CN102764671A - Method for preparing denitration catalyst by coal ash - Google Patents
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- CN102764671A CN102764671A CN2012102739019A CN201210273901A CN102764671A CN 102764671 A CN102764671 A CN 102764671A CN 2012102739019 A CN2012102739019 A CN 2012102739019A CN 201210273901 A CN201210273901 A CN 201210273901A CN 102764671 A CN102764671 A CN 102764671A
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Abstract
The invention relates to a method for preparing a denitration catalyst by coal ash. The method for preparing the denitration catalyst by the coal ash includes firstly, collecting the coal ash from a field, grinding the coal ash into fine powder, sieving the fine powder by a 40-mesh sieve, then placing the fine powder in a muffle for calcination, adding the calcined fine powder into diluted hydrochloride acid for pickling after the calcined fine powder is washed, enabling the calcined fine powder to react under the condition that the temperature ranges from 20 DEG C to 50 DEG C and the rotation speed of a rotor ranges from 100r/min to 300r/min, and then separating coal ash solid from acid solution; secondly, uniformly mixing the coal ash treated in the first step with NaOH solution at the solid-solution ratio ranging from 1:1 to 1:10 and calcining the mixture for standby application; thirdly, performing hydrothermal synthesis for the coal ash treated in the second step for 2 to 8 hours, ageing the coal ash for 1 to 4 hours, crystallizing the coal ash for 6 to 24 hours, and washing, filtering and drying a synthesized sample to obtain an amorphous molecular sieve product; fourthly, preparing adhesive and performing extrusion molding for the molecular sieve synthesized by the coal ash; fifthly, preparing dipping solution; and sixthly, dipping the molecular sieve sample obtained in the fourth step, then calcimining the molecular sieve sample and reducing the molecular sieve sample by H2 for 2 to 5 hours to obtain denitration catalyst grains. The molecular sieve catalyst is synthesized by the coal ash. Since a raw material of the molecular sieve catalyst is solid waste discharged from a coal-fired boiler, cost is low and waste resource utilization can be realized.
Description
One, technical field:
What the present invention relates to is that industrial waste gas is handled and the environment protection catalytic field of materials, and what be specifically related to is a kind of method of utilizing the fly-ash Preparation denitrating catalyst.
Two, background technology:
Antipollution importance has been carried as worldwide problem shrilly.Along with development and the growth in the living standard that modern industry is produced, the problem that atmosphere pollution has become people extremely to pay close attention to.NO since the seventies
xAtmosphere polluting problem by pay attention to day by day, it is found that: the injury of health, high-load nitric acid rain, photochemical fog, ozone reduce and some other problem all and low concentration of NO
xRelation is arranged, and its harmfulness much bigger than the original imagination of people.Yet China is coal production in the world and consumption big country, NO in the flue gas that coal burning produces
xDischarge capacity account for total release about 70%, and the trend of cumulative year after year is arranged, therefore, it is very urgent effectively to control in the flue gas discharging of nitrogen oxide, the fume emission in the thermal power plant of especially taking as the leading factor with fire coal.Meanwhile, in the process of fire coal, can produce a large amount of solid waste coal ash, contaminated environment.China still belongs to low-level to utilization of coal ash; Flyash still need be developed and go deep into to utilize significantly; Especially utilize chemical composition wherein; With the high value added product is that the Application and Development that leads is a direction of flyash future development, also is the hot issue that present insider extremely pays close attention to.Therefore, how cost-effective control coal-fired process discharged nitrous oxides is the problem that the coal-fired industry of China presses for solution with the efficient flyash of discarding that utilizes.
At present, the key of denitration method for flue gas is catalyst, and the quality of the performance of catalyst directly influences the effect of denitrating flue gas.At present, the catalyst component of denitrating catalyst all is V mostly
2O
5, it is a kind of extremely toxic substance, can produce harm to human respiratory and skin, in the Catalyst Production process, also can produce pollution.Patent CN1777477 and patent CN1792431 are with V
2O
5-WO
3(MoO
3)/TiO
2Be active component, denitration efficiency is high, is difficult for poisoning, but also has co-catalyst WO
3And MoO
3Cost of material high, problem such as addition is big.This has increased cost to a great extent, hindered should technology further popularization.Therefore, the at a low price synthetic and high catalyst of catalytic efficiency is the key point that addresses this problem.
