CN109939694A - A kind of honeycomb fashion low-temperature denitration catalyst and preparation method thereof - Google Patents
A kind of honeycomb fashion low-temperature denitration catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of cellular low-temperature denitration catalysts and preparation method thereof, the hydrotalcite of carbon nanotube and metavanadate intercalation that the present invention is obtained by the method for ion exchange, Mn, Cu atom being uniformly distributed in rule on its laminate, the Active components distribution of catalyst is uniform and is tightly combined with carrier, under the influence of the dual electronic effect of " carrier " and laminate, catalyst is enabled to play the catalytic effect that common loaded catalyst can not be reached.
Description
Technical field
The present invention relates to a kind of denitrating catalyst more particularly to a kind of cellular low-temperature denitration catalyst and its preparation sides
Method belongs to the preparation technical field of catalyst.
Background technique
Nitrogen oxides (NOX) it is one of major pollutants of atmospheric environment, it is to form acid rain and photochemical fog main
Substance, ecological environment and human lives to global range bring serious harm.Wherein, the nitrogen discharged in coal steam-electric plant smoke
Oxide (NOX) account for the overwhelming majority.
For the technology of denitrating flue gas, selective catalytic reduction (selectivecatalytic, SCR) method is with reaction temperature
It lower, the features such as purification efficiency is high, reliable for operation and secondary pollution is small, is widely used at present.Catalyst is SCR cigarette
Core in gas denitrating system, performance quality directly influence the whole denitration effect of SCR flue gas denitrification system.China's thermoelectricity
The SCR denitration device of factory is all made of high dirt arrangement, and reactor between economizer and air preheater, take by the flue gas in the region
With a large amount of flying dust.Therefore, during SCR system is run, catalyst is inevitably because various physical chemistry are made
It is failed with (poisoning, abrasion, thermal sintering, blocking/contamination etc.), leads to its reduced service life, the replacement speed of catalyst adds
Fastly, this causes tremendous influence to the denitration effect and economic cost of SCR system.
SCR technology is developed so far existing more than 30 years history, is that a kind of relatively more extensive flue gas of current foreign applications is de-
Nitre technology.But due to the shortcoming on catalytic theory and study on mechanism, this technology is caused to reach perfect degree far away.Mesh
Technology the most mature is with NH on former world3For the SCR technology (SCR) of reducing agent.The technology is using V-
Using vanadic anhydride as active component, and a small amount of WO is added in Ti series catalysts3Or MoO3As auxiliary agent to inhibit SO2It is oxidized to
SO3, improve activity, thermal stability and the anti-toxicity energy of catalyst, by the nitrogen oxides in flue gas and spray into going back in flue gas
Former agent (NH3) reduction reaction occurs, N is generated under the catalytic action of vanadic anhydride2And H2O.And ceramic honeycomb catalyst is
The core of SCR technology, it decides the nitric efficiency and economy of SCR technology, and construction cost accounts for Flue Gas Denitrification Engineering cost
20% or more, operating cost accounts for 30% or more, and the substrate titanium dioxide of denitrating catalyst at present is expensive, and with
Its chemical lifetime of the passage of time expires, it will the processing problem for facing denitrating catalyst, due to its main active constituent vanadium
It is extremely toxic substance, the cost of catalyst fixed-end forces is also larger, and the low temperature active of the catalyst is poor, uses temperature range
Narrow, operation temperature is generally 350~400 DEG C, its NOx removal rate is generally 80% or so under the operation temperature, easily in generation
Poison, the service life of catalyst averagely only have 2400h.
