CN113828313A - Catalyst for simultaneously desulfurizing and denitrifying boiler flue gas and preparation and application methods thereof - Google Patents
Catalyst for simultaneously desulfurizing and denitrifying boiler flue gas and preparation and application methods thereof Download PDFInfo
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Abstract
本发明涉及环境催化领域，具体涉及一种针对锅炉烟气同时脱硫脱硝的催化剂及其制备和应用方法。本发明公开了一种适用于锅炉烟气同时脱硫脱硝催化剂及其制备和应用，所述催化剂包括铁酸铜和负载在铁酸铜纳米颗粒上的氧化石墨烯(rGO)；所述氧化石墨烯(rGO)的负载量为铁酸铜纳米颗粒重量的0.1～10％。本发明的应用相较于同类型氧化脱硫脱硝工艺，反应所需温度较低，能够有效降低脱硫脱硝过程中的能耗，且负载型催化剂减少了过渡金属离子的浸出，脱除过程中无二次污染。同时催化剂有良好的磁性，易于回收利用，且用量少，可以大大降低成本。
The invention relates to the field of environmental catalysis, in particular to a catalyst for simultaneous desulfurization and denitrification of boiler flue gas and a preparation and application method thereof. The invention discloses a catalyst suitable for simultaneous desulfurization and denitration of boiler flue gas and its preparation and application. The catalyst comprises copper ferrite and graphene oxide (rGO) supported on copper ferrite nanoparticles; the graphene oxide The loading amount of (rGO) was 0.1-10% by weight of copper ferrite nanoparticles. Compared with the same type of oxidative desulfurization and denitration process, the application of the invention has lower reaction temperature, can effectively reduce the energy consumption in the desulfurization and denitrification process, and the supported catalyst reduces the leaching of transition metal ions, and there is no difference in the removal process. secondary pollution. At the same time, the catalyst has good magnetic properties, is easy to recycle and uses less, and can greatly reduce the cost.
Description
Technical Field
The invention relates to the field of environmental catalysis, in particular to a catalyst for simultaneously desulfurizing and denitrifying boiler flue gas and a preparation method and an application method thereof.
Background
With the development of economy, environmental problems are increasingly highlighted. Among them, flue gas discharged from industrial boilers is one of important sources of air pollution. After a large amount of flue gas discharged by an industrial boiler enters the atmosphere, NO and SO in the air2The concentration is rapidly increased, which causes many environmental problems such as acid rain, greenhouse effect, etc., and harms human health. At present, the flue gas desulfurization and denitration are respectively carried out by a more mature technology limestone-gypsum desulfurization method and a Selective Catalytic Reduction (SCR) method. However, the flue gas generated by the industrial boiler has the characteristics of large load fluctuation, complex components, strong corrosivity and the like, and the method is not suitable for small and medium-sized industrial boilers. Therefore, how to economically and efficiently remove NO and SO in flue gas2Has become one of the research hotspots in recent years.
In recent years, scholars at home and abroad have attempted to add one or more oxidants to the removal solution by oxidizing NO to other more soluble NO2To improve the removal efficiency of NO. Thus, many oxidants are widely used for NO and SO2The field of removal of (1). Compared with the common oxidation method, the advanced oxidation method (AOP) has the advantages of less oxidant consumption, high reaction speed, low operation cost and the like. This is done by catalyzing the precursor (persulfuric acid)Sodium, oxone, etc.) to hydroxyl radicals (. OH, 2.8V) and sulfate radicals (SO)4 ·-2.5 to 3.1V), and the free radical has strong oxidizing property and can oxidize NO and SO2So as to achieve the purpose of desulfurization and denitrification at the same time. Therefore, the preparation of the catalyst which is stable, relatively environment-friendly and has high catalytic activity is of great significance.
Disclosure of Invention
The invention aims to provide a catalyst for simultaneously desulfurizing and denitrifying boiler flue gas and a preparation and application method thereof, the temperature required by reaction is lower, the energy consumption in the desulfurizing and denitrifying process can be effectively reduced, the leaching of transition metal ions is reduced, and no secondary pollution is generated in the removing process. Meanwhile, the catalyst has good magnetism, is easy to recycle, has small dosage and can greatly reduce the cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a composite catalyst for simultaneously desulfurizing and denitrifying boiler flue gas, which comprises copper ferrite nano-particles and graphene oxide loaded on the copper ferrite nano-particles.
Preferably, the loading amount of the graphene oxide is 0.1-10% of the weight of the copper ferrite nanoparticles.
