CN106185912A - A kind of modified activated carbon and its production and use - Google Patents
A kind of modified activated carbon and its production and use Download PDFInfo
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- CN106185912A CN106185912A CN201610505911.9A CN201610505911A CN106185912A CN 106185912 A CN106185912 A CN 106185912A CN 201610505911 A CN201610505911 A CN 201610505911A CN 106185912 A CN106185912 A CN 106185912A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract
The invention provides a kind of modified activated carbon and its production and use, this modified activated carbon is prepared via a method which to obtain: 1) adds activated carbon in certain density aqueous solution of nitric acid and processes described activated carbon at a certain temperature, being washed with deionized described activated carbon after treatment drying for standby；2) to step 1) activated carbon of gained adds manganese nitrate aqueous solution and surface dispersant; enter in the electric furnace of nitrogen protection and activate; obtaining pre-modified activated carbon, the addition of wherein said surface dispersant is the 0.1～10% of manganese nitrate aqueous solution weight；3) by step 2) the pre-modified activated carbon of gained adds in aqueous slkali, and enter in the electric furnace of nitrogen protection and activate, obtain required modified activated carbon.The modified activated carbon of the present invention has higher specific surface area, bigger void volume and more void count, has loaded catalytic active component manganese simultaneously, improves ultralow temperature catalysis activity.
Description
Technical field
The present invention relates to contaminated air field of purification, specifically, relate to a kind of modified activated carbon and preparation method thereof and
Purposes.
Background technology
Nitrogen oxides is the primary pollution source of air, and it not only can cause acid rain, photochemical fog etc. to destroy earth ecology
The series of problems of environment, but also the health of human body in serious harm.Therefore, denitrification is the most effectively gone to become
An important topic attracted people's attention in field of Environment Protection at present.Ammonia selective catalytic reduction (selective catalytic
Reduction, SCR) due to maturation and efficiently become the denitration technology of the stationary source main flows such as thermal power plant, and its core is asked
Topic is that the development of catalyst.Many catalyst systems have been carried out going deep into systematic research by Chinese scholars at present, as
V2O5-WO3/TiO2,MnO2/TiO2,FeOx/TiO2,CuO/TiO2,Cr2O3/TiO2And CeO2/TiO2Deng.At present, industrialization should
NH3-SCR catalyst, how with TiO2For carrier, then upload a certain amount of V2O5、WO3、MoO3Deng.To this end, people are to denitration
The research of catalysis technique is deepening constantly, and to seek the wider array of denitrating catalyst of range, reduces or catalysis is completely eliminated
The toxicity of agent.
CN101480611B discloses a kind of vanadium-doped titanium-base flue gas denitration catalyst material and preparation method thereof, this invention
Disclose a kind of vanadium-doped titanium-base flue gas denitration catalyst material and preparation method thereof, guide for pore structure with surfactant
Agent, uses water solution system sol-gel process to prepare vanadium doping titanio catalysis material, and the doping of active component vanadium is with V2O5Meter
Being 0.5～20wt%, use at sol-gel process situ doping mode of loading, not only preparation method is simple, production cost
Low, and prepared denitration catalyst material specific surface area is relatively big, heat stability is higher, has higher denitration efficiency and wider
Active temperature windows, it is adaptable to coal-fired flue-gas removal of nitrogen oxide field.Use laboratory simulation flue gas evaluation to show, work as sky
Speed is 10000h-1, under conditions of NO content is 1000ppm, in the temperature range of 180～420 DEG C, the removal efficiency of NO reaches
More than 95%, the defect of denitration catalyst agent material prepared by this employing impregnation method is that service life is short, and catalyst exists
Toxicity.
CN101468314A discloses a kind of catalyst for low-temperature denitration of flue gas and preparation method thereof, and this invention relates to
A kind of catalyst for low-temperature denitration of flue gas and preparation method thereof.It uses SCR (SCR) technology, with oxidation
Vanadium be active component, titanium oxide be carrier.And this oxide catalyst has part oxygen replaced by fluorine, prepare the side of catalyst
Method, wherein active component vanadium oxide uses infusion process to be supported on carrier, and carrier titanium oxide is prepared by sol-gel process, fluorine
When the time of replacement oxygen can be to prepare carrier titanium oxide, or during load active component vanadium oxide.The present invention significantly improves
Low-temperature denitration activity and catalytic capability, more than the 200 DEG C NO removal efficiencies that i.e. can reach more than 90%, possess stronger commercial Application
It is worth, can be widely applied to the NH of nitrogen oxides in effluent3SCR, denitration prepared by this employing impregnation method
The defect of catalyst material is that service life is short, and catalyst exists toxicity.