The patent of at present domestic relevant denitrating catalyst is less.Patent (CN1792431) is to be supporter with the cordierite honeycomb ceramic, with V
2O
5-WO
3/ TiO
2-Al
2O
3Be active component, this catalyst low-temperature activity is high, anti-toxic is good, and not enough is that the catalyst cost is higher, and very high toxicity is arranged.Patent (CN1401416) also is that cordierite honeycomb ceramic is a supporter, and catalyst system and catalyzing is CuO/r-Al2O3, this catalyst environmental protection, catalytic activity height.Not enough is that this catalyst is prone to efflorescence, wears no resistance.
Three, summary of the invention:
The purpose of this invention is to provide a kind of method of utilizing the fly-ash Preparation denitrating catalyst, the high problem of cost when the method that it is used to solve the existing preparation denitrating catalyst prepares denitrating catalyst.
The technical solution adopted for the present invention to solve the technical problems is: this method of utilizing the fly-ash Preparation denitrating catalyst:
One, from collection in worksite flyash, grinds to form fine powder, excessively behind 40 mesh sieves; Get the flyash fine powder and place in the Muffle furnace, at 600 ℃ of-900 ℃ of temperature lower calcination 6h-10h, after temperature is 20 ℃-80 ℃ following washing 1h-4h; The watery hydrochloric acid or the dilute sulfuric acid that add 2mol/L-4mol/L carry out pickling, and the solid-to-liquid ratio of flyash and described acid solution is 1:10-1:15, is 20-50 ℃ in temperature; React under the condition of rotor 100r/min-300r/min, reaction 2h-10h separates acid solution then with the flyash solid-liquid; Separate the back solid and be washed with distilled water to neutrality, drying for standby;
Two, flyash that will be after step 1 is handled and mass fraction are that 40% NaOH solution mixes with solid-to-liquid ratio 1:1-1:10, and it is subsequent use behind 450 ℃ of-600 ℃ of temperature lower calcination 1h-2h, to be taken out to 25 ℃ of room temperatures;
Three, the flyash of handling through step 2 is 90 ℃-100 ℃ in temperature; Hydro-thermal Synthetic 2 h-8h under synthesis pressure 0.1Mpa-1.0Mpa; Aging 1-4h at 95 ℃ of-120 ℃ of following crystallization 6h-24h, uses the distilled water washing and filtering with synthetic sample under 20 ℃ of-50 ℃ of temperature; Drying promptly gets unformed zeolite product;
Four, to use mass fraction be 5% nitric acid and mass fraction is that 5% boehmite makes adhesive with 1:1-5:1, and the molecular sieve extrusion modling with flyash synthesizes after the moulding, is broken into required form and size as required;
Five, preparation dipping solution; Dipping solution is formed by a kind of or any several kinds of mixing in mass fraction is the Ce salting liquid of 1%-20%, Mg salting liquid that mass fraction is 1%-20%, mass fraction is 1%-20% La salting liquid, the Cu salting liquid that mass fraction is 1%-20%; The mass fraction of the solution for preparing is 20%; Wherein the volume of each metal salt solution equates that the volume of mixed liquor calculates according to prepared molecular sieve saturated extent of adsorption size during mixed preparing;
Six, use sieve sample with the step 4 gained to be immersed in 20h-30h in the solution of step 5 preparation, dipping drains the residual solution in the molecular sieve after finishing, and drying at room temperature 24h passes through 500-850 ℃ of roasting then, uses H
2Make the denitrating catalyst particle at 300-450 ℃ of reductase 12-5h.
Ce salt is a kind of or any several kinds mixture in cerous nitrate, cerous sulfate, cerium chloride, the cerium oxalate in the such scheme.
Mg salt is a kind of or any several kinds mixture in magnesium nitrate, magnesium sulfate, the magnesium chloride in the such scheme.
Cu salt is a kind of or any several kinds mixture in copper nitrate, copper sulphate, the copper chloride in the such scheme.
La salt is a kind of or any several kinds mixture in lanthanum nitrate, lanthanum chloride, the lanthanum sulfate in the such scheme.