Preferably, the molar ratio of Cu to Fe in the copper ferrite is 1:0.5 to 3.
The invention also provides a preparation method of the composite catalyst for simultaneously desulfurizing and denitrifying boiler flue gas, which comprises the following steps:
dissolving ferric nitrate and cupric nitrate in absolute ethyl alcohol to obtain a mixed solution, and dissolving graphene oxide in absolute ethyl alcohol to obtain a graphene oxide dispersion liquid;
and mixing the mixed solution with the graphene oxide dispersion liquid, adjusting the pH value, and performing hydro-thermal treatment to obtain the composite catalyst for simultaneously desulfurizing and denitrifying the boiler flue gas.
Preferably, the specific surface area of the graphene oxide is 100-150 m2/g。
Preferably, in the mixed solution, the molar ratio of copper nitrate to iron nitrate is 1: 0.5-3, wherein the dosage ratio of the copper nitrate to the absolute ethyl alcohol is 1.5-2.5 kg: 60L;
in the graphene oxide dispersion liquid, the dosage ratio of graphene oxide to absolute ethyl alcohol is 1kg: 13-17L.
Preferably, NaOH is used for adjusting the pH value to 10-12.
Preferably, the temperature of the hydrothermal treatment is 170-190 ℃ and the time is 18-22 h.
The invention also provides a method for simultaneously desulfurizing and denitrifying boiler flue gas by using the composite catalyst, which comprises the following steps:
mixing a catalyst and a potassium hydrogen persulfate solution to obtain a mixed solution; after the pH value of the mixed solution is adjusted, mixed flue gas is introduced under the heating condition.
Preferably, the concentration of the catalyst in the mixed solution is 0.05-0.1 g/L; the concentration of the potassium hydrogen persulfate solution is 0.02-0.05 mol/L.
Preferably, the pH value of the mixed solution is adjusted to be 2-7, and the heating temperature is 35-90 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the raw materials used in the invention have low toxicity, low cost and simple operation.
(2) According to the catalyst prepared by the invention, copper ferrite nano particles are uniformly dispersed on the surface of rGO, so that the agglomeration phenomenon of copper ferrite in the synthesis process is inhibited, the specific surface area of the catalyst is increased, and reaction sites are increased. The characteristics of large specific surface area and high electron transfer rate of the rGO are utilized, so that the conversion between transition metal ions is accelerated, and the generation rate of free radicals is further improved. Meanwhile, the introduced carbon-based functional group is also beneficial to the activation of PMS, and the efficiency of synergistic desulfurization and denitrification is obviously improved.
(3) The catalyst prepared by the invention has lower reaction temperature, can effectively reduce energy consumption in the desulfurization and denitrification process, reduces the leaching of transition metal ions by the supported catalyst, and has no secondary pollution in the removal process. Meanwhile, the catalyst has good magnetism, is easy to recycle, has small dosage and can greatly reduce the cost.
Drawings
FIG. 1 is a graph showing desulfurization and denitrification efficiencies at different reaction temperatures in application example 1.
FIG. 2 is a graph showing the desulfurization and denitrification efficiencies at different pH values of the solution of application example 2.
FIG. 3 is a graph showing the desulfurization and denitrification efficiencies at different catalyst loadings in application example 3.
FIG. 4 is a graph showing desulfurization and denitrification efficiencies at different PMS concentrations in application example 4.
Detailed Description
The invention provides a composite catalyst for simultaneously desulfurizing and denitrifying boiler flue gas, which comprises copper ferrite nano-particles and graphene oxide loaded on the copper ferrite nano-particles.
In the invention, the loading amount of the graphene oxide is 0.1-10% of the weight of the copper ferrite nanoparticles, more preferably 0.1-5%, still more preferably 0.1-1%, and still more preferably 1%.
In the invention, the molar ratio of Cu to Fe in the copper ferrite is 1:0.5 to 3; more preferably 1:0.5 to 2; still more preferably 1: 1-2; most preferably 1:2.
the invention also provides a preparation method of the composite catalyst for simultaneously desulfurizing and denitrifying boiler flue gas, which comprises the following steps:
dissolving ferric nitrate and cupric nitrate in absolute ethyl alcohol to obtain a mixed solution, and dissolving graphene oxide in absolute ethyl alcohol to obtain a graphene oxide dispersion liquid;
and mixing the mixed solution with the graphene oxide dispersion liquid, adjusting the pH value, and performing hydro-thermal treatment to obtain the composite catalyst for simultaneously desulfurizing and denitrifying the boiler flue gas.