CN101053838A discloses the cordierite-base CuO/ γ-Al for denitrating flue gas2O3Catalyst and preparation method and should
With, this invention relates to a kind of cordierite-base CuO/ γ-Al for denitrating flue gas2O3The percentage by weight of catalyst consists of: violet
Cordierite carrier is 78.7～93.8%, Al2O3Being 5～16%, CuO is 1.2～5.3%, uses and makes pottery with high strength cordierite honeycomb
Porcelain is matrix, is coated with carrier γ-Al thereon2O3The certain density CuO of rear dipping.The present invention has the coating using simple and efficient
Method, decreases γ-Al2O3The coating slight crack of film.Add γ-Al2O3Upper carrying capacity: improve the denitration activity of catalyst,
Life-span and the advantage of stability, although denitration catalyst agent material prepared by this employing coating process improves service life, but
Because employing copper as active component, cause use temperature range narrow, the problem that there is high temperature active difference.
CN101954281A discloses the cerium copper titanium compound oxide catalyst for denitrating flue gas and preparation method, this
Bright disclosing a kind of cerium copper titanium compound oxide catalyst for denitrating flue gas and preparation method, the component of this catalyst includes
CeO2, CuO and TiO2.Catalyst preparation uses coprecipitation, can reach preferable denitration effect.The advantage of this catalyst is: 1)
Nitrogen oxides in effluent is catalyzed reduction there is higher activity；2) the adaptive temperature window of catalyst is wider, 150～
In 450 DEG C of whole temperature ranges, all there is certain activity；3) catalyst can be effectively improved at SO2And H2Maneuverability under the conditions of O
Can, the bad working environments in the presence of sulfur dioxide and water etc. is had stronger adaptability, exercisable wider；4) prepare former
Material is easy to get, preparation technology is simple, and catalyst cost is relatively low, the defect of denitration catalyst agent material prepared by this employing coprecipitation
It is that service life is short.
CN101920213A discloses the low temperature SCR denitration catalyst with Metal-organic frame as carrier and preparation side thereof
Method, this invention designs a kind of low temperature SCR denitration catalyst with Metal-organic frame as carrier and preparation method thereof, belongs to big
Gas pollutant abatement technology and environment protection catalytic Material Field.Use infusion process in MOFs catalyst carrier, load Mn, Fe, Cu, V,
The oxide of one or more metallic elements of Ce is active component, through being dried, calcining and sieve, prepares metallic catalyst,
With catalyst in gross mass as standard, reactive metal oxides load capacity is 1～10%, the operating temperature of catalyst be 80～
200℃.Catalyst has bigger specific surface area, higher low-temperature catalytic activity and denitration effect, at flue-gas denitration process
In there is wide prospects for commercial application, the defect that this method exists is that high-temperature catalytic activity is low, and application range of products is narrow.
The denitration technology of the main flow that SCR technology is administered as nitrogen oxides, especially with activated carbon as base
The denitrating catalyst of body material has avirulence, the nitrogen oxides high removal efficiency when ultralow temperature, preferable sulfur resistance, longer
Service life.But in requiring in preparation technology, activated carbon, as the relatively low material of a kind of plasticity, becomes at extruded machine
The problem being always relatively difficult to during type overcome.
Summary of the invention
In order to overcome defect of the prior art, it is an object of the invention to provide a kind of modified activated carbon and preparation side thereof
Method and purposes, for realizing the purpose of the present invention, technical scheme is as follows:
The invention provides a kind of method preparing modified activated carbon, it is prepared via a method which to obtain:
1) in certain density aqueous solution of nitric acid, add activated carbon and at a certain temperature described activated carbon is carried out
Process, be washed with deionized described activated carbon after treatment drying for standby；
2) to step 1) activated carbon of gained adds manganese nitrate aqueous solution and surface dispersant, enter the electricity of nitrogen protection
Activating in stove, obtain pre-modified activated carbon, the addition of wherein said surface dispersant is manganese nitrate aqueous solution weight
0.1～10%；
3) by step 2) the pre-modified activated carbon of gained adds in aqueous slkali, and enter in the electric furnace of nitrogen protection and live
Change, obtain required modified activated carbon.
