CN104549370B - Photocatalysis cellular activated carbon net - Google Patents
Photocatalysis cellular activated carbon net Download PDFInfo
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- CN104549370B CN104549370B CN201410830775.1A CN201410830775A CN104549370B CN 104549370 B CN104549370 B CN 104549370B CN 201410830775 A CN201410830775 A CN 201410830775A CN 104549370 B CN104549370 B CN 104549370B
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Abstract
Photocatalysis cellular activated carbon net disclosed by the invention, using Alveolate activated carbon net as carrier, has loaded the TiO of Co, Pr and S on the net at Alveolate activated carbon2, described TiO2In photocatalyst Co: Pr: S: TiO2Mol ratio be 0.01～0.03: 0.005～0.015: 0.5～2.0: 0.9～1.2.Both kept the function of activated carbon adsorption organic pollution, there is again the ability of catalyst responding to visible light degradable organic pollutant.It is good that photocatalysis Alveolate activated carbon net has straight hole network structure, aeration and light transmission, and its specific surface area is 750～1050m2/ g, iodine sorption value is 900～1100mg/g, and carbon tetrachloride adsorption rate is 40～60%.At 30m3Confined space and with visible ray as light source, the formaldehyde clearance after 50min is 95.6～98.7%, and toluene is 90.3～93.6%, and ammonia is 92.8～96.0%.
Description
Technical field
The present invention relates to photocatalysis cellular activated carbon net and preparation method, especially Alveolate activated carbon net carrier and doping TiO2
The preparation of photocatalyst and the method that catalyst is carried on carrier.
Background technology
Activated carbon is widely used to administer air and water pollution as excellent adsorbent, conventional for granular active carbon and powder
End activated carbon.The ature of coal cellular activated carbon developed in recent years has the advantage that specific surface area is big, absorption property is strong, the most very
Paid attention to.Although it has many advantages, but the most saturated, use cost is high, even if being also difficult to be returned to previous level by regeneration.
With TiO2All of pollutant generation photolysis almost can be made under action of ultraviolet light to be changed into nothing as photocatalyst
Pest, and reaction condition is gentle (room temperature, normal pressure), although there is very much prospect, but there is TiO2Can not by excited by visible light,
Powdered form uses the drawbacks such as difficult recovery.This is carried out and has included to TiO2It is entrained in interior method to extend the sound to visible ray
Should, and and the method for exploitation fixed catalyst.
For overcoming the deficiency of activated carbon and photocatalysis technology, play the strong point of the two, the most by photocatalysis technology and absorption
The report that technology combines.The most conventional activated carbon supported TiO2Method have two kinds, one be by precursor load
On carrier, then reheat and make precursor be changed into TiO2；Another kind is by TiO2Nano-powder is loaded by various modes
On carrier.
CN1288077C discloses a kind of method directly being prepared Alveolate activated carbon by coal.The method is by coal dust, emulsifying coal
Tar, water-soluble binder, lubricant and water through raw material pulverizing, dispensing, kneading, extrusion molding, be dried, carbonization, work
Change and obtain.This invention has low cost, production equipment simplifies, the Alveolate activated carbon of preparation has unit volume specific surface area
Greatly, voidage acid-fast alkali-proof high, water-fast, comprcssive strength high, heat-resist, the advantage such as easy hot recycling or regenerated from washing.But
The physical property of material must be improved.
CN101857224 discloses the preparation method of a kind of resin-bonded Alveolate activated carbon, by dry powder blend, wet method kneading
The honeycomb that the step of preparation plasticity pug, vacuum pugging, extrusion molding, dry, cured and secondary heat treatment obtains
Activated carbon, owing to its phenolic resin is in addition to the mechanical strength that performance cementation improves this activated carbon, moreover it is possible to significantly improve honeybee
The thermostability of nest shaped activated carbon；Add porous mineral and more can be effectively improved mechanical strength and the specific surface area of Alveolate activated carbon；
This processing method heat treatment temperature ratio is relatively low, and energy consumption is little, it is possible to effectively reduce production cost；And preparation technology and equipment letter
Single, investment of production is smaller, reduce further cost.
CN101596457A discloses a kind of boron and other element coblended nano TiO 2 light catalyst and preparation method thereof,
Be use titanate esters and boric acid as titanium source and boron source, other doped chemical comprise transition metal, rare earth metal or nonmetal in
One or more, use acetic acid, nitric acid or citric acid as hydrolysis catalyst, alcohol and water mixture as reaction system,
Boron and other element coblended nano TiO 2 light catalyst is prepared by sol gel reaction and calcining.This method is used to prepare
Boron and other element coblended nano TiO 2, it is possible to absorb visible ray and also there is visible light catalysis activity.