Very more for the research of out of stock catalyst at present, either academia or industrial researcher endeavours
In developing novel out of stock catalyst, metal oxide catalyst is to study more denitrating catalyst system at present, activity
Component mainly has V2O5、WO3、Fe2O3、CuO、CrOx、MnOx、MoO3Or mixtures thereof with the metal oxides such as NiO, wherein V2O5、
Fe2O3It is higher with the catalytic denitration activity of MnOx.The carrier of catalyst mainly has TiO2、Al2O3、SiO2、ZrO2Active carbon and point
Son sieve etc..But the preparation of these catalyst all refers to the mixing of many oxide, and the difference of hybrid mode and preparation process are led
The distribution for causing catalyst activity component is not so uniform, therefore catalytic activity is not ideal enough, some powder catalyst ns Ox
Conversion ratio can reach 90% or more, and the activity for forming rear catalyst then will appear certain decline, and catalyst easily occurs
The poisoning of unknown cause causes its service life to fall short of, and there are no develop to be suitably applied taking off in industry's enlarging production
Sell catalyst.
Layered double hydroxide (LDHs) is a kind of anion lamellar compound, also known as hydrotalcite, and LDHs is by layer
Between anion and positively charged laminate accumulation made of, with embeddable anion structure, the structure of LDHs such as sandwich
Shape, both sides are made of the metal ion positive charge piece of divalent and trivalent, and centre is anion and hydrone, the main layer board of LDHs
With the particularity of the Nomenclature Composition and Structure of Complexes of interlayer object, the numerous special performances of LDHs are imparted, the anion of LDHs interlayer can be with
Anion with various specific functions swaps, so that synthesis has the intercalation configuration material of different performance.
Summary of the invention
The present invention is for present in the metal oxide catalyst in the V-Ti series catalysts of current industrial application and research
Deficiency, a kind of cellular low-temperature denitration catalyst and preparation method thereof is provided.
The technical scheme to solve the above technical problems is that
A kind of preparation method of honeycomb fashion low-temperature denitration catalyst, includes the following steps:
1) processing of carbon nanotube: the aqueous solution of oxidizing acid is added into carbon nanotube, under the conditions of 120~140 DEG C
Reflux 3~8 hours, centrifuge separation, is washed to neutrality, the carbon nanotube being acidified；Afterwards by the carbon nanotube of resulting acidification
It is added in the aqueous solution of anionic polyelectrolyte or anionic surfactant, ultrasonic wave dispersion, later under stirring condition
50~70 DEG C are reacted 4~10 hours, and the concentration of aqueous solution of the anionic polyelectrolyte or anionic surfactant is 1~
The weight ratio of 10g/L, the carbon nanotube and anionic polyelectrolyte or anionic surfactant is 1:(0.01~0.1),
Centrifuge separation removes unreacted anionic polyelectrolyte or anionic surfactant after reaction, obtains surface with negative electrical charge
Carbon nanotube；
2) preparation of LDHs: using water-soluble manganese salt, mantoquita and aluminium salt as raw material, the mixed of manganese salt, mantoquita and aluminium salt is prepared
Solution A is closed, molar ratio (Mn is controlled2++Cu2+):Al3+Aqueous slkali B is added dropwise to solution under constant agitation by=1:2
In A, pH value of solution=9~10 are kept in the process, and aqueous slkali B continues stirring ageing 3~5 hours, filters, instead after being added dropwise
After backwashing is washed to neutrality, and LDHs powder is obtained；
3) ion-exchange reactions: compound concentration is the metavanadate aqueous solution of 0.1~0.5mol/L, and step 1) is resulting
Carbon nanotube and step 2) resulting LDHs powder of the surface with negative electrical charge, which are added in metavanadate aqueous solution, obtains reactant
System, control carbon nanotube, metavanadate and LDHs powder mass ratio be 1:(3~5): (5~10), after reaction system is placed in
Ion-exchange reactions is carried out at 40~60 DEG C, reaction is filtered after 3~5 hours, is washed to neutrality, is obtained carbon nanotube and metavanadic acid root
The LDHs of intercalation；
4) mixed aid Ce: compound concentration is the cerium salt solution of 0.1~0.3mol/L, with bodies such as gained cerium salt solutions
Product impregnation steps 3) obtained in carbon nanotube and metavanadic acid root cutting layer LDHs, rear dry catalyst precarsor；
5) it is kneaded, forms: the resulting catalyst precarsor of step 4) and lubricant, binder, pore creating material being mixed, water is added
It is kneaded in kneading machine, squeezes out cellular catalyst green body with extruder after mixing, by gained catalyst body drying,
Roasting, obtains cellular low-temperature denitration catalyst.