In the invention, the specific surface area of the graphene oxide is preferably 100-150 m2/g, more preferably 110 to 130m2/g。
In the invention, the graphene oxide is added according to the proportion that the loading amount of the graphene oxide in the finished catalyst is 0.1-10% of the weight of the copper ferrite nanoparticles, and the further preferable ratio is 0.5-0.15.
In the present invention, the molar ratio of copper nitrate to iron nitrate in the mixed solution is preferably 1:0.5 to 3, and more preferably 1: 1 to 2.5.
In the present invention, the ratio of the amount of copper nitrate to absolute ethyl alcohol is preferably 1.5 to 2.5kg:60L, and more preferably 1.8 to 2.2kg: 60L.
In the invention, the dosage ratio of the graphene oxide to the absolute ethyl alcohol in the graphene oxide dispersion liquid is preferably 1kg: 13-17L, and more preferably 1kg: 14-16L.
According to the invention, NaOH is preferably adopted to adjust the pH value to 10-12, and further preferably, the pH value is adjusted to 11.
In the invention, the graphene oxide dispersion liquid is obtained by dissolving graphene oxide in absolute ethyl alcohol and performing ultrasonic treatment.
In the invention, the power of the ultrasonic strip is preferably 90-110W, the time is preferably 1.2-1.8 h, and further preferably, the power of the ultrasonic strip is 95-100W, and the time is 1.4-1.7 h.
In the invention, the temperature of the hydrothermal treatment is preferably 170-190 ℃ for 18-22 h, and the temperature is further preferably 175-185 ℃ for 19-20 h.
And after the hydrothermal treatment is finished, cooling the product system to room temperature, washing with ultrapure water, and drying in vacuum to constant weight to obtain the dry and pure composite catalyst for simultaneously desulfurizing and denitrifying boiler flue gas.
In the invention, the vacuum drying condition is preferably 70-90 ℃, more preferably 75-85 ℃, and still more preferably 80 ℃.
The invention also provides a method for simultaneously desulfurizing and denitrifying boiler flue gas by using the composite catalyst, which comprises the following steps:
mixing a catalyst and a potassium hydrogen persulfate solution to obtain a mixed solution; after the pH value of the mixed solution is adjusted, mixed flue gas is introduced under the heating condition to generate SO4·-And OH to SO in solution2And NO undergoes co-oxidation.
In the invention, the concentration of the catalyst in the mixed solution is preferably 0.05-0.1 g/L, the concentration of the potassium hydrogen persulfate in the mixed solution is preferably 0.02-0.05 mol/L, and the concentration of the catalyst in the mixed solution is more preferably 0.07-0.1 g/L, and the concentration of the potassium hydrogen persulfate in the mixed solution is 0.03-0.04 mol/L.
In the invention, the pH of the mixed solution is preferably adjusted to be 2-7, the heating temperature is preferably 35-90 ℃, the pH of the mixed solution is further preferably adjusted to be 2-4, and the heating temperature is 50-70 ℃.
In the invention, the flow rate of the mixed gas is 1L/min, and SO in the mixed gas2The concentration was 800ppm and the NO concentration was 450 ppm.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Graphene oxide was added to ethanol and treated in an ultrasonic bath for 1.5h to form a graphene oxide solution. Copper nitrate and ferric nitrate were dissolved in ethanol and stirred for 15 min. The two solutions were mixed and stirred for 30min to form a homogeneous suspension, and the pH of the solution was adjusted to 11 with 5mol/L NaOH solution. And carrying out hydrothermal treatment on the obtained solution at 180 ℃ for 20h in a muffle furnace, washing the solution with high-purity water, and drying the solution in a vacuum drying oven at 80 ℃ to constant weight to obtain the catalyst.
The copper nitrate used in this example was Cu (NO)3)2·3H2O, Fe (NO) being ferric nitrate3)3·9H2O; the graphene oxide is added according to the proportion that the loading amount of the graphene oxide in the finished catalyst is 1 percent of the weight of the copper ferrite nano particles; the molar ratio of the copper nitrate to the ferric nitrate is 1: 2;
in the copper nitrate and ferric nitrate anhydrous ethanol solution, the dosage ratio of the copper nitrate to the anhydrous ethanol is 1.3kg: 60L;
in the graphene oxide dispersion liquid, the dosage ratio of graphene oxide to absolute ethyl alcohol is 0.3kg: 60L.
