CN102000564B - Coal ash and attapulgite compound SCR denitration catalyst and preparation method thereof - Google Patents
Coal ash and attapulgite compound SCR denitration catalyst and preparation method thereof Download PDFInfo
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- CN102000564B CN102000564B CN2010105240075A CN201010524007A CN102000564B CN 102000564 B CN102000564 B CN 102000564B CN 2010105240075 A CN2010105240075 A CN 2010105240075A CN 201010524007 A CN201010524007 A CN 201010524007A CN 102000564 B CN102000564 B CN 102000564B
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Abstract
The invention discloses a coal ash and attapulgite compound SCR denitration catalyst and a preparation method thereof. Coal ash and attapulgite compound are used as catalyst carriers for carrying the compound material of manganese oxide. The preparation method comprises the following steps: mixing the coal ash with the attapulgite, making the mixture into coal ash and attapulgite compound catalyst carrier by scoring, molding, drying and burning, using the isopyknic immersion method to carry the compound carrier on the catalyst precursor, drying and burning so as to acquire the finished product. In the invention, the coal ash and the attapulgite cheaply obtained are used as the catalyst carriers, so the cost of the catalyst and the environmental loading of the catalyst are reduced, the mouldability and the heat stability are better, and the low-temperature activity of the catalyst is better because of the loading of manganese active component.
Description
One, technical field
The nitrogen oxide that the present invention relates to coal-fired flue-gas in the environmental technology field is handled specifically a kind of flyash-attapulgite composite SCR denitrating catalyst and preparation method thereof.
Two, background technology
China is coal-fired big country, and the coal-burning power plant produces amounts of dust, SOx, NOx and poisonous metal element etc. in process of production.The nitrogen oxide that discharges in the flue gas (NOx) is even more serious to the hazard ratio sulfide of environment, and the NOx in the atmosphere can cause destruction ecological environments such as acid rain, photochemical fog, surface water eutrophication and jeopardize a series of problems of human health.The discharging of NOx has caused global concern in the control atmosphere, also is emphasis and the difficult point in the present atmospheric environment protection of China simultaneously, and is therefore, particularly important to the processing of NOx.At present, the NOx control method that produces for burning of China mainly contains in control before the burning, the burning three types of controls and the control of burning back.Control is meant and selects low nitrogen fuel for use before the burning, but cost is very high, and practical applications is less; Control in the burning, promptly improve combustion system, in combustion process, reduce the generation (comprising low oxygen combustion technology, multiterminal combustion technology etc.) of nitrogen oxide; The control of burning back is meant at the flue afterbody installs denitrification apparatus additional, changes the NOx in the flue gas into harmless N
2Or useful fertilizer, comprise absorption process, absorption method, non-selective catalytic reduction (SNCR) and SCR (SCR) etc.
(selective catalytic reduction, advantage such as SCR) method is lower with its reaction temperature, and purifying rate is high, and is reliable, and secondary pollution is little has become the prefered method that removes NOx to SCR in developed country.The characteristics of SCR method be with ammonia or urea etc. as reducing agent under catalyst action with the NOx catalytic reduction, make reducing agent can be selectively with flue gas in NOx reaction generation N
2And H
2O.In the SCR technology, catalyst is a core, and its cost accounts for 20%～40% of SCR system synthesis basis, and the performance of catalyst directly influences the removal effect of NOx.Can find out that from present disclosed patent employed carrier of various (SCR) denitrating catalyst and active component have nothing in common with each other, carrier commonly used has TiO
2, molecular sieve, Al
2O
3With active carbon etc.Publication number is that the patent of CN1151705A, CN1777477A, CN1642636A is used single TiO
2Carrier, the chemical reaction mechanism that its active component and active component form also have essence different.Publication number is that the patent of CN1792431A adopts complex carrier, with double oxide Al
2O
3And TiO
2Be complex carrier, do framework material with ceramic honey comb simultaneously, the mode that adopts dipping and coating is with active material V
2O
5And WO
3Load on complex carrier and the framework material.