Technical solution of the present invention can also do following improvement.
Further, the oxidizing acid refers to the mixture of one or more of nitric acid, sulfuric acid, permanganic acid, hypochlorous acid.
Further, the anionic polyelectrolyte is one of kayexalate, sodium lignin sulfonate or both
Mixture, the anionic surfactant be neopelex.
Further, the manganese salt is manganese nitrate, manganese sulfate or manganese chloride, and the mantoquita is copper nitrate, copper sulphate or chlorination
Copper, the aluminium salt are aluminum nitrate, aluminum sulfate or aluminium chloride.
Further, the aqueous slkali B is sodium hydroxide solution, the mixed solution of sodium hydroxide and sodium carbonate, potassium hydroxide
Solution or ammonia spirit.
Further, the metavanadate is sodium metavanadate, potassium metavanadate or ammonium metavanadate.
Further, the cerium salt is ammonium ceric nitrate or cerous nitrate.
Further, the lubricant is glycerol or ethanol amine, and the binder is bentonite, silica solution, hydroxylmethyl cellulose
One of plain sodium, polyvinyl alcohol, the pore creating material are one of polyethylene glycol oxide, polymethyl methacrylate, sesbania powder
Or a variety of mixture.
Further, in step 5) with the poidometer of catalyst precarsor, mixed lubrication agent 3~5 in every 100 parts of catalyst precarsors
Part, 10~15 parts of binder, 5~8 parts of pore creating material.
The cellular low-temperature denitration catalyst that above-mentioned preparation method produces is also claimed in the present invention.
The characteristics of honeycomb fashion low-temperature denitration catalyst provided by the invention and preparation method thereof, is as follows:
1) architectural characteristic for utilizing hydrotalcite will have negative electricity by moditied processing rear surface by the method for ion exchange
The carbon nanotube and metavanadic acid root of lotus are inserted into the interlayer of hydrotalcite, so that catalyst is provided with carbon nanotube and V2O5Alternately arrange
" carrier " of column, and then can use the electronic effect of carbon nanotube to influence V2O5Electronics distribution, the electronics knot of modulation carrier
Structure, the final catalytic performance for influencing catalyst；
2) on the neatly stone veneer of the carbon nanotube and metavanadic acid root cutting layer obtained additionally by the method for ion exchange
Mn, Cu atom are uniformly distributed in rule, and the Active components distribution of catalyst is tightly combined uniformly and with carrier, at " carrier " and
Under the influence of the dual electronic effect of laminate, catalyst is enabled to play what common loaded catalyst can not be reached
Catalytic effect；
3) low-temperature catalytic activity of active component Mn is good in catalyst of the invention, can be improved the low temperature of catalyst entirety
Catalytic activity, although it is to SO2It is especially sensitive, but the presence of auxiliary agent Ce can greatly improve the anti-SO of Mn2Ability, Cu are also to urge
The active component of agent is distributed with Mn regular interval in neatly stone veneer, matches with the electronic effect of carrier, common to realize
The good catalytic performance of catalyst.
The beneficial effects of the present invention are:
1) technique of the invention greatly reduces the dosage of titanium dioxide, reduces cost of material and fixed-end forces cost, and
It is mild condition in production technology, simple to operation, it is suitably applied industry's enlarging production；
2) the out of stock preformed catalyst of honeycomb fashion made from technique of the invention, conversion rate of NOx can reach 90% or more, and
Low temperature active is good, it is minimum can be realized at 200 DEG C 90% or more conversion rate of NOx, the long service life of catalyst applying
90% conversion rate of NOx is still able to maintain when 3600h.