Specifically, the modified activated carbon of the present invention is prepared via a method which to obtain:
1) in the aqueous solution of nitric acid that weight percent content is 5-30%, activated carbon is added and to institute at 40-80 DEG C
State activated carbon to carry out processing 1-10h, be washed with deionized described activated carbon after treatment and at 50-90 DEG C, be dried 5-
10h is standby, and wherein said activated carbon is 1:5-1:10 with the mass volume ratio of aqueous solution of nitric acid；
2) to step 1) activated carbon of gained adds manganese nitrate aqueous solution and the table that weight percent content is 1-15%
Face dispersant, after soaking 1～25h, enters in the electric furnace of nitrogen protection and activates, and soak time is 1～20h, activation temperature
Being 200～450 DEG C, obtain pre-modified activated carbon, the addition of wherein said surface dispersant is manganese nitrate aqueous solution weight
0.1～10%；
3) by step 2) to add weight percent content be in 5-40% aqueous slkali for the pre-modified activated carbon of gained, soaks 1
～after 25h, enter in the electric furnace of nitrogen protection and activate, activation temperature is 350～700 DEG C, and soak time is 1～20h,
To required modified activated carbon.
In the preferred embodiment of the present invention, this activated carbon be cocoanut active charcoal, coal mass active carbon, active fruit shell carbon or
One in activated carbon from bamboo or a combination thereof.
In the preferred embodiment of the present invention, this surface dispersant is PEG400, cetomacrogol 1000, poly-second
One in glycol 2000 or dodecylbenzene sodium sulfonate or a combination thereof.
In the preferred embodiment of the present invention, the one during this alkali is sodium hydroxide, potassium hydroxide or ammonia or its group
Close.
Prepared according to the methods of the invention modified activated carbon.
The application in making denitrating catalyst of the prepared according to the methods of the invention modified activated carbon.
The modified activated carbon that the method for the present invention is prepared, has a specific surface area of increase, bigger void volume and relatively
Many void count, have loaded catalytic active component manganese simultaneously, improve catalysis activity, especially improve ultralow temperature catalysis and live
Property.
In order to overcome toxicity of the prior art, life-span short, high temperature active is poor, and range is narrow, and especially low temperature active is poor
Etc. defect, a kind of method that present invention also offers denitrating catalyst prepared with modified activated carbon as matrix material, it is logical
Cross what following method prepared:
1) modified activated carbon, kaolin powder, sodium carboxymethyl cellulose, cerium zirconium composite, stearic acid are added deionization
In water, obtain activated carbon pug by kneading effect；
2) carry out being squeezed into Alveolate activated carbon moulded pottery not yet put in a kiln to bake by above-mentioned activated carbon pug addition vacuum-extruder；
3) above-mentioned Alveolate activated carbon moulded pottery not yet put in a kiln to bake is placed in electric furnace drying；
4) above-mentioned dried activated carbon moulded pottery not yet put in a kiln to bake is immersed in cure process liquid, after dipping, obtains required denitration catalyst
Agent；
Wherein said modified activated carbon is prepared via a method which to obtain:
A) in the aqueous solution of nitric acid that weight percent content is 5-30%, activated carbon is added and to institute at 40-80 DEG C
State activated carbon to carry out processing 1-10h, be washed with deionized described activated carbon after treatment and at 50-90 DEG C, be dried 5-
10h is standby, and wherein said activated carbon is 1:5-1:10 with the mass volume ratio of aqueous solution of nitric acid；
B) in the activated carbon of step a) gained, manganese nitrate aqueous solution and the table that weight percent content is 1-15% is added
Face dispersant, after soaking 1～25h, enters in the electric furnace of nitrogen protection and activates, and soak time is 1～20h, activation temperature
Being 200～450 DEG C, soak time is 1～25h, obtains pre-modified activated carbon, and the addition of wherein said surface dispersant is nitre
The 0.1～10% of acid manganese aqueous solution weight；
C) the pre-modified activated carbon of step b) gained being added weight percent content is in 5-40% aqueous slkali, soaks 1
～after 25h, enter in the electric furnace of nitrogen protection and activate, activation temperature is 350～700 DEG C, and soak time is 1～20h,
To required modified activated carbon,
Wherein said cure process liquid consist of aluminum nitrate, carboxymethyl cellulose and water, its weight ratio is 8～25:
0.05～1.5:65～90.