The SCR technology of China is started late and is started from the nineties in 20th century, and vanadium titanium class catalyst applications is maximum in the at present domestic SCR denitration engineering, mainly contains V
2O
5/ TiO
2, V
2O
5-WO
3/ TiO
2, V
2O
5-MoO
3/ TiO
2And V
2O
5-WO
3-MoO
3/ TiO
2Deng, V wherein
2O
5/ TiO
2And V
2O
5-WO
3/ TiO
2Realized commercialization in succession.The vanadium catalyst series has advantages such as denitration efficiency height, selectivity be good, stable, but this type of catalyst temperature window is narrower, and the reaction temperature interval of vanadium series catalyst is at 300-400 ℃, V
2O
5Be prone to SO
2Be oxidized to SO
3, with the NH that escapes
3Generate NH with the steam reaction in the flue gas
4HSO
4, its viscosity is big, can cause down the obstruction and the corrosion of equipment and pipeline in the heating surface deposition.
In recent years discover that manganese-based catalyst has good low-temperature SCR characteristic; Publication number is that the patent of CN101658787 is carrier with the attapulgite; With the manganese metal oxide is that main active component makes the nano composite material catalyst; This catalyst as reducing agent, all has higher catalyzing N H with ammonia in temperature 150-350 ℃ scope
3The reductive NO reactive activity, but the granularity of this catalyst and preparation method only are applicable to the breadboard lab scale stage, do not possess the condition of suitability for industrialized production.Publication number is that the patent of CN101352681 discloses is the preparation of carrier impregnation load Mn, V, Cu, Co, Fe oxide low-temperature SCR catalyst with the activated carbon; It is carrier impregnation load MnO that the patent of publication number position CN101011659 discloses with the activated carbon
x/ CeO
2The preparation of low-temperature SCR catalyst.The catalyst advantage that with the activated carbon is preparing carriers is that the abundant specific area of absorbent charcoal carrier helps the dispersion of active component, and has certain anti-SO
2Performance, but the active carbon high-temp ablation is too serious in the activating and regenerating process, causes catalyst attrition excessive.
Three, summary of the invention
The present invention is the weak point for fear of above-mentioned prior art, provide a kind of inexpensive, environmental protection, efficient, have flyash-attapulgite composite SCR denitrating catalyst of low-temperature SCR performance and preparation method thereof.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of flyash of the present invention-attapulgite composite SCR denitrating catalyst are: said catalyst is to be catalyst carrier with flyash and attapulgite, the composite of load Mn oxide; Said Mn oxide accounts for the 1-10% of said catalyst carrier quality by the mass percent of manganese.
The characteristics of flyash of the present invention-attapulgite composite SCR denitrating catalyst also are: the divalence nitrate or the divalent sulfur acid salt solution of iron, copper or nickel are added as auxiliary agent, and the mass percent that the addition of said auxiliary agent accounts for catalyst carrier is 0.1-5%.
The characteristics of flyash of the present invention-attapulgite composite SCR denitrating catalyst also are: the mass ratio of Concave-convex clay rod described in the said catalyst carrier and said coal dust ash is 0.5-1.
The characteristics of flyash of the present invention-attapulgite composite SCR denitrating catalyst also are: by mass percentage, the content of attapulgite is not less than 65% in the said Concave-convex clay rod, and the content of dolomite is not more than 10%.
The preparation method's of flyash of the present invention-attapulgite composite SCR denitrating catalyst characteristics are: adopt equi-volume impregnating that catalyst precursor is loaded to the catalyst carrier surface, obtain flyash-attapulgite composite SCR denitrating catalyst after oven dry and the calcining; Said catalyst precursor is major catalyst presoma or major catalyst presoma and co-catalyst presoma; Said major catalyst presoma is Mn (NO
3)
2, divalence nitrate that said co-catalyst presoma is iron, copper, nickel or divalent sulfur hydrochlorate.
