CN114345102B - Composition with denitration function, preparation method and denitration method - Google Patents
Composition with denitration function, preparation method and denitration method Download PDFInfo
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Abstract
The invention relates to the technical field of environmental protection and catalysis, and discloses a composition with a denitration function, a preparation method and a denitration method. The composition comprises organic matters, activated carbon, organic acid, calcium-containing inorganic matters and optional auxiliary agents, wherein the organic matters are selected from at least one of alkanes with carbon atoms more than 5, alkenes with carbon atoms more than 5 and low-carbon monohydric alcohols. The denitration method includes contacting the composition with flue gas. The composition with the denitration function has high denitration efficiency, and compared with an amino denitration agent, the composition with the denitration function has no secondary pollution and is not easy to volatilize.
Description
Technical Field
The invention relates to the technical field of environmental protection and catalysis, and particularly relates to a composition with a denitration function, a preparation method and a denitration method.
Background
Nitrogen oxides (NOx) are one of the major atmospheric pollutants, and emission into the atmosphere causes environmental problems such as acid rain, photochemical smog, and the like. The national standard stipulates that the NOx emission of the coal-fired boiler is not higher than 50mg/Nm 3 In order to realize the ultra-low emission of NOx, a flue gas denitration technology is required. The main denitration methods at present are the SCR method (selective catalytic reduction method) and the SNCR method (selective non-catalytic reduction method).
The reducing agent used in both SCR and SNCR technologies is ammonia, liquid ammonia or urea. Ammonia water and liquid ammonia encounter various problems in use, such as high cost, poor safety, flammability and explosiveness, and are listed as dangerous chemicals by the state; the cigarette is toxic, harmful and has strong pungent smell, the human body is easy to hurt the human organs after inhaling the cigarette, and the environmental pollution is easy to be caused due to high ammonia escape property; the denitration efficiency is low; the transportation is difficult, and the special tank car is required to transport for a long distance. Urea is combustible in open fire and high heat, and toxic gas is decomposed at high temperature. The investment and operation cost of SCR is high, ammonia escapes, and the smoke gas is difficult to reach the standard and is discharged under the ultra-low load; the SNCR has the advantages of small investment and short construction period, but the denitration efficiency is still low at present.
CN201610329778.6 discloses a method for preparing a composite denitration agent by using a waste organic solvent, which has high denitration efficiency, but still needs an amino denitration agent, and inevitably has the problems of transportation and storage of the amino denitration agent, secondary pollution and the like.
CN201710421566.5 discloses an environment-friendly low-temperature composite denitration agent for combustion flue gas and a preparation method thereof, wherein the required raw materials need urea besides organic alcohol and organic amine, and the defect of transportation and storage of the urea still exists.
Therefore, the development of a safe, efficient and environment-friendly SNCR organic denitration agent is needed.
Disclosure of Invention
The invention aims to solve the problems that the existing denitration agent is low in denitration efficiency, narrow in denitration temperature window, ammonia escapes when ammonia is excessively sprayed, and the like, and provides a composition with a denitration function, a preparation method and a denitration method.
In order to achieve the above object, a first aspect of the present invention provides a composition having a denitration function, the composition including an organic substance, activated carbon, an organic acid, a calcium-containing inorganic substance, and optionally an auxiliary agent, wherein the organic substance is at least one selected from the group consisting of an alkane having more than 5 carbon atoms, an alkene having more than 5 carbon atoms, and a lower monohydric alcohol.
In a second aspect, the present invention provides a method of denitration comprising contacting the composition of the first aspect with flue gas.
Preferably, the temperature of the contacting is 650-1000 ℃.
Preferably, when the flow rate of the flue gas is 14000m 3 In terms of/h, the composition is used in an amount of 80 to 200L/h, more preferably 120 to 160L/h.
Preferably, the composition is used in an amount of 6 to 10L per 100g of NOx in the flue gas.
Preferably, the content of NOx in the smoke is 50-200mg/Nm 3 More preferably 100 to 150mg/Nm 3 。
Compared with the prior art, the invention has the following beneficial effects:
(1) The composition with the denitration function has high denitration efficiency, and when the composition is used for denitration by an SNCR (selective non-catalytic reduction) method, the denitration efficiency can exceed 75 percent, and deep denitration can be realized.