CN1015492994 discloses a kind of non-metallic element multiple doping nano titanium dioxide photocatalyst, mixes in this catalyst
By weight percentage, carbon is 30～50% to miscellaneous nonmetalloid content, and nitrogen is 8～30%, and sulfur is 1～2%, and at content is
In 100MG/L MBD liquid, add this catalyst of 2g/l, and degrade 2 hours under ultraviolet light, visible ray or daylight, its
Degradation rate is all more than 95%.This invention also discloses the preparation method of this photocatalyst.The photocatalyst provided due to the present invention
Doped with non-metals constituent content contained by is high, thus it not only has preferably response to ultraviolet light, visible ray or daylight, can make dye
Dyestuff in liquid is degraded rapidly, and low cost.Additionally the system of preparation method is simple, and process is easily-controllable, operates safety, and also has
Good repeatability.
CN101653720A disclose a kind of by the Alveolate activated carbon prepared in nanometer light catalyst solvent impregnation process
Technology, this technology, can be with nuisances such as decomposing formaldehydes under illumination condition owing to adding photocatalyst agent on cellular activated carbon
Matter, thus there is self-cleaning function.
Above-mentioned report relate to the preparation method of Alveolate activated carbon net, the preparation method of the photocatalyst that adulterates, and by catalyst
The technique being carried on Alveolate activated carbon, but there is not yet the patent identical with present invention or document report.
Summary of the invention
It is an object of the invention to: aim to provide the product with the function such as visible light photocatalytic degradation and activated carbon adsorption, physical arrangement
Performance is good, i.e. provides energy efficient degradation organic exhaust gas, the photocatalysis ature of coal Alveolate activated carbon of waste water and preparation method.
The technical scheme is that photocatalysis cellular activated carbon net, using Alveolate activated carbon net as carrier, in cellular work
Property charcoal has loaded the TiO of Co, Pr and S on the net2, described TiO2In photocatalyst Co: Pr: S: TiO2Mol ratio be
0.01～0.03: 0.005～0.015: 0.5～2.0: 0.9～1.2.
The size of Alveolate activated carbon net is 100～250mm × 100～250mm × 10～20mm, and the hole density of net is 30～50
Hole/cm2, the length of side that is shaped as in hole is square or equilateral triangle or the regular hexagon of 1～2mm.
The preparation method of photocatalysis cellular activated carbon net, prepares and has high density holes, high-specific surface area, straight hole structure, ventilative
The ature of coal cellular activated carbon net carrier good with light transmission, comprises the following steps: first, including: 1. raw material consists of: coal dust:
Inorganic filler: low temperature bonding agent: high-temperature agglomerant: lubricant: the mass ratio of water is 45～65: 2～15: 1～4:
10～20: 2～3: 10～15, wherein coal dust be bituminous coal with anchracite duff with 1: 0.2～0.8 mixture, inorganic filler is
One or more in Kaolin or attapulgite or clay or Maifanitum or meerschaum arbitrarily mix；Low temperature glues
Knot agent is that one or more in methylcellulose or hydroxypropyl methyl cellulose or carboxymethyl cellulose arbitrarily mix；
High-temperature agglomerant is that one or more in coal tar or sodium dihydrogen phosphate or aluminium dihydrogen phosphate arbitrarily mix；Coal tar
Bitumen content more than 35%, lubricant is edible oil or Polyethylene Glycol；The fineness of all non-aqueous solid materials is all crushed to
More than 200 mesh.2. pretreatment of raw material, including: raw material is sufficiently mixed and mediates, then through vacuum white silk system with old, system
Uniformly plasticity pug.3. pug is extruded into honeycomb ceramics, microwave drying, then carbonization in batch-type furnace under nitrogen protection,
Finally it is passed through steam or carbon dioxide activation, i.e. obtains ature of coal Alveolate activated carbon net.
Secondly, preparation is doped with the nano-TiO of the elements such as Co, Pr and S2Photocatalyst, makes it to utilize excited by visible light
Produce activated state oxygen, cause a series of redox reaction, make organic pollutant degradation.Including with CH4N2S is the raw material of sulfur,
After dissolving in dehydrated alcohol, then mix the addition of C o (NO3)2·6H2O and Pr (NO3)3·6H2O, drips Ti (OC again after dissolving4H9)4Again
Calcine at 500 DEG C, be ground to more than 200 mesh, prepare powdered form photocatalyst.