Beneficial effect:
1, the present invention utilizes the flyash synthetic zeolite catalyst, and raw material is the solid waste of discharged from coal-fired boiler, and is with low cost, wide material sources.Flyash is carried out processed both can reduce the problem of environmental pollution that flyash brings, can also realize utilization of waste as resource simultaneously, have remarkable social benefit and economic benefit.
2, the present invention compares with existing denitration, and this catalyst can make NO in the gas
xConcentration reduce 70%-95%.
3, specific area of the present invention is bigger, Heat stability is good, and denitration efficiency is high.
4, the present invention can extract useful element wherein, as the source of chemical raw material to the liquid that the classification preliminary treatment of flyash obtains.Increased the added value of flyash.
5, according to China's denitrating flue gas present situation and from the angle of Ash Utilization utilization; We are the feedstock production denitrating catalyst with flyash; Reduced the content of coal-fired plant flue gas nitrogen oxide on the one hand, also an important channel is provided on the other hand for utilization of coal ash and processing.
Four, description of drawings:
Fig. 1 is a process flow diagram of the present invention.
Five, the specific embodiment:
Below in conjunction with accompanying drawing the present invention is done further explanation:
Embodiment 1:
In conjunction with shown in Figure 1, this method of utilizing the fly-ash Preparation denitrating catalyst:, grind to form segmentation from collection in worksite flyash; After crossing 40 mesh sieves, get 50g flyash and place in the Muffle furnace, at 600 ℃ of temperature lower calcination 10h; Behind the washing 2.5h, behind the filtration drying, the adding volume is that the watery hydrochloric acid of the 2mol/L of 500ml is washed under temperature is 60 ℃; The two is 50 ℃ in temperature, reacts reaction 6h under the condition of rotor 100r/min; Then acid solution is separated with the flyash solid-liquid, separate the back solid and be washed with distilled water to neutrality, drying for standby.With the above-mentioned flyash after handling and mass fraction is that 40% NaOH solution mixes with solid-to-liquid ratio 1:5, and it is subsequent use behind 450 ℃ of temperature lower calcination 1h, to be taken out to room temperature.Flyash after then will calcining is 90 ℃ in temperature, hydro-thermal Synthetic 2 h under the synthesis pressure 0.9Mpa, and aging 1h at 95 ℃ of following crystallization 6h, uses the distilled water washing and filtering with synthetic sample under 25 ℃ of temperature, and drying promptly gets unformed zeolite product; To use mass fraction be 5% nitric acid and mass fraction is that 5% boehmite makes adhesive with 3:1, with flyash synthesize molecular sieve molded, after the moulding, being broken into diameter as required is the 10mm spheric granules.Spheric granules after the moulding fragmentation is immersed in 24h in the 500ml mixed liquor of lanthanum salt preparation of mantoquita, mass fraction 5% of magnesium salts that mass fraction is 5% cerium salt, mass fraction 5%, mass fraction 5%; Wherein four kinds of metal salt solutions of preparation are with volume ratio 1:1:1:1; Dipping drains the residual solution in the molecular sieve after finishing; Drying at room temperature 24h through 600 ℃ of roastings, uses H then
2Make the denitrating catalyst product at 300 ℃ of reductase 12 h.
In sum, the present invention proposes a kind of method of utilizing the fly-ash Preparation denitrating catalyst, at first flyash is carried out high-temperature calcination and goes out unburnt organic matter, then through classification preliminary treatment such as washing, pickling, in order to remove impurity in the flyash (like Fe
2O
3, MgO, K
2O, Na
2O, CaO).For the flyash after handling, adopt the synthetic method synthesis of molecular sieve of alkali fusion one hydro-thermal, the denitrating catalyst of cheap metal active components such as excessive then immersion process for preparing load C e, Mg, Cu, La.
The excessive infusion process that the present invention adopted; At first to analyze synthetic molecule sieve aperture pore structure and specific area; Measure the ability that carrier sucks solution in advance, calculate and add the maceration extract of excessive concentrations then, utilize the synthetic molecular sieve of flyash and the concentration difference of dipping solution; Make active component get into molecular sieve pore passage fast, and be adsorbed on the carrier in a large number.
