cotton of Mn oxide load.At this moment Mn oxide has been coated on substrate surface.
Fig. 1 is the photo after filter cotton Supported Manganese oxide of the present invention, and before load, the color of filter cotton is white, and after load, (Fig. 1) is dark, illustrates that a large amount of Mn oxides has loaded on filter cotton.
Fig. 2 is the electromicroscopic photograph before and after filter cotton Supported Manganese oxide, and the electromicroscopic photograph of the filter cotton different amplification that Fig. 2 a and d are not load, know filter cotton filament diameter 20 μ m by figure, and before load, its surface is comparatively smooth.Fig. 2 b is the electromicroscopic photograph after load, and the Mn oxide that is reacted generation by the smooth surface of the visible filter cotton of Fig. 2 b closely covers.The high power electromicroscopic photograph that Fig. 2 e is sample after load, the Mn oxide on visible filter cotton surface is irregular sheet, mutually condenses, lumps.
Soak the filter cotton sample after the Supported Manganese oxide with the sodium oxalate mixed solution of 5% sulfuric acid and 0.1mol/L, with inductive coupling plasma emission spectrograph, measure the manganese ion content in solution, calculating thus the manganese content of filter cotton after load is 15mg/g.
Analyze the sample ground on the filter cotton of load with the micro confocal laser Raman spectrometer, with 532nm laser as excitation source, gained spectrum as shown in Figure 3, occur four peaks in 200 ~ 1000 cm-1 scopes, its peak position is respectively: 502(w), 569(s), 648(s), 798(w) cm-1.Infer that thus the Mn oxide that loads on the filter cotton surface is the birnessite type Mn oxide.
Embodiment 2
Take 0.04 gram softex kw and be dissolved in 20 milliliters of ultra-pure waters, ultrasonic dissolution is to forming uniform solution.The softex kw solution of 0.25 gram filter cotton after cutting being put into to configuration soaks.Take 0.25 gram potassium permanganate, potassium permanganate is joined in the softex kw solution that is placed with filter cotton.Ultrasonicly dissolve fully to potassium permanganate, add subsequently 5 ml methanol, the solution of gained is positioned under room temperature to reaction 10 hours.The taking-up filter cotton is dried, and obtains the filter cotton of Mn oxide load.
Fig. 2 is the electromicroscopic photograph before and after filter cotton Supported Manganese oxide, and the Mn oxide that is reacted generation by the smooth surface of the visible filter cotton of Fig. 2 c closely covers.The high power electromicroscopic photograph that Fig. 2 f is sample after load, the Mn oxide on visible filter cotton surface still is irregular sheet, but its sheet below is in conjunction with the consolidation Mn oxide.
Soak the filter cotton sample after the Supported Manganese oxide with the sodium oxalate mixed solution of 5% sulfuric acid and 0.1mol/L, with inductive coupling plasma emission spectrograph, measure the manganese ion content in solution, calculating thus the manganese content of filter cotton after load is 20mg/g.
The Raman spectrum of Mn oxide on filter cotton prepared for this embodiment by Fig. 3.Analyze the sample ground on the filter cotton of load with the micro confocal laser Raman spectrometer, with 532nm laser as excitation source, gained spectrum as shown in Figure 3, occur four peaks in 200 ~ 1000 cm-1 scopes, its peak position is respectively: 502(w), 569(s), 648(s), 798(w) cm-1.Infer that thus the Mn oxide that loads on the filter cotton surface is the birnessite type Mn oxide.
Embodiment 3
Take 0.04 gram softex kw and be dissolved in 20 milliliters of ultra-pure waters, ultrasonic dissolution is to forming uniform solution.The softex kw solution of 0.25 gram filter cotton after cutting being put into to configuration soaks.Take 0.15 gram potassium permanganate, potassium permanganate is joined in the softex kw solution that is placed with filter cotton.Ultrasonicly dissolve fully to potassium permanganate, add subsequently 15 ml methanol, the solution of gained is positioned under room temperature to reaction 10 hours.The taking-up filter cotton is dried, and obtains the filter cotton of Mn oxide load.
Soak the filter cotton sample after the Supported Manganese oxide with the sodium oxalate mixed solution of 5% sulfuric acid and 0.1mol/L, with inductive coupling plasma emission spectrograph, measure the manganese ion content in solution, calculating thus the manganese content of filter cotton after load is 14mg/g.
Embodiment 4
Take 0.08 gram softex kw and be dissolved in 20 milliliters of ultra-pure waters, ultrasonic dissolution is to forming uniform solution.The softex kw solution of 0.25 gram filter cotton after cutting being put into to configuration soaks.Take 0.25 gram sodium permanganate, potassium permanganate is joined in the softex kw solution that is placed with filter cotton.Ultrasonicly dissolve fully to potassium permanganate, add subsequently 5 milliliters of ethanol, the solution of gained is positioned under room temperature to reaction 10 hours.The taking-up filter cotton is dried, and obtains the filter cotton of Mn oxide load.