(2) Compared with an amino denitration agent, the composition with the denitration function has no secondary pollution and is not easy to volatilize.
(3) The composition with the denitration function has higher safety, is convenient to transport and store, and does not have the danger of explosion.
(4) The composition with the denitration function can release part of heat during denitration, and is beneficial to reducing energy consumption.
(5) The composition with the denitration function can also remove SO in flue gas 2 。
(6) The composition having a denitration function of the present invention has low corrosiveness as compared with an amino-based denitration agent.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a composition with a denitration function, which comprises an organic matter, activated carbon, an organic acid, a calcium-containing inorganic matter and an optional auxiliary agent, wherein the organic matter is selected from at least one of alkane with the carbon number more than 5, alkene with the carbon number more than 5 and lower monohydric alcohol.
According to the present invention, the weight ratio of the organic material, the activated carbon, the organic acid, the calcium-containing inorganic material and the auxiliary agent may be selected within a wide range, but in order to improve the denitration efficiency of the composition, it is preferable that the content of the activated carbon is 15 to 25g, preferably 18 to 21g, the content of the organic acid is 5 to 100g, preferably 8 to 60g, the content of the calcium-containing inorganic material is 0.01 to 1g, preferably 0.05 to 0.11g, and the amount of the auxiliary agent is 0 to 1g, preferably 0.2 to 0.6g, per 100g of the organic material.
In the present invention, each component in the composition may be stored independently or may be stored after being mixed in a certain ratio.
According to the present invention, preferably, the alkane having carbon number greater than 5 is selected from at least one of hexane, cyclohexane, heptane, cycloheptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane and heptadecane.
According to the present invention, preferably, the olefin having a carbon number of more than 5 is selected from at least one of 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene.
According to the present invention, preferably, the lower monohydric alcohol has 1 to 5 carbon atoms; more preferably, the lower monohydric alcohol is selected from at least one of methanol, ethanol, propanol, and butanol.
According to the invention, the activated carbon can be selected within a wide range, preferably the activated carbon has a particle size of less than 30 μm, preferably 1-25 μm, more preferably 5-10 μm, and a specific surface area of more than 1200g/m 2 Preferably 1250 to 3000g/m 2 More preferably 1500 to 2000g/m 2 。
According to the present invention, the kind of the auxiliary agent is not particularly limited as long as it can promote the composition to form multiple active sites and groups to achieve a catalytic denitration effect, and preferably, the auxiliary agent is a water-soluble salt of the ia metal, and more preferably, the auxiliary agent is sodium chloride and/or potassium chloride.
According to the invention, preferably, the weight ratio of sodium chloride to potassium chloride is 1:0.5-2.
According to the invention, preferably, the organic acid is selected from monobasic and/or dibasic acids.
According to the present invention, the kind of the monobasic acid is not particularly limited, and preferably, the carbon number of the monobasic acid is 1 to 10; more preferably, the monobasic acid is selected from at least one of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid and benzoic acid.
According to the present invention, the kind of the dibasic acid is not particularly limited, and preferably, the number of carbon atoms of the dibasic acid is 1 to 10; more preferably, the dibasic acid is selected from at least one of adipic acid, oxalic acid, malonic acid, succinic acid, maleic acid and tartaric acid.
According to the present invention, preferably, the calcium-containing inorganic substance is at least one of calcium hydroxide, calcium chloride and calcium nitrate, and more preferably calcium hydroxide.
According to the invention, the weight ratio of the organic acid to the calcium-containing mineral is preferably between 100 and 600.
According to the present invention, in order to mix the components of the composition more uniformly so as to facilitate the denitration function, the composition preferably further comprises a solvent, wherein the solvent comprises water and/or benzene series; more preferably, the benzene series is benzene and/or toluene.
According to the invention, the water content of the composition is preferably between 5 and 50% by weight, preferably between 20 and 41% by weight.
According to the invention, the benzene series is preferably present in the composition in an amount of 0 to 5% by weight, preferably 0.8 to 3% by weight.