Specific embodiment
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment 1:
A kind of preparation method of honeycomb fashion low-temperature denitration catalyst, includes the following steps:
1) processing of carbon nanotube: weigh the Shenzhen 100g nanometer port Co., Ltd purchase 20~40nm of diameter, length 1~
The permanganic acid 500ml of 3mol/L is added thereto, is heated to flowing back 8 hours at 120 DEG C, be cooled to for 2 μm of single-walled carbon nanotube
Room temperature, centrifuge separation, clear water are washed to neutrality, the carbon nanotube being acidified；The carbon nanotube 50g of acidification is added to
500ml concentration is to be initially positioned at ultrasound 1 hour in 20Hz ultrasonic device in the lignin sulfonic acid sodium water solution of 10g/L, be placed on 50
It is reacted 10 hours under the conditions of DEG C stirred in water bath, centrifuge separation removes unreacted sodium lignin sulfonate after having reacted, and obtains table
Face has the carbon nanotube of negative electrical charge；
2) preparation of LDHs: using manganese nitrate, copper nitrate and aluminum nitrate as raw material, the manganese for being 0.6mol/L with salt manufacturing total concentration
The mixed solution A of salt, mantoquita and aluminium salt controls molar ratio (Mn2++Cu2+):Al3+=1:2 under constant agitation will
The sodium hydroxide solution of 1.0mol/L is added dropwise in solution A, keeps pH value of solution=9~10, aqueous slkali B drop in the process
It adds and continues stirring ageing 3 hours after finishing, filtering washs repeatedly to neutrality, obtains LDHs powder；
3) ion-exchange reactions: compound concentration is the sodium metavanadate aqueous solution 800ml of 0.3mol/L, by 10g step 1) institute
Carbon nanotube and 50g step 2) resulting LDHs powder of the surface obtained with negative electrical charge, which are added in metavanadate aqueous solution, to be obtained
Reaction system, after reaction system be placed at 50 DEG C carry out ion-exchange reactions, reaction is filtered after 3~5 hours, is washed into
Property, obtain the LDHs of carbon nanotube Yu metavanadic acid root cutting layer；
4) mixed aid Ce: compound concentration is the cerous nitrate aqueous solution of 0.2mol/L, with gained cerous nitrate aqueous solution
The LDHs of carbon nanotube obtained in incipient impregnation step 3) and metavanadic acid root cutting layer, after in dry in 80 DEG C of air dry ovens
Obtain catalyst precarsor；
5) it is kneaded, forms: by the resulting catalyst precarsor of step 4) and lubricant glycerol, binder bentonite, pore creating material
Polyethylene glycol oxide mixes, and 5 parts of glycerol, 10 parts of bentonite, polyethylene glycol oxide 5 are added in the catalyst precarsor of every 100 parts by weight
Part, in backward mixture plus water is kneaded in kneading machine, is made cellular with 22 punch die extrusion moldings after mixing and is urged
Gained catalyst green body is dried at 80 DEG C 12h, is placed at 600 DEG C and roasts for 24 hours to get cellular low temperature by agent green body
Denitrating catalyst C1.