Its three, by prepared powdery photocatalyst on ature of coal cellular activated carbon net carrier, including: first clean carrier, point
Do not use ultrasonic cleaning again after ammonia, nitric acid and soak with ethanol, dry；Then photocatalyst powder is carried on carrier, i.e.
Photocatalyst powder is mixed with certain proportion with epoxy resin, adds ethanol and make serosity, then by the coal through pretreatment
Honeycomb ceramic net is impregnated in serosity, takes out and dries, finally in 500 ± 100 DEG C, N in batch-type furnace2The lower roasting of protection,
I.e. prepare photocatalysis ature of coal ceramic honey comb net.Control the dipping of ature of coal ceramic honey comb net and dry number of times, photocatalyst can be increased
Load capacity.
The present invention has also carried out the organic gas clearances such as catalyst intensity of load, load factor, XRD, SEM, formaldehyde to sample
Mensuration, characterize the characteristic of photocatalysis cellular activated carbon net.
The invention has the beneficial effects as follows: the present invention provide photocatalysis Alveolate activated carbon net owing to specific surface area is big, aeration is good,
Thus improve the function of activated carbon adsorption organic pollutant, and there is good intensity, it is the most convenient to assemble and install and use；
Due to activated carbon adsorption effect, the photocatalyst for loading provides the machine thing pollutant of higher concentration, thus improves photocatalysis
Efficiency；Again due at nano-TiO2It is doped with the elements such as Co, Pr and S, enables it to utilize visible ray to produce catalytic action, fall
Low photocatalysis cost is the highest in the absorption efficiency of visible ray.Therefore, photocatalysis Alveolate activated carbon net is to combine visible ray
It is catalyzed, is adsorbed in the product of one process organic pollution.And preparation method is unique, basic non-environmental-pollution.Photocatalysis honeycomb
It is good that shaped activated carbon net has straight hole network structure, aeration and light transmission, and its specific surface area is 750～1050m2/ g, iodine adsorbs
Value is 900～1100mg/g, and carbon tetrachloride adsorption rate is 40～60%.At 30m3Confined space and with visible ray as light source,
Formaldehyde clearance after 50min is 95.6～98.7%, and toluene is 90.3～93.6%, and ammonia is 92.8～96.0%.
Detailed description of the invention
The preparation of ature of coal Alveolate activated carbon net
(1) raw material consists of: coal dust: inorganic filler: low temperature bonding agent: high-temperature agglomerant: lubricant: the mass ratio of water
Be 45～65: 2～15: 1～4: 10～20: 2～3: 10～15, inorganic filler be Kaolin, attapulgite, clay,
One or more in Maifanitum or meerschaum arbitrarily mix；Low temperature bonding agent is methylcellulose, hydroxypropyl methyl fiber
One or more in element or carboxymethyl cellulose arbitrarily mix；High-temperature agglomerant is coal tar, sodium dihydrogen phosphate or phosphoric acid
One or more in aluminum dihydrogen arbitrarily mix；The bitumen content of coal tar is more than 35%, and lubricant is edible oil or poly-second
Glycol；All non-aqueous solid materials are all crushed to more than 200 mesh；
(2) raw material mixing with mediate: coal dust, inorganic filler and low temperature bonding agent are added in blender be sufficiently stirred for 10～
30min, the uniform siccative obtained is placed in kneader, sequentially adds high-temperature agglomerant, lubricant and water, stirring mediate 15～
45min, makes uniform plasticity pug；
(3) pug practices system with old: is added by above-mentioned plasticity pug in vacuum deairing machine, keeps vacuum-0.06MPa
Above, pump the air in pug, repeat to practice system and make pug mix homogeneously for more than 2 times, then by close for pug plastic film wrapped
After sealing old 12～48h stand-by；
(4) extrusion molding: old good pug is equipped with on the extrusion shaping machine of cellular steel mould, with more than 8MPa's
Pressure is extruded, and obtains cellular wet idiosome；
(5) being dried: put in microwave dryer by cellular wet idiosome, controlling microwave frequency is 0.8～1.5GHz, is dried
10～30min, obtain the cellular idiosome being dried；
(6) carbonization and activation: put in atmosphere protection batch-type furnace by dry cellular activated carbon base substrate, with nitrogen for protection gas
Body, by for 3～8 DEG C/min ramp to 500～700 DEG C, carbonization 1～3h；Then by 5～10 DEG C/min ramp
To 700～900 DEG C, it is passed through steam or carbon dioxide simultaneously, activates 1～5h, obtain Alveolate activated carbon, cellular activity
Charcoal cuts into charcoal net, and loaded optic catalyst obtains photocatalysis cellular activated carbon net.