Embodiment 5
Take 0.04 gram hexadecyltrimethylammonium chloride and be dissolved in 20 milliliters of ultra-pure waters, ultrasonic dissolution is to forming uniform solution.The hexadecyltrimethylammonium chloride solution of 0.25 gram filter cotton after cutting being put into to configuration soaks.Take 0.25 gram ammonium permanganate, ammonium permanganate is joined in the hexadecyltrimethylammonium chloride solution that is placed with filter cotton.Ultrasonicly dissolve fully to ammonium permanganate, add subsequently 5 milliliters of ethylene glycol, the solution of gained is positioned under room temperature to reaction 10 hours.The taking-up filter cotton is dried, and obtains the filter cotton of Mn oxide load.
Embodiment 6
At room temperature measure the removal effect of the filter cotton of the Supported Manganese oxide that embodiment 1 ~ 5 obtains to formaldehyde in air.Take material prepared by 0.15g, inlet gas concentration at formaldehyde is 4 mg/m3, relative humidity 30 ~ 40%, air velocity is 1L/min, face velocity is 352.8cm/min, the time of staying ~ 0.1s, after with overdraught, continuously the scavenging material by ~ 0.15g embodiment 1 ~ 4 preparation reacts 1 hour with this understanding respectively, the removal effect of formaldehyde as shown in Figure 4, the filtering material of this material small amount under higher formaldehyde atmosphere under the time of staying in realistic application PARA FORMALDEHYDE PRILLS(91,95) removal effect is preferably arranged.
Material prepared by the embodiment 2 of take is example, has investigated the regeneration effect of the filter cotton of Supported Manganese oxide.The inlet gas concentration of setting formaldehyde is 0.5mg/m3, relative humidity 40%, air velocity is 1L/min, face velocity is 352.8cm/min, the scavenging material continuously prepared by 0.32g embodiment 2 with overdraught, with this understanding, as shown in Figure 5, the filter cotton of freshly prepd Supported Manganese oxide is still 70% at the clearance of reaction PARA FORMALDEHYDE PRILLS(91,95) after 80 hours to the clean-up effect of formaldehyde.Scavenging material reaction after 80 hours was 80 ℃ of lower thermal regenerations 2 hours, again under above-mentioned the same terms, measure the removal capacity of its PARA FORMALDEHYDE PRILLS(91,95), the removal effect of its PARA FORMALDEHYDE PRILLS(91,95) is identical with fresh sample, illustrates by this mode this scavenging material of can regenerating.
The material of above-mentioned filter cotton base material is acrylic fibers, can also select cotton, gauze, nonwoven etc. to have the fiber etc. of filtration of particulate matters function as base material; Above-mentioned ultrasonic dissolution method can also be used stirring means; The method of above-mentioned heated at constant temperature can adopt heated at constant temperature in water-bath or at room temperature, the heater of electric jacket, controllable temperature can; Drying can at room temperature or with the heater of controllable temperature be carried out drying.
The material for air purification of preparing according to said method can be applied to any needs and purify air in the purifier of middle formaldehyde and/or ozone; Perhaps directly scavenging material of the present invention is positioned in the space that needs purifying formaldehyde and/or ozone.Directly scavenging material of the present invention is positioned in the space that needs to purify, not only with low cost, and still can reach the effect of the airborne formaldehyde of extraordinary decomposition, ozone.
In addition, those skilled in the art also can do other variation in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (10)
1. a material for air purification, comprise base material and Mn oxide, Mn oxide loads on base material, it is characterized in that, described base material is the fiber with filtration of particulate matters function, birnessite type Mn oxide prepared by permanganate and reducing agent local reduction way by described Mn oxide.
2. the preparation method of a material for air purification, is characterized in that, the method comprises the following steps:
(1) quaternary ammonium salt and permanganate are dissolved in water, add base material;
(2) add reducing agent to arrive in step (1) gained solution, fully stir evenly;
(3) solution of step (2) gained is carried out to heated at constant temperature;
(4) take out base material and carry out drying, obtain finished product.
3. preparation method according to claim 2, is characterized in that, the mixture that described quaternary ammonium salt is a kind of or arbitrary proportion in softex kw and hexadecyltrimethylammonium chloride.
4. preparation method according to claim 2, is characterized in that, the mass ratio of described permanganate and base material is 1:0.2 ~ 1:2.
5. preparation method according to claim 2, is characterized in that, described permanganate is water miscible permanganate.
6. preparation method according to claim 5, is characterized in that, described water miscible permanganate is a kind of in sodium permanganate, potassium permanganate and ammonium permanganate or their any combination.
7. preparation method according to claim 2, is characterized in that, described reducing agent is a kind of in methyl alcohol, ethanol and ethylene glycol or their any combination.
8. preparation method according to claim 2, is characterized in that, described heating-up temperature is room temperature ~ 50 ℃, and the time is 0.5 ~ 12 hour; Described baking temperature is room temperature ~ 200 ℃.
9. preparation method according to claim 2, is characterized in that, the concentration of described quaternary ammonium salt is 0.1 ~ 10g/L, and permanganate is 1:10 ~ 1:300 with the amount of substance ratio of reducing agent.
10. the material for air purification that in material for air purification claimed in claim 1 or claim 2 to 9, the described preparation method of any one prepares is as in arbitrary purifier that needs purifying formaldehyde and/or ozone or directly described scavenging material is positioned over to the application of scavenging material in the space that needs purifying formaldehyde and/or ozone.
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