Embodiment 2:
A kind of preparation method of honeycomb fashion low-temperature denitration catalyst, includes the following steps:
1) processing of carbon nanotube: weigh the Shenzhen 100g nanometer port Co., Ltd purchase 20~40nm of diameter, length 1~
The nitric acid 500ml of 3mol/L is added thereto, is heated to flowing back 5 hours at 130 DEG C, is cooled to room for 2 μm of multi-walled carbon nanotube
Temperature, centrifuge separation, clear water are washed to neutrality, the carbon nanotube being acidified；The carbon nanotube 50g for weighing acidification is added to
500ml concentration is that it is small to be initially positioned at ultrasound 2 in 20Hz ultrasonic device in kayexalate (abbreviation PSS) aqueous solution of 6g/L
When, it is placed under the conditions of 60 DEG C of stirred in water bath and reacts 7 hours, centrifuge separation removes unreacted PSS after having reacted, and obtains table
Face has the carbon nanotube of negative electrical charge；
2) preparation of LDHs: using water-soluble manganese chloride, copper chloride and aluminium chloride as raw material, preparing total concentration is
The mixed solution A of the manganese chloride of 0.6mol/L, copper chloride and aluminium chloride controls molar ratio (Mn2++Cu2+):Al3+=1:2, not
Aqueous slkali B is added dropwise in solution A under disconnected stirring condition, aqueous slkali B is that 2:1 matches sodium hydroxide in molar ratio with sodium carbonate
At mixed solution, the molar concentration of sodium hydroxide is 1.0mol/L, and pH value of solution=9~10, alkali soluble are kept during dropwise addition
Liquid B continues stirring ageing 3~5 hours after being added dropwise, filtering washs repeatedly to neutrality, obtains LDHs powder；
3) ion-exchange reactions: compound concentration is the potassium metavanadate aqueous solution 1200ml of 0.1mol/L, by 5g step 1) institute
Carbon nanotube and 35g step 2) resulting LDHs powder of the surface obtained with negative electrical charge, which are added in metavanadate aqueous solution, to be obtained
Reaction system, after reaction system be placed at 40 DEG C carry out ion-exchange reactions, reaction is filtered after 5 hours, is washed to neutrality, is obtained
The LDHs of carbon nanotube and metavanadic acid root cutting layer；
4) mixed aid Ce: compound concentration is the ceric ammonium nitrate solution of 0.5mol/L, with bodies such as gained ceric ammonium nitrate solutions
Product impregnation steps 3) obtained in carbon nanotube and metavanadic acid root cutting layer LDHs, after in so dry that urge in 80 DEG C of air dry ovens
Agent precursor；
5) it is kneaded, forms: by the resulting catalyst precarsor of step 4) and lubricant ethanol amine, adhesive silicon sol, pore-creating
Agent sesbania powder mixes, and 3 parts of ethanol amine, 15 parts of silica solution, polyethylene glycol oxide 6 are added in the catalyst precarsor of every 100 parts by weight
Part, add water to be kneaded in kneading machine, cellular catalyst green body is squeezed out with 22 punch dies after mixing, by gained catalyst
Green body is dry at 100 DEG C, is placed at 600 DEG C and roasts for 24 hours, obtains cellular low-temperature denitration catalyst C2.
Embodiment 3:
A kind of preparation method of honeycomb fashion low-temperature denitration catalyst, includes the following steps:
1) processing of carbon nanotube: weigh the Shenzhen 100g nanometer port Co., Ltd purchase 20~40nm of diameter, length 1~
The sulfuric acid 500ml of 5mol/L is added thereto, is heated to flowing back 3 hours at 140 DEG C, is cooled to room for 2 μm of multi-walled carbon nanotube
Temperature, centrifuge separation, clear water are washed to neutrality, the carbon nanotube being acidified；The carbon nanotube 50g for weighing resulting acidification is added
In the sodium dodecyl benzene sulfonate aqueous solution for being 1g/L to 500ml concentration, it is initially positioned at ultrasound 1 hour in 20Hz ultrasonic device, after
It is placed under the conditions of 70 DEG C of stirred in water bath and reacts 4 hours, centrifuge separation removes unreacted dodecyl benzene sulfonic acid after having reacted