The analog detection test that utilizes embodiment 1 to carry out:
In a mould flue gas device, put into the out of stock catalyst of embodiment 1 preparation, simulate its distribution situation simultaneously, under inert atmosphere, N is used in pilot production
2Mist simulated flue gas with NO.Total gas flow rate is 2.5L/min-5L/min, and NO concentration is 300ppm-500ppm, detects with the concentration of flue gas analyzer to NO in the gas, and NO reduces 70%-80%.
Embodiment 2:
This method of utilizing the fly-ash Preparation denitrating catalyst: from collection in worksite flyash, grind to form segmentation, excessively behind 40 mesh sieves; Get 50g flyash and place in the Muffle furnace, at 700 ℃ of temperature lower calcination 8h, after temperature is 20 ℃ of following washing 4h; Behind the filtration drying, the adding volume is that the watery hydrochloric acid of the 2mol/L of 600ml is washed, and the two is 40 ℃ in temperature; React under the condition of rotor 200r/min, reaction 2h separates acid solution then with the flyash solid-liquid; Separate the back solid and be washed with distilled water to neutrality, drying for standby.With the above-mentioned flyash after handling and mass fraction is that 40% NaOH solution mixes with solid-to-liquid ratio 1:1, and it is subsequent use behind 600 ℃ of temperature lower calcination 2h, to be taken out to room temperature.Flyash after then will calcining is 100 ℃ in temperature, the synthetic 4h of hydro-thermal under the synthesis pressure 0.5Mpa, and aging 2h at 110 ℃ of following crystallization 24h, uses the distilled water washing and filtering with synthetic sample under 40 ℃ of temperature, and drying promptly gets unformed zeolite product; To use mass fraction be 5% nitric acid and mass fraction is that 5% boehmite makes adhesive with 1:1, with flyash synthesize molecular sieve molded, after the moulding, being broken into diameter as required is the 10mm spheric granules.Spheric granules after the moulding fragmentation is immersed in 20h in the 500ml mixed liquor of mantoquita, the preparation of mass fraction 6.67% lanthanum salt of magnesium salts, the mass fraction 6.67 of mass fraction 6.67%; Wherein three kinds of metal salt solutions of preparation are with volume ratio 1:1:1; Dipping drains the residual solution in the molecular sieve after finishing; Drying at room temperature 24h through 500 ℃ of roastings, uses H then
2Make the denitrating catalyst product at 450 ℃ of reduction 5h.
The analog detection test that utilizes embodiment 2 to carry out:
In a mould flue gas device, put into the out of stock catalyst of embodiment 2 preparations, simulate its distribution situation simultaneously, under inert atmosphere, N is used in pilot production
2Mist simulated flue gas with NO.Total gas flow rate is 8L/min-10L/min, and NO concentration is 500ppm-800ppm, detects with the concentration of flue gas analyzer to NO in the gas, and NO reduces 85-95%.
Embodiment 3:
This method of utilizing the fly-ash Preparation denitrating catalyst: from collection in worksite flyash, grind to form segmentation, excessively behind 40 mesh sieves; Get 50g flyash and place in the Muffle furnace, at 900 ℃ of temperature lower calcination 6h, after temperature is 80 ℃ of following washing 1h; Behind the filtration drying, adding volume is the dilute sulfuric acid dip of the 4mol/L of 750ml, and the two is 20 ℃ in temperature; React under the condition of rotor 300r/min, reaction 10h separates acid solution then with the flyash solid-liquid; Separate the back solid and be washed with distilled water to neutrality, drying for standby.With the above-mentioned flyash after handling and mass fraction is that 40% NaOH solution mixes with solid-to-liquid ratio 1:10, and it is subsequent use behind 500 ℃ of temperature lower calcination 1.5h, to be taken out to room temperature.Flyash after then will calcining is 95 ℃ in temperature, the synthetic 8h of hydro-thermal under the synthesis pressure 0.2Mpa, and aging 4h at 120 ℃ of following crystallization 18h, uses the distilled water washing and filtering with synthetic sample under 50 ℃ of temperature, and drying promptly gets unformed zeolite product; To use mass fraction be 5% nitric acid and mass fraction is that 5% boehmite makes adhesive with 5:1, with flyash synthesize molecular sieve molded, after the moulding, being broken into diameter as required is the 10mm spheric granules.Spheric granules after the moulding fragmentation is immersed in 24h in the 500ml mixed liquor of mantoquita preparation of magnesium salts that mass fraction is 6.67% cerium salt, mass fraction 6.67%, mass fraction 6.67%; Wherein three kinds of metal salt solutions of preparation are with volume ratio 1:1:1; Dipping drains the residual solution in the molecular sieve after finishing; Drying at room temperature 24h through 850 ℃ of roastings, uses H then
2Make the denitrating catalyst product at 400 ℃ of reduction 3h.