The preparation method's of flyash of the present invention-attapulgite composite SCR denitrating catalyst characteristics are to operate according to the following steps:
(1) preparation of catalyst carrier
A, with Concave-convex clay rod mix with flyash and stir compound, in said compound, adding mass concentration is the H of 9-10%
2SO
4Solution, add leave standstill after water stirs 24 hours sample a, amount of water is as the criterion stirring;
Said compound and said H
2SO
4The mass volume ratio of solution is 1g: 1mL or 1g: 2mL;
B, in said sample a, add water and stir, centrifugal back abandoning supernatant, repetitive operation is to supernatant pH=5-6, after the abandoning supernatant sample b;
C, said sample b is stirred, leave standstill 48-96 hour aftershaping under the room temperature and become bottom surface diameter 2-3mm, the cylindrical pellet of high 3-5mm;
D, with said cylindrical pellet 50 ℃ of dryings 5 hours, then in 105 ℃ of dryings 12 hours sample c, with said sample c place nitrogen atmosphere 300-600 ℃ down calcining 2 hours catalyst carrier;
(2) load of catalyst
E, get the 1-10g catalyst carrier, adopt equi-volume impregnating to add water after, survey its solid-to-liquid ratio;
F, the solid-to-liquid ratio that records according to step e take by weighing the catalyst carrier of certain mass and the catalyst precursor of certain volume; Both left standstill 24-48 hour after mixing; Then at 50-70 ℃ of dry 3-5 hour; 100-120 ℃ dry 10-12 hour, place at last under the nitrogen atmosphere in 300-600 ℃ of calcining 2 hours finished product.
Manganese nitrate is decomposed into Mn oxide (MnOx) after high-temperature calcination; Though the activity of such catalysts component is a Mn oxide, the species of Mn oxide are many, are difficult to represent its content; So active component is represented with the percentage that the quality of Mn in the load presoma accounts for the catalyst carrier quality in the catalyst that makes; Be designated as MnX/FA-PG, wherein X representes that the quality of Mn in the load presoma accounts for the percentage of catalyst carrier quality, and FA-PG representes flyash-attapulgite composite catalyzing agent carrier.
Compared with present technology, beneficial effect of the present invention is embodied in:
1, one of raw material used in the present invention flyash is the solid waste of thermal power plant discharging, and the big utilization rate of discharge capacity is low, and environment is brought very big harm.The present invention carries out modification through pickling to industrial waste flyash and increases its specific area; And through mixed according to a certain ratio as to have a Cheap highly effective catalyst of higher mechanical strength and heat endurance with natural nano attapulgite with binder effect; Not only greatly reduce the preparation cost of denitrating catalyst, also have environmental benefit preferably.
2, one of raw material used in the present invention attapulgite belongs to the natural nano-mineral material, and having the cross section is cellular crystals one-dimensional channels, to H
2O, NH
3The little molecule of isopolarity has extremely strong selective absorption performance; Attapulgite has bigger interior external surface area, on surface texture after the modification, more approaches active carbon and NACF than common metal oxide, thereby might possess with activated carbon (fiber) active near low-temperature SCR.The present invention has facilitation as one of catalyst carrier raw material to improving denitration activity and efficient with attapulgite.
Making full use of character such as its good moldability when 3, one of raw material used in the present invention attapulgite is as catalyst carrier mixes according to certain proportioning with industrial waste flyash as binder; After the pickling modification, process flyash-attapulgite composite molding catalyst, more help promoting as industrial catalyst with higher mechanical strength and heat endurance.
4, the manganese-based catalyst that uses of the present invention has good low-temperature SCR catalytic activity, manganese is carried on the complex carrier that makes through infusion process, compares more simplely with coprecipitation method, and the catalyst that makes has good low-temperature SCR performance.
5, the adding of auxiliary components such as iron, copper, nickel helps improving and the rugged catalyst performance among the present invention.
Four, description of drawings
Fig. 1 is the change curve of the catalyst denitration efficiency for preparing of embodiment 1 with reaction temperature.
Fig. 2 is the change curve of the catalyst denitration efficiency for preparing of embodiment 2 with reaction temperature.
Fig. 3 is the change curve of the catalyst denitration efficiency for preparing of embodiment 3 with reaction temperature.
Fig. 4 is the change curve of the catalyst denitration efficiency for preparing of embodiment 4 with reaction temperature.
Fig. 5 is the change curve of the catalyst denitration efficiency for preparing of embodiment 5 with reaction temperature.
Fig. 6 is the change curve of the catalyst denitration efficiency for preparing of embodiment 6 with reaction temperature.