Sodium obtains the carbon nanotube that surface has negative electrical charge；
2) preparation of LDHs: using manganese sulfate, copper sulphate and aluminum sulfate as raw material, the sulfuric acid that total concentration is 0.6mol/L is prepared
The mixed solution A of manganese, copper sulphate and aluminum sulfate controls molar ratio (Mn2++Cu2+):Al3+=1:2 under constant agitation will
The potassium hydroxide solution of 1.0mol/L is added dropwise in solution A, keeps pH value of solution=9~10, potassium hydroxide in the process
Solution continues stirring ageing 3~5 hours after being added dropwise, filtering washs repeatedly to neutrality, obtains LDHs powder；
3) ion-exchange reactions: compound concentration is the ammonium metavanadate aqueous solution 1000ml of 0.5mol/L, by 12g step 1) institute
Carbon nanotube and 120g step 2) resulting LDHs powder of the surface obtained with negative electrical charge are added in ammonium metavanadate aqueous solution
Reaction system, after reaction system be placed at 60 DEG C carry out ion-exchange reactions, be filtered after reacting for 3 hours, washing to neutrality,
Obtain the LDHs of carbon nanotube and metavanadic acid root cutting layer；
4) mixed aid Ce: compound concentration is the cerous nitrate aqueous solution of 0.3mol/L, with gained cerous nitrate aqueous solution
The LDHs of carbon nanotube obtained in incipient impregnation step 3) and metavanadic acid root cutting layer, after in dry in 80 DEG C of air dry ovens
Obtain catalyst precarsor；
5) be kneaded, form: by the resulting catalyst precarsor of step 4) and lubricant glycerol, binder hydroxymethyl cellulose,
Pore creating material polymethyl methacrylate mixes, and 4 parts of glycerol, hydroxylmethyl cellulose are added in the catalyst precarsor of every 100 parts by weight
Plain 12 parts, 8 parts of polymethyl methacrylate, add water to be kneaded in kneading machine, are squeezed out after mixing with 22 punch dies cellular
Catalyst green body, gained catalyst green body is dry at 100 DEG C, be placed at 600 DEG C and roast for 24 hours, obtain cellular low temperature
Denitrating catalyst C3.
Embodiment 4:
A kind of preparation method of honeycomb fashion low-temperature denitration catalyst, includes the following steps:
1) processing of carbon nanotube: weigh the Shenzhen 100g nanometer port Co., Ltd purchase 20~40nm of diameter, length 1~
The hypochlorous acid 500ml of 5mol/L is added thereto, is heated to flowing back 5 hours at 120 DEG C, be cooled to for 2 μm of multi-walled carbon nanotube
Room temperature, centrifuge separation, clear water are washed to neutrality, the carbon nanotube being acidified；The carbon nanotube 50g for weighing resulting acidification adds
Enter in the sodium dodecyl benzene sulfonate aqueous solution for being 4g/L to 500ml concentration, be initially positioned at ultrasound 1 hour in 20Hz ultrasonic device,
It is placed under the conditions of 70 DEG C of stirred in water bath and reacts 4 hours, centrifuge separation removes unreacted detergent alkylate sulphur after having reacted
Sour sodium obtains the carbon nanotube that surface has negative electrical charge；
2) preparation of LDHs: using manganese sulfate, copper sulphate and aluminum sulfate as raw material, the sulfuric acid that total concentration is 0.6mol/L is prepared
The mixed solution A of manganese, copper sulphate and aluminum sulfate controls molar ratio (Mn2++Cu2+):Al3+=1:2 under constant agitation will
The ammonia spirit of 1.0mol/L is added dropwise in solution A, keeps pH value of solution=9~10 in the process, and ammonia spirit is added dropwise
After continue stirring ageing 3~5 hours, filtering, washed repeatedly to neutrality, obtain LDHs powder；
3) ion-exchange reactions: compound concentration is the ammonium metavanadate aqueous solution 1000ml of 0.4mol/L, by 10g step 1) institute
Carbon nanotube and 60g step 2) resulting LDHs powder of the surface obtained with negative electrical charge, which are added in ammonium metavanadate aqueous solution, to be obtained
Reaction system, after reaction system be placed at 60 DEG C carry out ion-exchange reactions, be filtered after reacting for 3 hours, wash to neutrality, obtain