In the preferred embodiment of the present invention, step 1) in modified activated carbon, kaolin powder, carboxymethyl cellulose
Sodium, cerium zirconium composite, stearic acid, the weight ratio of deionized water be 40～65:5～20:1～10:1～10:0.5～5.0:20～
40；The mineral composition of described kaolin powder be silicon dioxide 60～65%, aluminium oxide 10～15%, ferrum oxide 0.1～
0.2%, calcium oxide 0.1～0.4%, titanium oxide 0.01～0.1%；Described cerium zirconium composite consists of cerium oxide, zirconium oxide, oxygen
Changing praseodymium and lanthana, its weight ratio is 50～60:30～40:5～10:5～10.
In the preferred embodiment of the present invention, in step 2) in, activated carbon pug addition vacuum-extruder is squeezed
Being pressed into cellular, vacuum is 0.5～2.0MPa, and extrusion pressure is 500～2000KN.
In the preferred embodiment of the present invention, in step 3) in, Alveolate activated carbon moulded pottery not yet put in a kiln to bake is placed in electric furnace drying,
Wherein baking temperature be 150～300 DEG C, drying time be 5～20h.
In the preferred embodiment of the present invention, in step 4) in, dried activated carbon moulded pottery not yet put in a kiln to bake is immersed at hardening
In reason liquid, after dipping, obtain required denitrating catalyst；Wherein dip time is 5～15min, dipping face height be 10～
30mm。
In the preferred embodiment of the present invention, described activated carbon is cocoanut active charcoal, coal mass active carbon, active fruit shell carbon
Or the one in activated carbon from bamboo or a combination thereof.
In the preferred embodiment of the present invention, described surface dispersant is PEG400, cetomacrogol 1000, gathers
One in ethylene glycol 2000 or dodecylbenzene sodium sulfonate or a combination thereof.
In the preferred embodiment of the present invention, one during described alkali is sodium hydroxide, potassium hydroxide or ammonia or its
Combination.
Prepared according to the methods of the invention denitrating catalyst.
The present invention establishes a kind of denitrating catalyst with modified activated carbon as matrix material and preparation method, urges in denitration
Activated carbon is carried out nitric acid pretreatment and twice-modified by agent preparation process, has obtained that there is high-specific surface area, big space
Volume and more void count, catalyst has high catalytic activity simultaneously, greatly reduce catalyst reaction temperature (
140 DEG C, nitrogen oxide removal efficiency is up to 99.9%), widen the use temperature range of catalyst, catalyst avirulence simultaneously,
Designing denitration of boiler smoke and during chemical engineering industry denitrating flue gas, it is not required to external energy and promotes flue-gas temperature passively to raise to improve
Reaction rate, reduces cost and puts into.