Fig. 7 is the change curve of the catalyst denitration efficiency for preparing of embodiment 7 with reaction temperature.
Five, the specific embodiment
Embodiment 1:Mn1/FA-PG
The preparation of catalyst carrier in the present embodiment:
With the 50g Concave-convex clay rod mix with 100g flyash and stir compound, in compound, adding the 150mL mass concentration is the H of 9-10%
2SO
4Solution, add leave standstill after water stirs 24 hours sample a, amount of water is as the criterion stirring; In sample a, add water and stir, centrifugal back abandoning supernatant, repetitive operation is to supernatant pH=5-6, after the abandoning supernatant sample b; B stirs with sample, leave standstill under the room temperature to put into SET type twin-screw wet method extruding granulator after 48 hours, and be bottom surface diameter 2-3mm through the extrusion aftershaping, the cylindric carrier granular of high 3-5mm; With cylindrical pellet 50 ℃ of dryings 5 hours, then in 105 ℃ of dryings 12 hours sample c, with sample c place 300 ℃ of nitrogen atmospheres down calcining 2 hours catalyst carrier;
The load of catalyst in the present embodiment:
Get the 5g catalyst carrier, after the employing equi-volume impregnating added water, surveying its solid-to-liquid ratio was 1g: 0.4mL; Get the Mn (NO of mass fraction 50%
3)
2Solution 2.9mL wherein contains Mn (NO
3)
22.3g adding distil water is diluted to 28mL, is added to after stirring in the 70g catalyst carrier; Left standstill under the room temperature 48 hours; Then at 70 ℃ of dry 3h, 100 ℃ of dryings 12 hours, place at last under the nitrogen atmosphere in 300 ℃ of calcinings 2 hours Mn1/FA-PG catalyst finished product.
But by the best catalytic reaction temperature of the catalyst of Fig. 1 knowledge capital embodiment preparation is 300 ℃, and denitration efficiency is about 80%.
Embodiment 2:Mn10/FA-PG
The preparation of catalyst carrier in the present embodiment:
With the 50g Concave-convex clay rod mix with 50g flyash and stir compound, in compound, adding the 200mL mass concentration is the H of 9-10%
25O
4Solution, add leave standstill after water stirs 24 hours sample a, amount of water is as the criterion stirring; In sample a, add water and stir, centrifugal back abandoning supernatant, repetitive operation is to supernatant pH=5-6, after the abandoning supernatant sample b; B stirs with sample, leave standstill under the room temperature to put into SET type twin-screw wet method extruding granulator after 50 hours, and be bottom surface diameter 2-3mm through the extrusion aftershaping, the cylindric carrier granular of high 3-5mm; With cylindrical pellet 50 ℃ of dryings 5 hours, then in 105 ℃ of dryings 12 hours sample c, with sample c place 500 ℃ of nitrogen atmospheres down calcining 2 hours catalyst carrier;
The load of catalyst in the present embodiment:
Get the 3g catalyst carrier, after the employing equi-volume impregnating added water, surveying its solid-to-liquid ratio was 1g: 0.55mL; Get the Mn (NO of mass fraction 50%
3)
2Solution 37.1mL wherein contains Mn (NO
3)
229.3g adding distil water is diluted to 49.5mL, is added to after stirring in the 90g catalyst carrier; Left standstill under the room temperature 36 hours; Then at 50 ℃ of dry 5h, 105 ℃ of dryings 12 hours, place at last under the nitrogen atmosphere in 500 ℃ of calcinings 2 hours Mn10/FA-PG catalyst finished product.
But by the best catalytic reaction temperature of the catalyst of Fig. 2 knowledge capital embodiment preparation is 200 ℃, and denitration efficiency is about 90%.