The LDHs of carbon nanotube and metavanadic acid root cutting layer；
4) mixed aid Ce: compound concentration is the ammonium ceric nitrate aqueous solution of 0.2mol/L, with gained ammonium ceric nitrate aqueous solution
The LDHs of carbon nanotube obtained in incipient impregnation step 3) and metavanadic acid root cutting layer, after in dry in 80 DEG C of air dry ovens
Obtain catalyst precarsor；
5) it is kneaded, forms: by the resulting catalyst precarsor of step 4) and lubricant glycerol, binder polyvinyl alcohol, pore-creating
Agent polymethyl methacrylate mixes, and 5 parts of glycerol is added in the catalyst precarsor of every 100 parts by weight, 12 parts of polyvinyl alcohol, gathers
7 parts of methyl methacrylate, water is added to be kneaded in kneading machine, squeezes out cellular catalyst base with 22 punch dies after mixing
Body, gained catalyst green body is dry at 100 DEG C, it is placed at 600 DEG C and roasts for 24 hours, obtain cellular low-temperature denitration catalyst
C4。
In order to test the catalytic performance for the cellular low-temperature denitration catalyst that preparation method of the invention produces, carry out
Following test:
1, conversion rate of NOx is tested
Test object: the resulting C1 catalyst of embodiment 1；
Test process: C1 catalyst is cut into the hole 5*5, length 100mm；Flue gas composition: NO=600ppm, NH3=
600ppm, O2=4%, H2O=4.52%；Reaction temperature: every 20 DEG C of tests, one denitrification rate since 180 DEG C, until
420 DEG C of stoppings, the test result of denitrification rate are shown in Table 1.
2, catalyst life is tested
Test object: the resulting C2 catalyst of embodiment 2；
Test process: C2 catalyst is cut into the hole 5*5, length 100mm；Flue gas composition: NO=600ppm, NH3=
600ppm, O2=4%, H2O=4.52%；The reaction time: reaction temperature control is tested at 260~280 DEG C every 50 hours
Primary point denitrification rate, until 3600 hours stop, catalyst life test the results are shown in Table 2.
The denitrification rate test result of 1 catalyst C1 of table
The life test result of 2 catalyst C2 of table
As can be seen from Table 1, the resulting catalyst of the present invention starts to can reach 90% or more denitration at 200 DEG C
Rate, operation interval extend to 420 DEG C from 200 DEG C, show that the resulting catalyst low-temperature activity of the present invention is good, use humidity province
Between it is wide, separately from the point of view of the catalyst life test result of table 2, the conversion rate of NOx of catalyst is until 3600h remains to maintain
It is enough to show that the resulting catalyst of the present invention has for 85% or more (the still higher than existing V-Ti series catalysts industrially applied)
Long service life, is not susceptible to catalyst poisoning, is suitably applied in industrialized large-scale production.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of honeycomb fashion low-temperature denitration catalyst, which comprises the steps of:
1) processing of carbon nanotube: the aqueous solution of oxidizing acid is added into carbon nanotube, flows back 3 under the conditions of 120~140 DEG C
~8 hours, centrifuge separation was washed to neutrality, the carbon nanotube being acidified；The carbon nanotube by resulting acidification is added to afterwards
In the aqueous solution of anionic polyelectrolyte or anionic surfactant, ultrasonic wave dispersion, later 50~70 under stirring condition
DEG C reaction 4~10 hours, the concentration of aqueous solution of the anionic polyelectrolyte or anionic surfactant was 1~10g/L, institute
The weight ratio for stating carbon nanotube and anionic polyelectrolyte or anionic surfactant is 1:(0.01~0.1), after reaction from
Heart separation removes unreacted anionic polyelectrolyte or anionic surfactant, obtains the carbon nanometer that surface has negative electrical charge
Pipe；
2) preparation of LDHs: using water-soluble manganese salt, mantoquita and aluminium salt as raw material, the mixing for preparing manganese salt, mantoquita and aluminium salt is molten
Liquid A controls molar ratio (Mn2++Cu2+):Al3+Aqueous slkali B is added dropwise in solution A by=1:2 under constant agitation,