Wherein coal dust be bituminous coal with anchracite duff with 1: 0.2～0.8 mixture.
Photocatalyst is as follows for doping photocatalyst preparation method: take a certain amount of CH4N2S (thiourea) pulverizes with mortar, adds
The absolute ethyl alcohol and stirring of 1～2 times of weight is dissolved, and adds and the addition of C o (NO3)2·6H2O、Pr(NO3)3·6H2O, stirring, so
After slowly drip butyl titanate Ti (OC4H9)4, stir 0.5-2h, at 60 DEG C, vacuum drying obtains white crystal, is aged 2d
Calcining 1～2h at latter 500 DEG C, sample is being ground to more than 200 mesh, i.e. obtains Co, Pr, S codope TiO2Photocatalyst
Finished product；Wherein Co: Pr: S: TiO2Mol ratio is 0.01～0.03: 0.005～0.015: 0.5～2.0: 0.9～1.2.
It is to be first to clean cellular activated carbon net carrier: by ature of coal honeycomb in the method for cellular activated carbon net by photocatalyst
Active carbon net carrier is immersed in the ammonia spirit that mass fraction is 26%, and liquid and impurity are removed in ultrasonic cleaning 20min hypsokinesis, uses
Deionized water wash 3 times；Remove liquid and impurity with the nitric acid ultrasonic cleaning 20min hypsokinesis that mass fraction is 45% again, spend from
Sub-water washs 3 times.Then remove liquid and impurity with the hypsokinesis of alcohol dipping 10min, be washed with deionized 3 times, finally exist
Dry 3h for 105 DEG C；
Followed by by photocatalyst on cellular activated carbon net carrier: weigh a certain amount of epoxy resin and 5～20g respectively
Photocatalyst powder be placed in beaker, add 100～400ml ethanol, stir under 7000r/min rotating speed with high-speed shearing machine
Mix 1h, then the ature of coal ceramic honey comb net through pretreatment be impregnated in the ethanol serosity of epoxy resin, 15min take out after
Vacuum drying 5h at 60 DEG C, finally in 500 DEG C, N in batch-type furnace2The lower roasting 2h of protection, i.e. prepares photocatalysis ature of coal honeycomb
Ceramic network.Control ature of coal ceramic honey comb net dipping in the ethanol serosity of epoxy resin and dry number of times, increasing photocatalyst
Load capacity.
Described cellular steel mould is 20～50 holes/cm2Square or cylinder cellular steel mould.
Embodiment 1
1, (1) raw material and consisting of: coal dust: inorganic filler: low temperature bonding agent: high-temperature agglomerant: lubricant: water
Mass ratio is 45～65: 2～15: 1～4: 10～20: 2～3: 10～15, wherein coal dust be bituminous coal with anchracite duff with
The mixture of 1: 0.2～0.8, inorganic filler is in Kaolin or attapulgite or clay or Maifanitum or meerschaum
One or more arbitrarily mix；Low temperature bonding agent be methylcellulose or hydroxypropyl methyl cellulose or carboxymethyl fine
One or more in dimension element arbitrarily mix；High-temperature agglomerant is in coal tar or sodium dihydrogen phosphate or aluminium dihydrogen phosphate
One or more arbitrarily mix；The bitumen content of coal tar is more than 35%, and lubricant is edible oil or Polyethylene Glycol；
The fineness of all non-aqueous solid materials is all crushed to more than 200 mesh.
(2) raw material mixing with mediate: coal dust, inorganic filler and low temperature bonding agent are added in blender be sufficiently stirred for 10～
30min, obtains uniform siccative and is placed in kneader, sequentially adds high-temperature agglomerant, lubricant and water, stirring mediate 15～
45min, makes uniform plasticity pug.
(3) pug practices system with old: added in vacuum deairing machine by above-mentioned plasticity pug, holding vacuum-0.06MPa with
On, pump the air in pug, repeat to practice system and make pug mix homogeneously for more than 2 times, then pug plastic film wrapped is sealed
After old 12～48h stand-by.