Embodiment 4:
This method of utilizing the fly-ash Preparation denitrating catalyst: from collection in worksite flyash, grind to form segmentation, excessively behind 40 mesh sieves; Get 60g flyash and place in the Muffle furnace, at 900 ℃ of temperature lower calcination 6h, after temperature is 80 ℃ of following washing 1h; Behind the filtration drying, adding volume is the dilute sulfuric acid dip of the 4mol/L of 750ml, and the two is 20 ℃ in temperature; React under the condition of rotor 300r/min, reaction 10h separates acid solution then with the flyash solid-liquid; Separate the back solid and be washed with distilled water to neutrality, drying for standby.With the above-mentioned flyash after handling and mass fraction is that 40% NaOH solution mixes with solid-to-liquid ratio 1:10, and it is subsequent use behind 500 ℃ of temperature lower calcination 1.5h, to be taken out to room temperature.Flyash after then will calcining is 95 ℃ in temperature, the synthetic 8h of hydro-thermal under the synthesis pressure 0.2Mpa, and aging 4h at 120 ℃ of following crystallization 18h, uses the distilled water washing and filtering with synthetic sample under 50 ℃ of temperature, and drying promptly gets unformed zeolite product; To use mass fraction be 5% nitric acid and mass fraction is that 5% boehmite makes adhesive with 5:1, with flyash synthesize molecular sieve molded, after the moulding, being broken into diameter as required is the 10mm spheric granules.Spheric granules after the moulding fragmentation is immersed in 24h in the 500ml solution that mass fraction is the preparation of 20% cerium salt, and dipping drains the residual solution in the molecular sieve after finishing, and drying at room temperature 24h through 850 ℃ of roastings, uses H then
2Make the denitrating catalyst product at 400 ℃ of reduction 3h.
Embodiment 5:
This method of utilizing the fly-ash Preparation denitrating catalyst: from collection in worksite flyash, grind to form segmentation, excessively behind 40 mesh sieves; Get 50g flyash and place in the Muffle furnace, at 600 ℃ of temperature lower calcination 10h, after temperature is 60 ℃ of following washing 2.5h; Behind the filtration drying, the adding volume is that the watery hydrochloric acid of the 2mol/L of 500ml is washed, and the two is 50 ℃ in temperature; React under the condition of rotor 100r/min, reaction 6h separates acid solution then with the flyash solid-liquid; Separate the back solid and be washed with distilled water to neutrality, drying for standby.With the above-mentioned flyash after handling and mass fraction is that 40% NaOH solution mixes with solid-to-liquid ratio 1:5, and it is subsequent use behind 450 ℃ of temperature lower calcination 1h, to be taken out to room temperature.Flyash after then will calcining is 90 ℃ in temperature, hydro-thermal Synthetic 2 h under the synthesis pressure 0.9Mpa, and aging 1h at 95 ℃ of following crystallization 6h, uses the distilled water washing and filtering with synthetic sample under 25 ℃ of temperature, and drying promptly gets unformed zeolite product; To use mass fraction be 5% nitric acid and mass fraction is that 5% boehmite makes adhesive with 3:1, with flyash synthesize molecular sieve molded, after the moulding, being broken into diameter as required is the 10mm spheric granules.Spheric granules after the moulding fragmentation is immersed in 24h in the 500ml solution of magnesium salts of mass fraction 20%, dipping drains the residual solution in the molecular sieve after finishing, and drying at room temperature 24h through 600 ℃ of roastings, uses H then
2Make the denitrating catalyst product at 300 ℃ of reductase 12 h.