Application example 1
SO2And the removal efficiency of NO under catalytic conditions was tested as follows: the catalyst prepared in example 1 was added to oxoneIn the solution, the specific reaction conditions are as follows: the volume of the solution is 500mL, the concentration of the catalyst in the solution is 0.05g/L, the concentration of the potassium hydrogen persulfate solution is 0.03mol/L, the pH value is 3, the simulated flue gas is 1L/min, and the SO in the simulated flue gas2The concentration is 800ppm, the NO concentration is 450ppm, and the test reaction temperature is SO under the conditions of 25 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and 90 ℃ respectively2And the removal efficiency of NO. The flue gas treated by the solution enters a flue gas analyzer, and the real-time concentration of the flue gas at the time interval of 8 seconds can be tested. SO after 20 minutes of reaction2And NO concentration tends to be stable as SO2And the initial and final concentrations of NO represent SO, respectively2And the removal efficiency of NO.
As shown in FIG. 1, the catalyst can effectively increase SO2And the NO removal efficiency is remarkably improved along with the increase of the temperature, and the desulfurization efficiency is stabilized at about 95 percent. When the temperature is increased to 60 ℃, the denitration efficiency tends to be flat. The results were: when the reaction temperature is 60 ℃, SO in the flue gas2The removal efficiency of the catalyst and NO is the best, and is respectively 95% and 95%.
Example 2
Graphene oxide was added to ethanol and treated in an ultrasonic bath for 1.2h to form a graphene oxide solution. Copper nitrate and ferric nitrate were dissolved in ethanol and stirred for 18 min. The two solutions were mixed and stirred for 35min to form a homogeneous suspension, and the pH of the solution was adjusted to 10 with 6mol/L NaOH solution. The obtained solution was subjected to hydrothermal treatment in a muffle furnace at 185 ℃ for 18 hours, washed with high-purity water, and dried in a vacuum drying oven at 80 ℃ to constant weight to obtain a catalyst.
The copper nitrate used in this example was Cu (NO)3)2·3H2O, Fe (NO) being ferric nitrate3)3·9H2O; the graphene oxide is added according to the proportion that the loading amount of the graphene oxide in the finished catalyst is 0.1 percent of the weight of the copper ferrite nano particles; the molar ratio of the copper nitrate to the ferric nitrate is 1: 0.5;
in the copper nitrate and ferric nitrate anhydrous ethanol solution, the dosage ratio of the copper nitrate to the anhydrous ethanol is 1kg: 60L;
in the graphene oxide dispersion liquid, the dosage ratio of graphene oxide to absolute ethyl alcohol is 0.1kg: 60L.
Application example 2
SO2And the removal efficiency of NO under catalytic conditions was tested as follows: the catalyst prepared in example 2 was added to a solution of potassium hydrogen persulfate under the following reaction conditions: the volume of the solution is 500mL, the reaction temperature is 90 ℃, the concentration of the catalyst in the solution is 0.07g/L, the concentration of the potassium hydrogen persulfate solution is 0.02mol/L, the simulated flue gas is 1L/min, and the SO in the simulated flue gas2Concentration of 800ppm, NO concentration of 450ppm, and test solution pH of 2, 3, 4, 5, 6, 7, 8, 9, 10, and 112And the removal efficiency of NO. The flue gas treated by the solution enters a flue gas analyzer, and the real-time concentration of the flue gas at the time interval of 8 seconds can be tested. SO after 20 minutes of reaction2And NO concentration tends to be stable as SO2And the initial and final concentrations of NO represent SO, respectively2And the removal efficiency of NO.
As shown in FIG. 2, the catalyst can effectively increase SO2And the NO removal efficiency is obviously higher under the acidic condition, and the desulfurization efficiency is stabilized to be more than 95%. As the pH increases, the denitration efficiency gradually decreases. The results were: SO in the flue gas when the pH is 32The removal efficiency of the catalyst and NO is optimal, and is respectively 98% and 94%.
Example 3
Graphene oxide was added to ethanol and treated in an ultrasonic bath for 1.8h to form a graphene oxide solution. Copper nitrate and ferric nitrate were dissolved in ethanol and stirred for 12 min. The two solutions were mixed and stirred for 30min to form a homogeneous suspension, and the pH of the solution was adjusted to 12 with 5mol/L NaOH solution. The obtained solution was subjected to hydrothermal treatment in a muffle furnace at 175 ℃ for 22 hours, washed with high-purity water, and dried in a vacuum drying oven at 80 ℃ to constant weight to obtain a catalyst.