Embodiment 3:Mn5/FA-PG
The preparation of catalyst carrier in the present embodiment:
With the 30g Concave-convex clay rod mix with 50g flyash and stir compound, in compound, adding the 80mL mass concentration is the H of 9-10%
2SO
4Solution, add leave standstill after water stirs 24 hours sample a, amount of water is as the criterion stirring; In sample a, add water and stir, centrifugal back abandoning supernatant, repetitive operation is to supernatant pH=5-6, after the abandoning supernatant sample b; B stirs with sample, leave standstill under the room temperature to put into SET type twin-screw wet method extruding granulator after 60 hours, and be bottom surface diameter 2-3mm through the extrusion aftershaping, the cylindric carrier granular of high 3-5mm; With cylindrical pellet 50 ℃ of dryings 5 hours, then in 105 ℃ of dryings 12 hours sample c, with sample c place 300 ℃ of nitrogen atmospheres down calcining 2 hours catalyst carrier;
The load of catalyst in the present embodiment:
Get the 5g catalyst carrier, after the employing equi-volume impregnating added water, surveying its solid-to-liquid ratio was 1g: 0.52mL; Get the Mn (NO of mass fraction 50%
3)
2Solution 14.4mL wherein contains Mn (NO
3)
211.4g adding distil water is diluted to 36.4mL, is added to after stirring in the 70g catalyst carrier; Left standstill under the room temperature 48 hours; Then at 50 ℃ of dry 5h, 105 ℃ of dryings 12 hours, place at last under the nitrogen atmosphere in 300 ℃ of calcinings 2 hours Mn5/FA-PG catalyst finished product.
But by the best catalytic reaction temperature of the catalyst of Fig. 3 knowledge capital embodiment preparation is 250 ℃, and denitration efficiency is about 90%.
Embodiment 4:Mn7/FA-PG
The preparation of catalyst carrier in the present embodiment:
With the 40g Concave-convex clay rod mix with 60g flyash and stir compound, in compound, adding the 200mL mass concentration is the H of 9-10%
2SO
4Solution, add leave standstill after water stirs 24 hours sample a, amount of water is as the criterion stirring; In sample a, add water and stir, centrifugal back abandoning supernatant, repetitive operation is to supernatant pH=5-6, after the abandoning supernatant sample b; B stirs with sample, leave standstill under the room temperature to put into SET type twin-screw wet method extruding granulator after 72 hours, and be bottom surface diameter 2-3mm through the extrusion aftershaping, the cylindric carrier granular of high 3-5mm; With cylindrical pellet 50 ℃ of dryings 5 hours, then in 105 ℃ of dryings 12 hours sample c, with sample c place 400 ℃ of nitrogen atmospheres down calcining 2 hours catalyst carrier;
The load of catalyst in the present embodiment:
Get the 8g catalyst carrier, after the employing equi-volume impregnating added water, surveying its solid-to-liquid ratio was 1g: 0.5mL; Get the Mn (NO of mass fraction 50%
3)
2Solution 26.0mL wherein contains Mn (NO
3)
220.5g adding distil water is diluted to 45mL, is added to after stirring in the 90g catalyst carrier; Left standstill under the room temperature 48 hours; Then at 50 ℃ of dry 5h, 105 ℃ of dryings 12 hours, place at last under the nitrogen atmosphere in 400 ℃ of calcinings 2 hours Mn7/FA-PG catalyst finished product.
But by the best catalytic reaction temperature of the catalyst of Fig. 4 knowledge capital embodiment preparation is 200 ℃, and denitration efficiency is about 90%.
Embodiment 5:Mn5-Cu5/FA-PG
The preparation of catalyst carrier in the present embodiment:
With the 50g Concave-convex clay rod mix with 50g flyash and stir compound, in compound, adding the 100mL mass concentration is the H of 9-10%
2SO
4Solution, add leave standstill after water stirs 24 hours sample a, amount of water is as the criterion stirring; In sample a, add water and stir, centrifugal back abandoning supernatant, repetitive operation is to supernatant pH=5-6, after the abandoning supernatant sample b; B stirs with sample, leave standstill under the room temperature to put into SET type twin-screw wet method extruding granulator after 84 hours, and be bottom surface diameter 2-3mm through the extrusion aftershaping, the cylindric carrier granular of high 3-5mm; With cylindrical pellet 50 ℃ of dryings 5 hours, then in 105 ℃ of dryings 12 hours sample c, with sample c place 600 ℃ of nitrogen atmospheres down calcining 2 hours catalyst carrier;
The load of catalyst in the present embodiment:
Get the 10g catalyst carrier, after the employing equi-volume impregnating added water, surveying its solid-to-liquid ratio was 1g: 0.55mL; Get the Mn (NO of mass fraction 50%
3)
2Solution 18.5mL wherein contains Mn (NO
3)
214.6g, analyze pure Cu (NO
3)
23H
2O particle 17.02g; Both mix the back adding distil water and are diluted to 49.5mL; Be added to after stirring in the 90g catalyst carrier, left standstill under the room temperature 36 hours, then at 70 ℃ of dry 3h; 120 ℃ of dryings 10 hours, place at last under the nitrogen atmosphere in 600 ℃ of calcinings 2 hours Mn5-Cu5/FA-PG catalyst finished product.