(4) extrusion molding: old good pug is equipped with on the extrusion shaping machine of cellular steel mould, with more than 8MPa's
Pressure is extruded, and obtains cellular wet idiosome.
(5) being dried: put in microwave dryer by cellular wet idiosome, controlling microwave frequency is 0.8～1.5GHz, is dried
10～30min, obtain the cellular idiosome being dried.
(6) carbonization and activation: dry cellular idiosome is put in atmosphere protection batch-type furnace, with nitrogen as protective gas,
By for 3～8 DEG C/min ramp to 500～700 DEG C, carbonization 1～3h.Then by 5～10 DEG C/min ramp to 700～
900 DEG C, it is passed through steam or carbon dioxide simultaneously, activates 1～5h, obtain ature of coal Alveolate activated carbon.
2, doping Co, Pr, S element ti O2The preparation of photocatalyst
Take a certain amount of CH4N2S (thiourea) pulverizes with mortar, and the absolute ethyl alcohol and stirring adding 1～2 times of weight is dissolved, then adds
Enter and the addition of C o (NO3)2·6H2O、Pr(NO3)3·6H2O, stirring, the most slowly drip Ti (OC4H9)4(butyl titanate),
Stirring 1h, at 60 DEG C, vacuum drying obtains white crystal, calcines 1～2h after ageing 2d at 500 DEG C, and sample is being ground to 200
More than mesh, i.e. obtain Co, Pr, S codope TiO2Photocatalyst finished product.Wherein Co: Pr: S: TiO2Mol ratio be 0.01～
0.03: 0.005～0.015: 0.5～2.0: 0.9～1.2.
3, photocatalyst is in carrier
(1) Vehicle element: be immersed in the ammonia spirit that mass fraction is 26% by ature of coal cellular activated carbon net carrier is super
Sound cleans 20min hypsokinesis and removes liquid and impurity, is washed with deionized 3 times.Ultrasonic clearly with the nitric acid that mass fraction is 45% again
Wash 20min hypsokinesis and remove liquid and impurity, be washed with deionized 3 times.Then liquid and miscellaneous is removed with the hypsokinesis of alcohol dipping 10min
Matter, is washed with deionized 3 times.Finally dry 3hr at 105 DEG C.
(2) photocatalyst is in carrier: weigh respectively a certain amount of epoxy resin and 5～20g photocatalyst powder put
In beaker, add 100～400ml ethanol, under 7000r/min rotating speed, stir 1h with high-speed shearing machine, then will pass through
The ature of coal ceramic honey comb net of pretreatment is impregnated in the ethanol serosity of epoxy resin, 15min take out after at 60 DEG C vacuum drying
5h, finally in 500 DEG C, N in batch-type furnace2The lower roasting 2h of protection, i.e. prepares photocatalysis ature of coal cellular activated carbon net.Control coal
Honeycomb ceramic net dipping in the ethanol serosity of epoxy resin and dry number of times, can increase the load capacity of photocatalyst.
4, performance detection
(1) intensity of load: by activated carbon supported TiO2Catalysis material is fixed in small-sized wind tunnel, and wind speed is 5m/s, 1h
Rear mensuration weight-loss ratio.
(2) load factor: by activated carbon supported TiO2Catalysis material is roasting 2h at 1000 DEG C, and activated carbon is completely burned off,
Remaining containing TiO2Solid, containing TiO on unit of account mass activity charcoal2The load factor of solid.
(3) SEM: observe catalysis material configuration of surface.
(4) XRD: observe TiO2Crystalline state.
(5) mensuration of iodine sorption value is according to GB/T 7702.7-2008
(6) mensuration 7702.20-2008 of specific surface area
(7) the mensuration GB/T 7702.13-1997 of carbon tetrachloride adsorption rate
(8) formaldehyde determination uses GB/T 18204.26-2000 standard, and ammonia measures and uses indophenol blue colorimetry, and toluene measures
Use GB/T 14677-1993 standard.Analyze sample be taken respectively from: at 30m3Room in place equipped with 2 50W xenons
Lamp lamp (falling the ultraviolet light of 200-400nm with ultraviolet ray intercepting glass membrane filtration), 12 pieces of photocatalysis cellular activated carbon nets and
1 typhoon amount is 3m3The blower fan of/min, allows the volatilization of liquid phase formaldehyde make indoor reach finite concentration (C0), it is then turned on light source and wind
Machine makes formaldehyde pass through the circulation degraded of photocatalytic active carbon net, measures the concentration C after photodissociation after 50min1, then the clearance R of formaldehyde:
Same method measures toluene and the clearance of ammonia.