In the present invention, the inorganic substance containing calcium may react with part of the organic acid to form organic calcium, for example: at least one of calcium formate, calcium acetate, calcium propionate, calcium butyrate, calcium caprylate, calcium benzoate, calcium adipate, calcium oxalate, calcium malonate, calcium succinate, calcium maleate and calcium tartrate. At high temperature, the generated organic calcium interacts with organic matters, residual organic acid and active carbon to remove NOx in the flue gas. The organic calcium generated by the reaction of the inorganic substance containing calcium and part of the organic acid can be replaced by the purchased organic calcium, but in consideration of cost, the inorganic substance containing calcium and the organic acid are used for preparing the organic calcium.
In the present invention, there is no particular requirement for the preparation of the composition, and the respective components may be mixed uniformly. In a preferred embodiment of the present invention, the present invention further provides a method for preparing the composition having a denitration function according to the first aspect, the method comprising first mixing an organic material, an organic acid and a calcium-containing inorganic material, and then second mixing the product of the first mixing with activated carbon and optionally an auxiliary agent.
The organic matter is at least one of alkane with the carbon number more than 5, alkene with the carbon number more than 5 and low-carbon monohydric alcohol. The specific selection of each component is as before, and is not described herein again.
According to the preparation method of the composition with a denitration function, the first mixing time is preferably 30-60min, and the temperature is preferably 15-30 ℃.
According to the preparation method of the composition having a denitration function of the present invention, preferably, the second mixing time is 60 to 90min, and the temperature is 15 to 30 ℃.
According to the preparation method of the composition with a denitration function, preferably, the organic matter is first mixed with organic acid and calcium-containing inorganic matter in the form of solution, the mass fraction of the organic matter solution is more than 90wt%, preferably 90-99wt%, and the solvent in the organic matter solution is water and/or benzene series; more preferably, the benzene series is benzene and/or toluene.
According to the preparation method of the composition with a denitration function, when the organic matter in the organic matter solution is selected from the lower monohydric alcohols, the solvent in the organic matter solution is preferably water; and when the organic matters in the organic matter solution are selected from alkanes with more than 5 carbon atoms and/or alkenes with more than 5 carbon atoms, the solvent in the organic matter solution is benzene series.
According to the preparation method of the composition having a denitration function of the present invention, preferably, the calcium-containing inorganic substance is reacted with an organic acid in the form of a solution, and the organic acid is reacted with the calcium-containing inorganic substance in the form of a solution; more preferably, the mass fraction of the organic acid solution is more than 10wt%, and further preferably 20 to 95wt%; more preferably, the mass fraction of the calcium-containing inorganic substance solution is 0.01 to 20wt%, preferably 0.1 to 1wt%, and even more preferably, the calcium-containing inorganic substance solution is a saturated solution of calcium hydroxide, and the mass fraction of calcium hydroxide in the saturated solution of calcium hydroxide is 0.16wt%.
According to the preparation method of the composition having a denitration function of the present invention, preferably, the calcium-containing inorganic substance is at least one of calcium hydroxide, calcium chloride and calcium nitrate, and more preferably, calcium hydroxide.
According to the preparation method of the composition with a denitration function, the auxiliary agent is preferably mixed with the first mixed product and the activated carbon in a second mixing mode in the form of a solution, the mass fraction of the auxiliary agent solution is 1-15wt%, preferably 5-12wt%, and the solvent in the auxiliary agent solution is water.
According to the preparation method of the composition having a denitration function of the present invention, preferably, the carbon number of the monoacid is 1 to 10; more preferably, the monobasic acid is selected from at least one of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid and benzoic acid.
According to the preparation method of the composition having a denitration function of the present invention, preferably, the number of carbon atoms of the dibasic acid is 1 to 10; more preferably, the dibasic acid is selected from at least one of adipic acid, oxalic acid, malonic acid, succinic acid, maleic acid and tartaric acid.
In a second aspect, the present invention provides a method of denitration comprising contacting the composition of the first aspect with flue gas.
According to the invention, the temperature of the contact is preferably between 650 and 1000 ℃.