But by the best catalytic reaction temperature of the catalyst of Fig. 5 knowledge capital embodiment preparation is 250 ℃, and denitration efficiency is about 85%.
Embodiment 6:Mn3-Fe0.5/FA-PG
The preparation of catalyst carrier in the present embodiment:
With the 30g Concave-convex clay rod mix with 50g flyash and stir compound, in compound, adding the 80mL mass concentration is the H of 9-10%
2SO
4Solution, add leave standstill after water stirs 24 hours sample a, amount of water is as the criterion stirring; In sample a, add water and stir, centrifugal back abandoning supernatant, repetitive operation is to supernatant pH=5-6, after the abandoning supernatant sample b; B stirs with sample, leave standstill under the room temperature to put into SET type twin-screw wet method extruding granulator after 96 hours, and be bottom surface diameter 2-3mm through the extrusion aftershaping, the cylindric carrier granular of high 3-5mm; With cylindrical pellet 50 ℃ of dryings 5 hours, then in 105 ℃ of dryings 12 hours sample c, with sample c place 300 ℃ of nitrogen atmospheres down calcining 2 hours catalyst carrier;
The load of catalyst in the present embodiment:
Get the 1g catalyst carrier, after the employing equi-volume impregnating added water, surveying its solid-to-liquid ratio was 1g: 0.52mL; Get the Mn (NO of mass fraction 50%
3)
2Solution 8.7mL wherein contains Mn (NO
3)
26.8g, analyze pure FeSO
47H
2O particle 1.75g; Both mix the back adding distil water and are diluted to 36.4mL; Be added to after stirring in the 70g catalyst carrier, left standstill under the room temperature 24 hours, then at 60 ℃ of dry 4h; 100 ℃ of dryings 10 hours, place at last under the nitrogen atmosphere in 300 ℃ of calcinings 2 hours Mn3-Fe0.5/FA-PG catalyst finished product.
But by the best catalytic reaction temperature range of the catalyst of Fig. 6 knowledge capital embodiment preparation is 200-300 ℃, and denitration efficiency is about 90%.
Embodiment 7:Mn5-Ni0.1/FA-PG
The preparation of catalyst carrier in the present embodiment:
With the 50g Concave-convex clay rod mix with 50g flyash and stir compound, in compound, adding the 100mL mass concentration is the H of 9-10%
2SO
4Solution, add leave standstill after water stirs 24 hours sample a, amount of water is as the criterion stirring; In sample a, add water and stir, centrifugal back abandoning supernatant, repetitive operation is to supernatant pH=5-6, after the abandoning supernatant sample b; B stirs with sample, leave standstill under the room temperature to put into SET type twin-screw wet method extruding granulator after 96 hours, and be bottom surface diameter 2-3mm through the extrusion aftershaping, the cylindric carrier granular of high 3-5mm; With cylindrical pellet 50 ℃ of dryings 5 hours, then in 105 ℃ of dryings 12 hours sample c, with sample c place 400 ℃ of nitrogen atmospheres down calcining 2 hours catalyst carrier;
The load of catalyst in the present embodiment:
Get the 1g catalyst carrier, after the employing equi-volume impregnating added water, surveying its solid-to-liquid ratio was 1g: 0.55mL; Get the Mn (NO of mass fraction 50%
3)
2Solution 14.4mL wherein contains Mn (NO
3)
211.4g, analyze pure Ni (NO
3)
26H
2O particle 0.35g; Both mix the back adding distil water and are diluted to 38.5mL; Be added to after stirring in the 70g catalyst carrier, left standstill under the room temperature 24 hours, then at 60 ℃ of dry 4h; 100 ℃ of dryings 10 hours, place at last under the nitrogen atmosphere in 400 ℃ of calcinings 2 hours Mn5-Ni0.1/FA-PG catalyst finished product.