Embodiment 6:
This method of utilizing the fly-ash Preparation denitrating catalyst: from collection in worksite flyash, grind to form segmentation, excessively behind 40 mesh sieves; Get 50g flyash and place in the Muffle furnace, at 700 ℃ of temperature lower calcination 8h, after temperature is 20 ℃ of following washing 4h; Behind the filtration drying, the adding volume is that the watery hydrochloric acid of the 2mol/L of 600ml is washed, and the two is 40 ℃ in temperature; React under the condition of rotor 200r/min, reaction 2h separates acid solution then with the flyash solid-liquid; Separate the back solid and be washed with distilled water to neutrality, drying for standby.With the above-mentioned flyash after handling and mass fraction is that 40% NaOH solution mixes with solid-to-liquid ratio 1:1, and it is subsequent use behind 600 ℃ of temperature lower calcination 2h, to be taken out to room temperature.Flyash after then will calcining is 100 ℃ in temperature, the synthetic 4h of hydro-thermal under the synthesis pressure 0.5Mpa, and aging 2h at 110 ℃ of following crystallization 24h, uses the distilled water washing and filtering with synthetic sample under 40 ℃ of temperature, and drying promptly gets unformed zeolite product; To use mass fraction be 5% nitric acid and mass fraction is that 5% boehmite makes adhesive with 1:1, with flyash synthesize molecular sieve molded, after the moulding, being broken into diameter as required is the 10mm spheric granules.Spheric granules after the moulding fragmentation is immersed in 20h in the 500ml solution of mantoquita preparation of mass fraction 20%, dipping drains the residual solution in the molecular sieve after finishing, and drying at room temperature 24h through 500 ℃ of roastings, uses H then
2Make the denitrating catalyst product at 450 ℃ of reduction 5h.
Embodiment 7:
This method of utilizing the fly-ash Preparation denitrating catalyst: from collection in worksite flyash, grind to form segmentation, excessively behind 40 mesh sieves; Get 50g flyash and place in the Muffle furnace, at 700 ℃ of temperature lower calcination 8h, after temperature is 20 ℃ of following washing 4h; Behind the filtration drying, the adding volume is that the watery hydrochloric acid of the 2mol/L of 600ml is washed, and the two is 40 ℃ in temperature; React under the condition of rotor 200r/min, reaction 2h separates acid solution then with the flyash solid-liquid; Separate the back solid and be washed with distilled water to neutrality, drying for standby.With the above-mentioned flyash after handling and mass fraction is that 40% NaOH solution mixes with solid-to-liquid ratio 1:1, and it is subsequent use behind 600 ℃ of temperature lower calcination 2h, to be taken out to room temperature.Flyash after then will calcining is 100 ℃ in temperature, the synthetic 4h of hydro-thermal under the synthesis pressure 0.5Mpa, and aging 2h at 110 ℃ of following crystallization 24h, uses the distilled water washing and filtering with synthetic sample under 40 ℃ of temperature, and drying promptly gets unformed zeolite product; To use mass fraction be 5% nitric acid and mass fraction is that 5% boehmite makes adhesive with 1:1, with flyash synthesize molecular sieve molded, after the moulding, being broken into diameter as required is the 10mm spheric granules.Spheric granules after the moulding fragmentation is immersed in 20h in the 500ml mixed liquor of mantoquita, mass fraction 10% lanthanum salt preparation of mass fraction 10%; Wherein two kinds of metal salt solutions of preparation are with volume ratio 1:1; Dipping drains the residual solution in the molecular sieve after finishing; Drying at room temperature 24h through 500 ℃ of roastings, uses H then
2Make the denitrating catalyst product at 450 ℃ of reduction 5h.