According to the invention, preferably, when the flow rate of the flue gas is 14000m 3 In the case of the/h, the compositions are used in amounts of from 80 to 200L/h, more preferably from 120 to 160L/h.
According to the invention, the composition is preferably used in an amount of 6 to 10L per 100g of NOx in the fumes.
According to the invention, preferably, the content of NOx in the flue gas is 50-200mg/Nm 3 More preferably 100 to 150mg/Nm 3 。
The present invention will be described in detail below by way of examples. In the following examples of the present invention, the following examples,
"Room temperature" is about "25 ℃.
Denitration efficiency = (a) 1 -A 2 )÷A 1 ×100％，
Wherein A is 1 NOx (including NO and NO) in the flue gas discharged from the outlet of the furnace when only the burner is operated 2 ) The content of (A); a. The 2 NOx (including NOx) in flue gas discharged from a furnace outlet after the composition is sprayed into the furnace while the burner is in operationNO and NO 2 ) The content of (a).
Example 1
100g of hexane solution (the mass fraction is 98wt%, and the solvent of the hexane solution is benzene), 40g of formic acid aqueous solution (the mass fraction is 94 wt%) and 40g of saturated solution of calcium hydroxide are subjected to first mixing in a first-stage reactor at room temperature, after 30min, the first mixed product is fed into a second-stage reactor, and at the same time, 18g of activated carbon (the particle size of the activated carbon is 5 mu m, and the specific surface area is 2000 g/m) is added into the second-stage reactor 2 ) And 1g of sodium chloride aqueous solution (with the mass fraction of 10 wt%) and 1g of potassium chloride aqueous solution (with the mass fraction of 10 wt%) are subjected to second mixing at room temperature, and the denitration composition is obtained after 60 min.
Example 2
100g of hexane solution (the mass fraction is 98wt%, and the solvent of the hexane solution is benzene), 40g of maleic acid aqueous solution (the mass fraction is 20 wt%) and 40g of saturated solution of calcium hydroxide are subjected to first mixing in a first-stage reactor at room temperature, after 30min, the first mixed product is sent into a second-stage reactor, and simultaneously 18g of activated carbon (the particle size of the activated carbon is 10 mu m, and the specific surface area is 1500 g/m) is added into the second-stage reactor 2 ) And 1g of sodium chloride aqueous solution (the mass fraction is 10 wt%) and 1g of potassium chloride aqueous solution (the mass fraction is 10 wt%) are subjected to second mixing at room temperature, and the composition with the denitration function is obtained after 60 min.
Example 3
80g of hexane solution (the mass fraction is 98wt%, and the solvent of the hexane solution is benzene), 50g of formic acid aqueous solution (the mass fraction is 94 wt%) and 50g of saturated solution of calcium hydroxide are subjected to first mixing in a first-stage reactor at room temperature, the first mixed product is fed into a second-stage reactor after 30min, and 16g of activated carbon (the particle size of the activated carbon is 5 mu m, and the specific surface area is 2000 g/m) is added into the second-stage reactor at the same time 2 ) And 2g of sodium chloride aqueous solution (the mass fraction is 10 wt%) and 2g of potassium chloride aqueous solution (the mass fraction is 10 wt%) are subjected to second mixing at room temperature, and the composition with the denitration function is obtained after 60 min.
Example 4
100g of 1-octan are introduced into a first reactorAlkene solution (the mass fraction is 95wt%, the solvent of the 1-octene solution is benzene), 40g formic acid aqueous solution (the mass fraction is 94 wt%) and 40g saturated solution of calcium hydroxide are subjected to first mixing at room temperature, after 30min, the first mixed product is sent into a secondary reactor, and simultaneously 18g activated carbon (the particle size of the activated carbon is 25 mu m, and the specific surface area is 1250 g/m) is added into the secondary reactor 2 ) And 1g of sodium chloride aqueous solution (the mass fraction is 10 wt%) and 1g of potassium chloride aqueous solution (the mass fraction is 10 wt%) are subjected to second mixing at room temperature, and the composition with the denitration function is obtained after 60 min.