Embodiment 2
1, the preparation of ature of coal Alveolate activated carbon net
(1) pretreatment of raw material: 7200g coal dust (6000g bituminous coal+1200g anthracite, be more than 200 mesh), 200g
Clay (more than 200 mesh), 300g hydroxypropyl methyl cellulose, 250g Polyethylene Glycol add in blender, are sufficiently stirred for 30min,
Adding 2000g coal tar (bitumen content is more than 35%) and 1160ml water, 25min is mediated in stirring.It is placed in vacuum the most again
In pug mill, vacuum remains-0.08MPa, pumps the air in pug, practices 25min processed and makes pug mix homogeneously.Then
By stand-by after the pug plastic film wrapped old 12h of sealing, obtain uniform plasticity pug.
(2) extrusion molding is with dry: be equipped with on the extrusion shaping machine of cellular steel mould by old good pug, with 15MPa
Pressure extrusion, obtain cellular wet idiosome, a size of 220mm × 110mm × 15mm, hole density is 46 holes/cm2.Put again
Entering in microwave dryer, controlling microwave frequency is that 1GHz is dried 20min, obtains the cellular idiosome being dried.
(3) carbonization and activation: dry cellular idiosome is put in atmosphere protection batch-type furnace, with nitrogen as protective gas,
By 5 DEG C/min ramp to 700 DEG C, carbonization 1h；Then by 8 DEG C/min ramp to 850 DEG C, it is passed through water simultaneously and steams
Gas activation 1h, obtains ature of coal Alveolate activated carbon.
2, doping Co, Pr, S element ti O2The preparation of photocatalyst
Take the CH of 45g4N2S pulverizes, and adds 90ml absolute ethyl alcohol and stirring and dissolves, adds the Co (NO of 39g3)2·6H2O、24g
Pr (NO3)3·6H2O, stirring, the most slowly drip 2040gTi (OC4H9)4(butyl titanate), stirs 1h, at 60 DEG C
Vacuum drying obtains white crystal, calcines 1～2h after ageing 2d at 500 DEG C, and sample is being ground to more than 200 mesh, i.e. obtains
Co, Pr, S codope TiO2Photocatalyst finished product.
3, photocatalyst is in carrier
It is 30～40 holes/cm by 20 pieces a size of 100～250mm × 100～250mm × 10～20mm, hole density2, the length of side be
The ature of coal ceramic honey comb net carrier of 1.5mm square hole is immersed in the ammonia spirit of 26% in batches, spend after ultrasonic cleaning 20min from
Sub-water washs；It is washed with deionized after the nitric acid ultrasonic cleaning 20min of 45%；Afterwards with spend after alcohol dipping 10min from
Sub-water washs, and dries 3h at 105 DEG C.The photocatalyst powder weighing 54g epoxy resin and 450g again is placed in beaker,
Add 9000ml ethanol, under 7000r/min rotating speed, stir 1h with high-speed shearing machine, then by the ature of coal honeybee through pretreatment
Nest ceramic network immerse, 15min take out after at 60 DEG C vacuum drying 5h, finally in 500 DEG C, N in batch-type furnace2The lower roasting of protection
Burn 2h, i.e. prepare photocatalysis ature of coal ceramic honey comb net.
4, performance detection
(1) intensity of load: the weight-loss ratio of sample is less than 1.5%, shows that photocatalyst load on carrier is stronger.
(2) load factor: the photocatalyst rate on unit mass carrier is 15.0%.
(3) SEM: do not formed uniform films by SEM figure visible light catalytic material surface, but with individual particle or the form of aggregate
Exist.
(4) XRD: the TiO in catalyst as seen from the figure2Having 79% is Detitanium-ore-type, and 21% is rutile-type.
(5) measured value of iodine sorption value is 950mg/g.
(6) carbon tetrachloride adsorption rate measured value is 45%.
(7) specific area measuring value is 800m2/g
(8) recording formaldehyde clearance is 97%, and toluene is 93%, and ammonia is 91%.
Embodiment 3
Adulterate TiO according to embodiment 2 step 22The preparation method of photocatalyst is removed and mixes S element, only reservation doping Co,
Pr element, remaining step is same as in Example 1, and the measurement result of properties of product is as follows:
(1) intensity of load: the weight-loss ratio of sample is less than 1.5%, shows that photocatalyst load on carrier is stronger.
(2) load factor: the photocatalyst rate on unit mass carrier is 15.0%.