The invention have the characteristics that 1. this technique employing nitric acid pretreatment and twice-modified activated carbon, will as carrier
Activated carbon, through nitric acid pretreatment, can remove impurity such as being attached to a large amount of ions of activated carbon surface, colloidal sol so that activated carbon overhead
Put adsorption potential to increase, optimize the pore passage structure of activated carbon, pore volume and the specific surface area of activated carbon is greatly improved, is conducive to carrying
High active component load on the activated carbon, has the most also carried out oxidation processes to activated carbon, increase effectively activated carbon table
The content of the oxygen-containing functional group in face, improves the polarity of absorbent charcoal carrier, strengthens the bond strength between carrier and active component,
Reduce active component loss during use.After nitric acid pretreatment, in activated carbon, add manganese nitrate aqueous solution and table
Face dispersant, enters in the electric furnace of nitrogen protection and activates, obtain pre-modified activated carbon.Above-mentioned pre-modified activated carbon is added
In aqueous slkali, entering in the electric furnace of nitrogen protection and activate, activation obtains required modified activated carbon after terminating, and this modification is lived
Property charcoal has higher specific surface area, and (specific surface area is up to 3900m2/ g), bigger void volume, more void count, with
Time supporting catalytic active component manganese；2. using the Kaolin of specific components as plastification material, improve activated carbon pug can
Plasticity, improves the mechanical strength of product；3. pug is carried out extrusion forming process, obtain Faveolate denitration catalyst, increase
The contact area of reaction bed, improves the activity of catalyst with this；4. product is carried out end face hardening process, it is ensured that urge
The mechanical strength of agent and anti-stifled ash performance.Drying of the present invention obtains denitrating catalyst and processes the purification examination of simulated fire power-plant flue gas
Testing and show, the clearance of nitrogen oxides harmful gas is all higher than 95%, and the reaction temperature of flue gas, at 50～200 DEG C, has been widened de-
The use temperature range of denox catalyst, has more design alternative space during for Power Station Design ultralow temperature denitrating catalyst.
Detailed description of the invention
Embodiment 1
(1) modified activated carbon is prepared
1) in the aqueous solution of nitric acid that weight percent content is 20%, cocoanut active charcoal is added and to institute at 50 DEG C
State activated carbon carry out process 6h, be washed with deionized described activated carbon after treatment and at 90 DEG C be dried 8h standby, its
Described in the mass volume ratio of activated carbon and aqueous solution of nitric acid be 1:8；
2) to step 1) to add weight percent content in the activated carbon of gained be the manganese nitrate aqueous solution of 10% and poly-second
Glycol 1000, after soaking 3h, enters in the electric furnace of nitrogen protection and activates, and soak time is 5h, and activation temperature is 400 DEG C,
Obtaining pre-modified activated carbon, wherein the addition of cetomacrogol 1000 is the 1% of manganese nitrate aqueous solution weight；
3) by step 2) to add weight percent content be in 10% aqueous slkali for the pre-modified activated carbon of gained, soaks 3h
After, entering in the electric furnace of nitrogen protection and activate, activation temperature is 500 DEG C, and soak time is 4h, obtains required modification and lives
Property charcoal.
Described activated carbon is commercially available cocoanut active charcoal, and specific surface area is equal to 1000m2/ g, void volume 0.4ml/g, space
650/g of quantity.
The modified specific surface area of activated carbon that obtains is equal to 3900m2/ g, void volume 0.8ml/g, void count 1700
Individual/g.
(2) preparation denitrating catalyst with above-mentioned activated carbon as matrix material
Step 1) prepare activated carbon pug:
By above-mentioned modified activated carbon, kaolin powder, sodium carboxymethyl cellulose, cerium zirconium composite, stearic acid add go from
In sub-water, obtain activated carbon pug by kneading effect.
Described modified activated carbon, kaolin powder, sodium carboxymethyl cellulose, cerium zirconium composite, stearic acid, deionized water
Weight ratio is 55:15:7:7:3.5:35.
The mineral composition of described kaolin powder is silicon dioxide 55%, aluminium oxide 12%, ferrum oxide 0.15%, calcium oxide
0.3%, titanium oxide 0.1%.
Described cerium zirconium composite consists of cerium oxide, zirconium oxide, praseodymium oxide, lanthana, and its weight ratio is 55:30:6:8.
Described sodium carboxymethyl cellulose, stearic purity requirement >=99.9%.
Step 2) prepare activated carbon moulded pottery not yet put in a kiln to bake:
Carrying out being squeezed into cellular by activated carbon pug addition vacuum-extruder, vacuum is 1.5MPa, and extrusion pressure is
1000KN。
Step 3) dry moulded pottery not yet put in a kiln to bake:
Alveolate activated carbon base substrate is placed in electric furnace drying, wherein baking temperature be 250 DEG C, drying time be 10h.
Step 4) end face cure process:
Being immersed in by product in cure process liquid, dip time is 10min, and dipping face height is 20mm.
Wherein cure process liquid consist of aluminum nitrate, carboxymethyl cellulose, deionized water, weight ratio is 20:1.0:70.