Example 5
In a first-stage reactor, 100g of ethanol solution (the mass fraction is 98wt%, the solvent of the ethanol solution is water), 40g of formic acid aqueous solution (the mass fraction is 94 wt%) and 40g of saturated solution of calcium hydroxide are subjected to first mixing at room temperature, after 30min, the first mixed product is sent into a second-stage reactor, and at the same time, 18g of activated carbon (the particle size of the activated carbon is 25 mu m, and the specific surface area is 1250 g/m) is added into the second-stage reactor 2 ) And 1g of sodium chloride aqueous solution (with the mass fraction of 10 wt%) and 1g of potassium chloride aqueous solution (with the mass fraction of 10 wt%) are subjected to second mixing at room temperature, and the denitration composition is obtained after 60 min.
Example 6
A composition having a denitration function was prepared according to the method of example 1, except that the aqueous sodium chloride solution and the aqueous potassium chloride solution were not added.
Example 7
A composition having a denitration function was prepared by the same method as in example 1, except that the activated carbon had a particle size of 50 μm and a specific surface area of 800g/m 2 。
Example 8
A composition having a denitration function was prepared according to the method of example 1, except that hexane was replaced with decane.
Example 9
A composition having a denitration function was prepared according to the method of example 1, except that the solvent of the hexane solution was replaced with toluene.
Example 10
A composition having a denitration function was prepared by following the procedure of example 1 except that the amount of the formic acid aqueous solution was 25g, the amount of the saturated solution of calcium hydroxide was 25g, and the amount of the activated carbon was 10g.
Comparative example 1
A composition having a denitration function was prepared according to the method of example 1, except that activated carbon was not added.
Comparative example 2
A composition having a denitration function was prepared according to the method of example 1, except that the hexane solution was not added.
Comparative example 3
A composition having a denitration function was prepared according to the method of example 1, except that the aqueous formic acid solution was not added.
Comparative example 4
A composition having a denitration function was prepared according to the method of example 1, except that a saturated solution of calcium hydroxide was not added.
Test example 1
25t of coal powder is combusted in an industrial boiler per hour, NOx in smoke gas generated by the coal powder is reduced to 113mg/Nm after the smoke gas is combusted by a NOx combustor, and the NOx in the smoke gas discharged from a hearth outlet is reduced to 113mg/Nm 3 。
To test the denitration rate of the composition prepared in example 1, the composition prepared in example 1 was sprayed into a furnace while a burner was operated, wherein the burner was operated at a temperature of 900 ℃ and a flue gas flow rate of 14000m 3 H is used as the reference value. The effect of the amount of the composition on the NOx content of the flue gas exiting the furnace outlet was examined and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the NOx emission value is gradually reduced with the increase of the dosage of the composition, the trend is gradually slowed down, and the denitration efficiency reaches 77.9 percent at most.
Comparative test 1
The test was carried out in accordance with the procedure of test example 1, except that the composition prepared in example 1 was replaced with an aqueous urea solution having a mass fraction of 8 wt%. The results are shown in Table 2.
TABLE 2
| Injection amount of urea aqueous solution (L/h) | NOx emission value (mg/Nm) 3 ) | Denitration efficiency (%) |
| 0 | 113 | 0 |
| 20 | 81 | 28.3 |
| 40 | 76 | 32.7 |
| 60 | 74 | 34.5 |
| 80 | 72 | 36.3 |
| 100 | 69 | 38.9 |
| 120 | 68 | 39.8 |
| 130 | 67 | 40.7 |
Comparing table 2 with table 1, it can be seen that, when the urea aqueous solution and the composition are added in the same mass, the denitration efficiency of the composition is significantly higher than that of the urea aqueous solution, the maximum denitration efficiency of the urea aqueous solution is only 40.7%, and the maximum denitration efficiency of the composition can reach 77%. On the premise of meeting the emission requirement, the composition has the advantages of less dosage and higher efficiency.