(3) SEM: being schemed from SEM, catalysis material surface does not forms uniform films, but with individual particle or the shape of aggregate
Formula exists.
(4) XRD: as seen from the figure, the TiO in catalyst2Having 79% is Detitanium-ore-type, and 21% is rutile-type.
(5) measured value of iodine sorption value is 940mg/g.
(6) carbon tetrachloride adsorption rate measured value is 46%.
(7) specific area measuring value is 804m2/g
(8) formaldehyde clearance is 85%, and toluene is 83%, and ammonia is 79%.
Compareing with embodiment 1 result and show, the clearance that formaldehyde, toluene, ammonia are has decline, and this is due to undoped p S
Element influences photocatalyst is to visible absorption, and other performance indications have almost no change.
Embodiment 4
Adulterate TiO according to embodiment 2 step 22The preparation method of photocatalyst is removed and mixes S element, only reservation doping Co,
Pr element, remaining step is same as in Example 1, and the measurement result of properties of product is as follows:
(1) intensity of load: the weight-loss ratio of sample is less than 1.5%, shows that photocatalyst load on carrier is stronger.
(2) load factor: the photocatalyst rate on unit mass carrier is 15.0%.
(3) SEM: as seen from the figure, catalysis material surface does not forms uniform films, but deposits with the form of individual particle or aggregate
?.
(4) XRD: as seen from the figure, the TiO in catalyst2Having 79% is Detitanium-ore-type, and 21% is rutile-type.
(5) measured value of iodine sorption value is 940mg/g.
(6) carbon tetrachloride adsorption rate measured value is 46%.
(7) specific area measuring value is 804m2/g
(8) formaldehyde clearance is 82%, and toluene is 79%, and ammonia is 73%.
Compareing with embodiment 1 result and show, the clearance that formaldehyde, toluene, ammonia are has decline, this be due to undoped p Co,
On the one hand Pr element have impact on photocatalyst to visible absorption, also affects photocatalysis efficiency, and other performance indications are the most several
It is not changed in.
Claims (4)
1. the preparation method of photocatalysis cellular activated carbon net, using Alveolate activated carbon net as carrier, at online load C o of Alveolate activated carbon, the TiO of Pr and S2Photocatalyst, described TiO2In photocatalyst Co: Pr: S: TiO2Mol ratio be 0.01～0.03: 0.005～0.015: 0.5～2.0: 0.9～1.2；The size of Alveolate activated carbon net is 100～250mm × 100～250mm × 10～20mm, and the hole density of net is 30～50 holes/cm2, the length of side that is shaped as in hole is square, triangle or the regular hexagon of 1～2mm；Alveolate activated carbon net is ature of coal Alveolate activated carbon net；
It is characterized in that comprising the following steps: 1) raw material consists of: coal dust: inorganic filler: low temperature bonding agent: high-temperature agglomerant: lubricant: the mass ratio of water is 45～65: 2～15: 1～4: 10～20: 2～3: 10～15, wherein coal dust be bituminous coal with anchracite duff with 1: 0.2～0.8 mixture, inorganic filler is that one or more in Kaolin, attapulgite, Maifanitum or meerschaum arbitrarily mix；Low temperature bonding agent is that one or more in methylcellulose, hydroxypropyl methyl cellulose or carboxymethyl cellulose arbitrarily mix；High-temperature agglomerant is that one or more in coal tar, sodium dihydrogen phosphate or aluminium dihydrogen phosphate arbitrarily mix；The bitumen content of coal tar is more than 35%, and lubricant is edible oil or Polyethylene Glycol；The fineness of all non-aqueous solid materials is all crushed to more than 200 mesh；
2) pretreatment of raw material, including: raw material it is sufficiently mixed and mediates, then through vacuum white silk system with old, making uniform plasticity pug；
3) plasticity pug is extruded into honeycomb ceramics, microwave drying, then carbonization in batch-type furnace under nitrogen protection, is finally passed through steam or carbon dioxide activation, i.e. obtains Alveolate activated carbon net, i.e. ature of coal Alveolate activated carbon net；
Photocatalyst is doping photocatalyst, and its preparation method is as follows: take a certain amount of CH4N2S mortar pulverizes, and the absolute ethyl alcohol and stirring adding 1～2 times of weight is dissolved, and adds the addition of C o (NO3)2·6H2O、Pr(NO3)3·6H2O, stirring, the most slowly dropping butyl titanate Ti (OC4H9)4, stir 0.5-2h, at 60 DEG C, vacuum drying obtains white crystal, calcines 1～2h after ageing 2d at 500 DEG C, and sample is ground to more than 200 mesh again, i.e. obtains Co, Pr, S codope TiO2Photocatalyst finished product；Wherein Co: Pr: S: TiO2Mol ratio is 0.01～0.03: 0.005～0.015: 0.5～2.0: 0.9～1.2；
Photocatalyst in the method for Alveolate activated carbon net is, by prepared powdery photocatalyst on Alveolate activated carbon net carrier, including: first clean Alveolate activated carbon net carrier, be respectively adopted ultrasonic cleaning again after ammonia, nitric acid and soak with ethanol, dry；Then photocatalyst powder is carried on Alveolate activated carbon net carrier, will photocatalyst powder mix with certain proportion with epoxy resin, add ethanol and make serosity, then the Alveolate activated carbon net through pretreatment is impregnated in serosity, take out and dry, finally in 500 ± 100 DEG C, N in batch-type furnace2The lower roasting of protection, i.e. prepares photocatalysis cellular activated carbon net；Control the dipping of Alveolate activated carbon net and dry number of times, the load capacity of photocatalyst can be increased.