Embodiment 2
(1) modified activated carbon is prepared
1) in the aqueous solution of nitric acid that weight percent content is 20%, cocoanut active charcoal is added and to institute at 50 DEG C
State activated carbon carry out process 6h, be washed with deionized described activated carbon after treatment and at 90 DEG C be dried 8h standby, its
Described in the mass volume ratio of activated carbon and aqueous solution of nitric acid be 1:8；
2) to step 1) activated carbon of gained adds manganese nitrate aqueous solution and the poly-second two that weight percent content is 5%
Alcohol 1000, after soaking 4h, enters in the electric furnace of nitrogen protection and activates, and soak time is 5h, and activation temperature is 350 DEG C,
To pre-modified activated carbon, wherein the addition of cetomacrogol 1000 is the 0.5% of manganese nitrate aqueous solution weight；
3) by step 2) to add weight percent content be in 8% aqueous slkali for the pre-modified activated carbon of gained, after soaking 3h,
Entering in the electric furnace of nitrogen protection and activate, activation temperature is 450 DEG C, and soak time is 4h, obtains required modified active
Charcoal.
Described activated carbon is commercially available cocoanut active charcoal, and specific surface area is equal to 1000m2/ g, void volume 0.4ml/g, space
650/g of quantity.
The modified specific surface area of activated carbon that obtains is equal to 2700m2/ g, void volume 0.6ml/g, void count 1000
Individual/g.
(2) preparation denitrating catalyst with above-mentioned activated carbon as matrix material
Step 1) prepare activated carbon pug:
By above-mentioned modified activated carbon, kaolin powder, sodium carboxymethyl cellulose, cerium zirconium composite, stearic acid add go from
In sub-water, obtain activated carbon pug by kneading effect.
Described modified activated carbon, kaolin powder, sodium carboxymethyl cellulose, cerium zirconium composite, stearic acid, deionized water
Weight ratio is 55:17:5:5:2.5:25.
The mineral composition of described kaolin powder is silicon dioxide 55%, aluminium oxide 12%, ferrum oxide 0.15%, calcium oxide
0.3%, titanium oxide 0.1%.
Described cerium zirconium composite consists of cerium oxide, zirconium oxide, praseodymium oxide, lanthana, and its weight ratio is 50:35:5:5.
Described sodium carboxymethyl cellulose, stearic purity requirement >=99.9%.
Step 2) prepare activated carbon moulded pottery not yet put in a kiln to bake:
Carrying out being squeezed into cellular by activated carbon pug addition vacuum-extruder, vacuum is 1.0MPa, and extrusion pressure is
900KN。
Step 3) dry moulded pottery not yet put in a kiln to bake:
Alveolate activated carbon base substrate is placed in electric furnace drying, wherein baking temperature be 200 DEG C, drying time be 10h.
Step 4) end face cure process:
Being immersed in by product in cure process liquid, dip time is 10min, and dipping face height is 15mm.
Wherein cure process liquid consist of aluminum nitrate, carboxymethyl cellulose, deionized water, weight ratio is 15:0.5:65.
Embodiment 3
(1) modified activated carbon is prepared
1) in the aqueous solution of nitric acid that weight percent content is 20%, cocoanut active charcoal is added and to institute at 50 DEG C
State activated carbon carry out process 6h, be washed with deionized described activated carbon after treatment and at 90 DEG C be dried 8h standby, its
Described in the mass volume ratio of activated carbon and aqueous solution of nitric acid be 1:8；
2) to step 1) to add weight percent content in the activated carbon of gained be the manganese nitrate aqueous solution of 15% and poly-second
Glycol 1000, after soaking 6h, enters in the electric furnace of nitrogen protection and activates, and soak time is 5h, and activation temperature is 450 DEG C,
Obtaining pre-modified activated carbon, wherein the addition of cetomacrogol 1000 is the 4% of manganese nitrate aqueous solution weight；
3) by step 2) to add weight percent content be in 15% aqueous slkali for the pre-modified activated carbon of gained, soaks 4h
After, entering in the electric furnace of nitrogen protection and activate, activation temperature is 550 DEG C, and soak time is 5h, obtains required modification and lives
Property charcoal.