Test example 2
25t of coal powder is combusted in an industrial boiler per hour, NOx in smoke gas generated by the coal powder is reduced to 113mg/Nm after the smoke gas is combusted by a NOx combustor, and the NOx in the smoke gas discharged from a hearth outlet is reduced to 113mg/Nm 3 。
To test the denitration rate of the compositions prepared in the above examples and comparative examples, the compositions prepared in the above examples and comparative examples were sprayed into a furnace while a burner was operated, wherein the burner was operated at a combustion temperature of 900 ℃ and a flue gas flow rate of 14000m 3 The amount of the composition sprayed was 150L/h. The NOx content of the flue gas exiting the furnace outlet was recorded and the results are shown in Table 3.
TABLE 3
As can be seen from Table 3, higher denitration efficiency can be obtained by using the combination of the invention compared with the comparative example, and the denitration efficiency is higher than 45%.
The denitration efficiency of the composition of examples 1, 2, 3, 4, 6, 8 and 9 of the present invention is preferably higher than 60%, and the denitration efficiency of the composition of examples 1, 2, 3, 8 and 9 of the present invention is more than or equal to 70%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (19)
1. The composition with the denitration function is characterized by comprising organic matters, activated carbon, organic acids, calcium-containing inorganic matters and optional auxiliaries, wherein the organic matters are selected from at least one of alkanes with carbon atoms more than 5, alkenes with carbon atoms more than 5 and lower monohydric alcohols, the carbon atoms of the lower monohydric alcohols are 1-5, the auxiliaries are water-soluble salts of metals IA, the organic acids are selected from monobasic acids and/or dibasic acids, the carbon atoms of the monobasic acids are 1-10, and the carbon atoms of the dibasic acids are 1-10;
the content of the activated carbon is 15-25g, the content of the organic acid is 5-100g, the content of the calcium-containing inorganic substance is 0.01-1g, and the dosage of the auxiliary agent is 0-1g per 100g of organic substance.
2. The composition according to claim 1, wherein the activated carbon is present in an amount of 18-21g per 100g of organic matter.
3. The composition according to claim 1, wherein the organic acid is contained in an amount of 8 to 60g per 100g of the organic matter.
4. The composition according to claim 1, wherein the calcium-containing inorganic substance is contained in an amount of 0.05-0.11g per 100g of the organic substance.
5. The composition according to claim 1, wherein the adjuvant is used in an amount of 0.2 to 0.6g per 100g of organic matter.
6. The composition of claim 1, wherein the alkane having a carbon number greater than 5 is selected from at least one of hexane, cyclohexane, heptane, cycloheptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and heptadecane;
and/or the olefin with the carbon number more than 5 is selected from at least one of 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.
7. The composition of claim 1, wherein the lower monohydric alcohol is selected from at least one of methanol, ethanol, propanol, and butanol.
8. The composition of claim 1, wherein the activated carbon has a particle size of less than 30 μm and a specific surface area of greater than 1200g/m 2 。
9. The composition of claim 1, wherein the adjuvant is sodium chloride and/or potassium chloride.
10. The composition of claim 1, wherein the monobasic acid is selected from at least one of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, and benzoic acid;
and/or the dibasic acid is at least one selected from adipic acid, oxalic acid, malonic acid, succinic acid, maleic acid and tartaric acid.
11. The composition of claim 1, wherein the calcium-containing mineral is at least one of calcium hydroxide, calcium chloride, and calcium nitrate.
12. The composition of claim 1, wherein the composition further comprises a solvent, and the solvent comprises water and/or benzene series.
13. A method of denitration comprising contacting the composition of any of claims 1 to 12 with flue gas.
14. The method of claim 13, wherein the temperature of the contacting is 650-1000 ℃.
15. The method of claim 13, wherein the flue gas flow rate is 14000m 3 When the dosage is per hour, the dosage of the composition is 80 to 200L/hour.
16. The method of claim 13, wherein the flue gas flow rate is 14000m 3 When the dosage is per hour, the dosage of the composition is 120 to 160L/hour.
17. The method of claim 13, wherein the composition is used in an amount of 6-10L per 100g of NOx in the flue gas.
18. The method of claim 13, wherein the content of NOx in the flue gas is 50-200mg/Nm 3 。
19. The method of claim 13, wherein the NOx content of the flue gas is 100-150mg/Nm 3 。
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