Claims (5)
1. method of utilizing the fly-ash Preparation denitrating catalyst is characterized in that: this method of utilizing the fly-ash Preparation denitrating catalyst:
One, from collection in worksite flyash, grinds to form fine powder, excessively behind 40 mesh sieves; Get the flyash fine powder and place in the Muffle furnace, at 600 ℃ of-900 ℃ of temperature lower calcination 6h-10h, after temperature is 20 ℃-80 ℃ following washing 1h-4h; The watery hydrochloric acid or the dilute sulfuric acid that add 2mol/L-4mol/L carry out pickling, and the solid-to-liquid ratio of flyash and described acid solution is 1:10-1:15, is 20-50 ℃ in temperature; React under the condition of rotor 100r/min-300r/min, reaction 2h-10h separates acid solution then with the flyash solid-liquid; Separate the back solid and be washed with distilled water to neutrality, drying for standby;
Two, flyash that will be after step 1 is handled and mass fraction are that 40% NaOH solution mixes with solid-to-liquid ratio 1:1-1:10, and it is subsequent use behind 450 ℃ of-600 ℃ of temperature lower calcination 1h-2h, to be taken out to room temperature;
Three, the flyash of handling through step 2 is 90 ℃-100 ℃ in temperature; Hydro-thermal Synthetic 2 h-8h under synthesis pressure 0.1Mpa-1.0Mpa; Aging 1-4h at 95 ℃ of-120 ℃ of following crystallization 6h-24h, uses the distilled water washing and filtering with synthetic sample under 20 ℃ of-50 ℃ of temperature; Drying promptly gets unformed zeolite product;
Four, to use mass fraction be 5% nitric acid and mass fraction is that 5% boehmite makes adhesive with 1:1-5:1, and the molecular sieve extrusion modling with flyash synthesizes after the moulding, is broken into required form and size as required;
Five, preparation dipping solution; Dipping solution is formed by a kind of or any several kinds of mixing in mass fraction is the Ce salting liquid of 1%-20%, Mg salting liquid that mass fraction is 1%-20%, mass fraction is 1%-20% La salting liquid, the Cu salting liquid that mass fraction is 1%-20%; The mass fraction of the solution for preparing is 20%; Wherein the volume of each metal salt solution equates that the volume of mixed liquor calculates according to prepared molecular sieve saturated extent of adsorption size during mixed preparing;
Six, use sieve sample with the step 4 gained to be immersed in 20h-30h in the solution of step 5 preparation, dipping drains the residual solution in the molecular sieve after finishing, and drying at room temperature 24h passes through 500-850 ℃ of roasting then, uses H
2Make the denitrating catalyst particle at 300-450 ℃ of reductase 12-5h.
2. the method for utilizing the fly-ash Preparation denitrating catalyst according to claim 1 is characterized in that: described Ce salt is a kind of or any several kinds mixture in cerous nitrate, cerous sulfate, cerium chloride, the cerium oxalate.
3. the method for utilizing the fly-ash Preparation denitrating catalyst according to claim 1 is characterized in that: described Mg salt is a kind of or any several kinds mixture in magnesium nitrate, magnesium sulfate, the magnesium chloride.
4. the method for utilizing the fly-ash Preparation denitrating catalyst according to claim 1 is characterized in that: described Cu salt is a kind of or any several kinds mixture in copper nitrate, copper sulphate, the copper chloride.
5. the method for utilizing the fly-ash Preparation denitrating catalyst according to claim 1 is characterized in that: described La salt is a kind of or any several kinds mixture in lanthanum nitrate, lanthanum chloride, the lanthanum sulfate.
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| CN110589851B (en) * | 2018-06-12 | 2023-03-31 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve, copper-based SAPO-34 denitration catalyst, preparation method and application thereof, and denitration method |
| CN110586178B (en) * | 2018-06-12 | 2023-03-03 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve and Cu/SAPO-34 denitration catalyst, preparation method and application thereof, and denitration method |
| CN113398980B (en) * | 2021-06-15 | 2022-07-15 | 东北大学 | Coal ash based X zeolite-TiO2Preparation method of composite photocatalyst |
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| CN113649061A (en) * | 2021-08-25 | 2021-11-16 | 华能(福建漳州)能源有限责任公司 | Method for synthesizing denitration catalyst by coal-fired power plant fly ash self-digestion |
| CN113908693A (en) * | 2021-09-14 | 2022-01-11 | 安徽元琛环保科技股份有限公司 | Method for preparing catalyst coating slurry by regenerating and blowing ash of waste SCR catalyst and application thereof |
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| CN113976095A (en) * | 2021-11-29 | 2022-01-28 | 刘磊 | Preparation method of waste polymethyl methacrylate catalytic cracking catalyst |
| CN115532278A (en) * | 2022-09-23 | 2022-12-30 | 深圳能源环保股份有限公司 | Method for preparing denitration catalyst by modifying waste incineration fly ash and denitration catalyst |
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| CN116328854A (en) * | 2023-02-21 | 2023-06-27 | 山东科技大学 | Preparation method and application of catalyst for preparing oil by pyrolysis of waste plastics |
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