Described activated carbon is commercially available cocoanut active charcoal, and specific surface area is equal to 1000m2/ g, void volume 0.4ml/g, space
650/g of quantity.
The modified specific surface area of activated carbon that obtains is equal to 3000m2/ g, void volume 0.6ml/g, void count 1200
Individual/g.
(2) preparation denitrating catalyst with above-mentioned activated carbon as matrix material
Step 1) prepare activated carbon pug:
By above-mentioned modified activated carbon, kaolin powder, sodium carboxymethyl cellulose, cerium zirconium composite, stearic acid add go from
In sub-water, obtain activated carbon pug by kneading effect.
Described modified activated carbon, kaolin powder, sodium carboxymethyl cellulose, cerium zirconium composite, stearic acid, deionized water
Weight ratio is 50:20:8:8:5:35.
The mineral composition of described kaolin powder is silicon dioxide 55%, aluminium oxide 12%, ferrum oxide 0.15%, calcium oxide
0.3%, titanium oxide 0.1%.
Described cerium zirconium composite consists of cerium oxide, zirconium oxide, praseodymium oxide, lanthana, and its weight ratio is 55:35:7:8.
Described sodium carboxymethyl cellulose, stearic purity requirement >=99.9%.
Step 2) prepare activated carbon moulded pottery not yet put in a kiln to bake:
Carrying out being squeezed into cellular by activated carbon pug addition vacuum-extruder, vacuum is 2.0MPa, and extrusion pressure is
1500KN。
Step 3) dry moulded pottery not yet put in a kiln to bake:
Alveolate activated carbon base substrate is placed in electric furnace drying, wherein baking temperature be 300 DEG C, drying time be 15h.
Step 4) end face cure process:
Being immersed in by product in cure process liquid, dip time is 10min, and dipping face height is 25mm.
Wherein cure process liquid consist of aluminum nitrate, carboxymethyl cellulose, deionized water, weight ratio is 25:1.5:75.
The denitrating catalyst product size prepared in embodiment 1 is 40mm × 40mm × 80mm, catalyst endoporus hole
Footpath 5mm, inwall wall thickness is 1.5mm, and outer wall wall thickness is 2mm.Active component contained by denitrating catalyst is manganese.The density of product is
500g/l, is shown in Table 1 for the simulated fire power-plant flue gas composition measured, this consumption ratio of nitrogen oxide removal efficiency, ammonia is shown in Table 2
With table 3.
The coal steam-electric plant smoke composition of table 1 simulated determination
| Gas | NO | NH3 | SO2 | O2 | N2 |
| Volume fraction % | 0～0.10 | 0～0.10 | 0.02～0.05 | 5.00 | 94.75 |
The clearance of table 2 nitrogen oxides
This consumption ratio of table 3 reducing agent ammonia
Claims (7)
1. the method preparing modified activated carbon, it is characterised in that it is prepared via a method which to obtain:
1) in certain density aqueous solution of nitric acid, add activated carbon and at a certain temperature described activated carbon processed,
It is washed with deionized described activated carbon after treatment drying for standby；
2) to step 1) activated carbon of gained adds manganese nitrate aqueous solution and surface dispersant, enter in the electric furnace of nitrogen protection
Activate, obtain pre-modified activated carbon, the addition of wherein said surface dispersant be manganese nitrate aqueous solution weight 0.1～
10%；
3) by step 2) the pre-modified activated carbon of gained adds in aqueous slkali, and enter in the electric furnace of nitrogen protection and activate,
To required modified activated carbon.
Method the most according to claim 1, it is characterised in that it is prepared via a method which to obtain:
1) in the aqueous solution of nitric acid that weight percent content is 5-30%, activated carbon is added and to described work at 40-80 DEG C
Property charcoal carry out process 1-10h, be washed with deionized described activated carbon after treatment and at 50-90 DEG C be dried 5-10h standby
With, wherein said activated carbon is 1:5-1:10 with the mass volume ratio of aqueous solution of nitric acid；
2) to step 1) activated carbon of gained adds manganese nitrate aqueous solution that weight percent content is 1-15% and surface is divided
Powder, after soaking 1～25h, enters in the electric furnace of nitrogen protection and activates, and soak time is 1～20h, and activation temperature is 200
～450 DEG C, obtain pre-modified activated carbon, the addition of wherein said surface dispersant be manganese nitrate aqueous solution weight 0.1～
10%；
3) by step 2) to add weight percent content be in 5-40% aqueous slkali for the pre-modified activated carbon of gained, soaks 1～25h
After, entering in the electric furnace of nitrogen protection and activate, activation temperature is 350～700 DEG C, and soak time is 1～20h, obtains institute
The modified activated carbon needed.