2. the preparation method of as claimed in claim 1 photocatalysis cellular activated carbon net, is characterized in that concrete grammar prepared by cellular activated carbon net: 1) wherein coal dust be bituminous coal powder with anchracite duff with 1: 0.2～0.8 mixture；
2) raw material mixing and kneading: 10～30min will be sufficiently stirred in coal dust, inorganic filler and low temperature bonding agent addition blender, the uniform siccative obtained is placed in kneader, sequentially adding high-temperature agglomerant, lubricant and water, stirring is mediated 15～45min, is made uniform plasticity pug；
3) pug practices system with old: added by above-mentioned plasticity pug in vacuum deairing machine, keep more than vacuum-0.06MPa, pump the air in pug, repeat to practice system and make pug mix homogeneously for more than 2 times, stand-by after then pug plastic film wrapped being sealed old 12～48h；
4) extrusion molding: be equipped with on the extrusion shaping machine of cellular steel mould by old good pug, extrudes with the pressure of more than 8MPa, obtains cellular wet idiosome, and cut into charcoal net；
5) being dried: put in microwave dryer by cellular wet idiosome, controlling microwave frequency is 0.8～1.5GHz, is dried 10～30min, obtains the cellular idiosome being dried；
6) carbonization and activation: dry green honeycomb body is put in atmosphere protection batch-type furnace, with nitrogen as protective gas, by for 3～8 DEG C/min ramp to 500～700 DEG C, carbonization 1～3h；Then by 5～10 DEG C/min ramp to 700～900 DEG C, it is passed through steam or carbon dioxide simultaneously, activates 1～5h, obtain Alveolate activated carbon net, and loaded optic catalyst obtains photocatalysis cellular activated carbon net.
The preparation method of photocatalysis cellular activated carbon net the most according to claim 2, it is characterized in that it being first to clean Alveolate activated carbon net carrier: be immersed in the ammonia spirit that mass fraction is 26% by Alveolate activated carbon net carrier, liquid and impurity are removed in ultrasonic cleaning 20min hypsokinesis, are washed with deionized 3 times；Remove liquid and impurity with the nitric acid ultrasonic cleaning 20min hypsokinesis that mass fraction is 45% again, be washed with deionized 3 times, then remove liquid and impurity with the hypsokinesis of alcohol dipping 10min, be washed with deionized 3 times, finally dry 3h at 105 DEG C；
Followed by by photocatalyst on Alveolate activated carbon net carrier: weigh respectively a certain amount of epoxy resin and 5～20g photocatalyst powder be placed in beaker, add 100～400ml ethanol, under 7000r/min rotating speed, 1h is stirred with high-speed shearing machine, then the Alveolate activated carbon net through pretreatment is impregnated in the ethanol serosity of epoxy resin, 15min take out after at 60 DEG C vacuum drying 5h, finally in 500 DEG C, N in batch-type furnace2The lower roasting 2h of protection, i.e. prepares photocatalysis cellular activated carbon net；Control Alveolate activated carbon net dipping in the ethanol serosity of epoxy resin and dry number of times, increasing the load capacity of photocatalyst.
The preparation method of photocatalysis cellular activated carbon net the most according to claim 2, it is characterised in that described cellular steel mould is 20～50 holes/cm2Square or cylinder cellular steel mould.
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