But by the best catalytic reaction temperature range of the catalyst of Fig. 7 knowledge capital embodiment preparation is 250-300 ℃, and denitration efficiency is about 90%.
Claims (3)
1. flyash-attapulgite composite SCR denitrating catalyst is characterized in that: said catalyst is to be catalyst carrier with flyash and attapulgite, the composite of load Mn oxide; Said Mn oxide accounts for the 1-10% of said catalyst carrier quality by the mass percent of manganese;
The divalence nitrate or the divalent sulfur acid salt solution of iron, copper or nickel are added as auxiliary agent, and the mass percent that the addition of said auxiliary agent accounts for catalyst carrier is 0.1-5%;
The mass ratio of Concave-convex clay rod described in the said catalyst carrier and said coal dust ash is 0.5-1;
By mass percentage, the content of attapulgite is not less than 65% in the said Concave-convex clay rod, and the content of dolomite is not more than 10%.
2. the preparation method of the described flyash of claim 1-attapulgite composite SCR denitrating catalyst; It is characterized in that: adopt equi-volume impregnating that catalyst precursor is loaded to the catalyst carrier surface, obtain flyash-attapulgite composite SCR denitrating catalyst after oven dry and the calcining; Said catalyst precursor is major catalyst presoma and co-catalyst presoma; Said major catalyst presoma is Mn (NO
3)
2, divalence nitrate that said co-catalyst presoma is iron, copper, nickel or divalent sulfur hydrochlorate.
3. preparation method according to claim 2 is characterized in that operating according to the following steps:
(1) preparation of catalyst carrier
A, with Concave-convex clay rod mix with flyash and stir compound, in said compound, adding mass concentration is the H of 9-10%
2SO
4Solution, add leave standstill after water stirs 24 hours sample a, amount of water is as the criterion stirring;
Said compound and said H
2SO
4The mass volume ratio of solution is 1g: 1mL or 1g: 2mL;
B, in said sample a, add water and stir, centrifugal back abandoning supernatant, repetitive operation is to supernatant pH=5-6, after the abandoning supernatant sample b;
C, said sample b is stirred, leave standstill 48-96 hour aftershaping under the room temperature and become bottom surface diameter 2-3mm, the cylindrical pellet of high 3-5mm;
D, with said cylindrical pellet 50 ℃ of dryings 5 hours, then in 105 ℃ of dryings 12 hours sample c, with said sample c place nitrogen atmosphere 300-600 ℃ down calcining 2 hours catalyst carrier;
(2) load of catalyst
E, get the 1-10g catalyst carrier, adopt equi-volume impregnating to add water after, survey its solid-to-liquid ratio;
F, the solid-to-liquid ratio that records according to step e take by weighing the catalyst carrier of certain mass and the catalyst precursor of certain volume; Both left standstill 24-48 hour after mixing; Then at 50-70 ℃ of dry 3-5 hour; 100-120 ℃ dry 10-12 hour, place at last under the nitrogen atmosphere in 300-600 ℃ of calcining 2 hours finished product.
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| CN102847543A (en) * | 2012-09-25 | 2013-01-02 | 中国石油化工股份有限公司 | Coal ash-attapulgite iron manganese base low-temperature denitration catalyst, and preparation method thereof |
| CN102935362B (en) * | 2012-11-15 | 2014-08-06 | 合肥工业大学 | Method for improving low-temperature activity of coal ash-attapulgite manganese based selective catalytic reduction (SCR) catalyst |
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| CN104248986B (en) * | 2013-06-28 | 2016-06-29 | 中国石油化工股份有限公司 | The preparation method of the composite mesoporous carrier of spherical attapulgite and loaded catalyst and its preparation method and application and ethyl acetate |
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| CN111672491B (en) * | 2020-06-22 | 2022-07-15 | 山东科技大学 | Impregnated SCR flue gas denitration catalyst carrier prepared from coal slag and preparation method thereof |
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