PH value of solution=9~10 are kept in the process, and aqueous slkali B continues stirring ageing 3~5 hours after being added dropwise, filtering is washed repeatedly
It washs to neutrality, obtains LDHs powder；
3) ion-exchange reactions: compound concentration is the metavanadate aqueous solution of 0.1~0.5mol/L, by the resulting surface of step 1)
The resulting LDHs powder of carbon nanotube and step 2) with negative electrical charge, which is added in metavanadate aqueous solution, obtains reaction system, control
The mass ratio of carbon nanotube processed, metavanadate and LDHs powder is 1:(3~5): (5~10), after reaction system is placed in 40~
Ion-exchange reactions is carried out at 60 DEG C, reaction is filtered after 3~5 hours, is washed to neutrality, is obtained carbon nanotube and metavanadic acid root cutting layer
LDHs；
4) mixed aid Ce: compound concentration is the cerium salt solution of 0.1~0.3mol/L, is soaked in equal volume with gained cerium salt solution
The LDHs of carbon nanotube obtained in stain step 3) and metavanadic acid root cutting layer, rear dry catalyst precarsor；
5) it is kneaded, forms: the resulting catalyst precarsor of step 4) and lubricant, binder, pore creating material are mixed, add water in mixed
It is kneaded in mill, squeezes out cellular catalyst green body with extruder after mixing, by gained catalyst body drying, roasting
It burns, obtains cellular low-temperature denitration catalyst.
2. preparation method according to claim 1, which is characterized in that the anionic polyelectrolyte is polystyrolsulfon acid
The mixture of one of sodium, sodium lignin sulfonate or both, the anionic surfactant are neopelex.
3. preparation method according to claim 1 or 2, which is characterized in that the oxidizing acid is nitric acid, sulfuric acid, Gao Meng
The mixture of one or more of acid, hypochlorous acid.
4. preparation method according to claim 1 or 2, which is characterized in that the metavanadate is sodium metavanadate, metavanadic acid
Potassium or ammonium metavanadate；The cerium salt is ammonium ceric nitrate or cerous nitrate.
5. preparation method according to claim 1 or 2, which is characterized in that the manganese salt is manganese nitrate, manganese sulfate or chlorination
Manganese, the mantoquita are copper nitrate, copper sulphate or copper chloride, and the aluminium salt is aluminum nitrate, aluminum sulfate or aluminium chloride.
6. preparation method according to claim 1 or 2, which is characterized in that the aqueous slkali B is sodium hydroxide solution, hydrogen
Any one of the mixed solution of sodium oxide molybdena and sodium carbonate, potassium hydroxide solution, ammonia spirit.
7. preparation method according to claim 1 or 2, which is characterized in that the lubricant be glycerol or ethanol amine, it is described
Binder be one of bentonite, silica solution, sodium cellulose glycolate, polyvinyl alcohol, the pore creating material be polyethylene glycol oxide,
One of polymethyl methacrylate, sesbania powder or a variety of mixtures.
8. preparation method according to claim 7, which is characterized in that with the poidometer of catalyst precarsor in step 5), often
3~5 parts of mixed lubrication agent, 10~15 parts of binder, 5~8 parts of pore creating material in 100 parts of catalyst precarsors.
9. the cellular low-temperature denitration catalyst that preparation method according to any one of claims 1 to 8 is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111495379A (en) * | 2020-04-30 | 2020-08-07 | 南京赤博环保科技有限公司 | Denitration catalyst and preparation method and application thereof |
| CN111545219A (en) * | 2020-05-01 | 2020-08-18 | 赵玉平 | Catalyst for preparing acrolein by propylene oxidation and preparation method thereof |
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2019
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111495379A (en) * | 2020-04-30 | 2020-08-07 | 南京赤博环保科技有限公司 | Denitration catalyst and preparation method and application thereof |
| CN111545219A (en) * | 2020-05-01 | 2020-08-18 | 赵玉平 | Catalyst for preparing acrolein by propylene oxidation and preparation method thereof |
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Application publication date: 20190628 |