Method the most according to claim 1 and 2, it is characterised in that described activated carbon is cocoanut active charcoal, ature of coal activity
One in charcoal, active fruit shell carbon or activated carbon from bamboo or a combination thereof.
Method the most according to claim 1 and 2, it is characterised in that described surface dispersant is PEG400, poly-second
One in glycol 1000, Macrogol 2000 or dodecylbenzene sodium sulfonate or a combination thereof.
Method the most according to claim 1 and 2, it is characterised in that described alkali is in sodium hydroxide, potassium hydroxide or ammonia
One or a combination thereof.
Modified activated carbon prepared by method the most according to claim 1 and 2.
Modified activated carbon prepared by method the most according to claim 1 and 2 application in making denitrating catalyst.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108744960A (en) * | 2018-06-14 | 2018-11-06 | 华北电力大学（保定） | A kind of flue gas and desulfurizing and denitrifying demercuration and recycling unit and method |
| CN111578275A (en) * | 2020-04-03 | 2020-08-25 | 乐清市亿得利燃烧器有限公司 | Combustor with low emission of nitrogen oxides |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352681A (en) * | 2008-08-29 | 2009-01-28 | 浙江大学 | Low-temperature SCR catalyst using nitrogen-dopped activated carbon as carrier and preparation technique thereof |
| CN101480603A (en) * | 2008-12-30 | 2009-07-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Nitrous oxides gas adsorbing substance and preparation method thereof |
| CN104084189A (en) * | 2014-06-30 | 2014-10-08 | 华南理工大学 | Nano metallic particle-loading activated carbon catalyst as well as preparation method and application thereof |
| CN104415756A (en) * | 2013-08-22 | 2015-03-18 | 上海郎特电力环保科技有限公司 | Modified active carbon and preparation method thereof |
| CN105032403A (en) * | 2015-07-07 | 2015-11-11 | 四川大学 | Catalyst used for low temperature desulphurization and denitration of flue gas and preparation method thereof |
-
2016
- 2016-06-30 CN CN201610505911.9A patent/CN106185912A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352681A (en) * | 2008-08-29 | 2009-01-28 | 浙江大学 | Low-temperature SCR catalyst using nitrogen-dopped activated carbon as carrier and preparation technique thereof |
| CN101480603A (en) * | 2008-12-30 | 2009-07-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Nitrous oxides gas adsorbing substance and preparation method thereof |
| CN104415756A (en) * | 2013-08-22 | 2015-03-18 | 上海郎特电力环保科技有限公司 | Modified active carbon and preparation method thereof |
| CN104084189A (en) * | 2014-06-30 | 2014-10-08 | 华南理工大学 | Nano metallic particle-loading activated carbon catalyst as well as preparation method and application thereof |
| CN105032403A (en) * | 2015-07-07 | 2015-11-11 | 四川大学 | Catalyst used for low temperature desulphurization and denitration of flue gas and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 傅成诚等: "NaOH改性活性炭的表面特征及吸附甲醛的性能", 《化工环保》 * |
| 张东辉等: "改性活性炭纤维负载锰铈复合氧化物低温选择性催化还原脱硝", 《北京科技大学学报》 * |
| 詹亮等: "正交实验法在超级活性炭研制中的应用", 《煤炭转化》 * |
| 谷端律等: "高表面积活性炭的开发", 《新型碳材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108744960A (en) * | 2018-06-14 | 2018-11-06 | 华北电力大学（保定） | A kind of flue gas and desulfurizing and denitrifying demercuration and recycling unit and method |
| CN111578275A (en) * | 2020-04-03 | 2020-08-25 | 乐清市亿得利燃烧器有限公司 | Combustor with low emission of nitrogen oxides |
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Application publication date: 20161207 |