The copper nitrate used in this example was Cu (NO)3)2·3H2O, Fe (NO) being ferric nitrate3)3·9H2O; the oxygen isAdding graphene according to the proportion that the loading amount of graphene oxide in the finished catalyst is 10% of the weight of copper ferrite nano particles; the molar ratio of the copper nitrate to the ferric nitrate is 1: 3;
in the copper nitrate and ferric nitrate anhydrous ethanol solution, the dosage ratio of the copper nitrate to the anhydrous ethanol is 1.5kg: 60L;
in the graphene oxide dispersion liquid, the dosage ratio of graphene oxide to absolute ethyl alcohol is 0.5kg: 60L.
Application example 3
SO2And the removal efficiency of NO under catalytic conditions was tested as follows: the catalyst prepared in example 3 was added to a solution of potassium hydrogen persulfate under the following reaction conditions: the volume of the solution is 500mL, the reaction temperature is 40 ℃, the concentration of the potassium hydrogen persulfate solution is 0.05mol/L, the pH value is 4, the simulated flue gas is 1L/min, and SO in the simulated flue gas2The concentration is 800ppm, the NO concentration is 450ppm, and the concentrations of the tested catalyst in the solution are respectively 0.01g/L, 0.03g/L, 0.05g/L, 0.06g/L, 0.07g/L and 0.10g/L of SO2And the removal efficiency of NO. The flue gas treated by the solution enters a flue gas analyzer, and the real-time concentration of the flue gas at the time interval of 8 seconds can be tested. SO after 20 minutes of reaction2And NO concentration tends to be stable as SO2And the initial and final concentrations of NO represent SO, respectively2And the removal efficiency of NO.
As shown in FIG. 3, the catalyst can effectively increase SO2And the removal efficiency of NO is obviously higher along with the increase of the dosage of the catalyst, and the desulfurization efficiency is stabilized to be more than 95 percent. When the amount of the catalyst used was increased to 0.05g/L, the denitration efficiency tended to be stable. The results were: the dosage of the catalyst is 0.05g/L, and SO in the flue gas2The removal efficiency of the catalyst and NO is the best, and the removal efficiency is 99% and 92% respectively.
Example 4
Graphene oxide was added to ethanol and treated in an ultrasonic bath for 1.5h to form a graphene oxide solution. Copper nitrate and ferric nitrate were dissolved in ethanol and stirred for 15 min. The two solutions were mixed and stirred for 30min to form a homogeneous suspension, and the pH of the solution was adjusted to 11 with 5mol/L NaOH solution. And carrying out hydrothermal treatment on the obtained solution at 180 ℃ for 20h in a muffle furnace, washing the solution with high-purity water, and drying the solution in a vacuum drying oven at 80 ℃ to constant weight to obtain the catalyst.
The copper nitrate used in this example was Cu (NO)3)2·3H2O, Fe (NO) being ferric nitrate3)3·9H2O; the graphene oxide is added according to the proportion that the loading amount of the graphene oxide in the finished catalyst is 2 percent of the weight of the copper ferrite nano particles; the molar ratio of the copper nitrate to the ferric nitrate is 1: 2.2;
in the copper nitrate and ferric nitrate anhydrous ethanol solution, the dosage ratio of the copper nitrate to the anhydrous ethanol is 1.3kg: 60L;
in the graphene oxide dispersion liquid, the dosage ratio of graphene oxide to absolute ethyl alcohol is 0.2kg: 60L.
Application example 4
SO2And the removal efficiency of NO under catalytic conditions was tested as follows: the catalyst prepared in example 4 was added to a solution of potassium hydrogen persulfate under the following reaction conditions: the volume of the solution is 500mL, the reaction temperature is 60 ℃, the concentration of the catalyst in the solution is 0.05g/L, the pH value is 3, the simulated flue gas is 1L/min, and SO in the simulated flue gas2The concentration is 800ppm, the NO concentration is 450ppm, and the concentrations of the tested potassium hydrogen persulfate solution are respectively SO under the conditions of 0.001mol/L, 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L and 0.05mol/L2And the removal efficiency of NO. The flue gas treated by the solution enters a flue gas analyzer, and the real-time concentration of the flue gas at the time interval of 8 seconds can be tested. SO after 20 minutes of reaction2And NO concentration tends to be stable as SO2And the initial and final concentrations of NO represent SO, respectively2And the removal efficiency of NO.
As shown in FIG. 4, the catalyst can effectively increase SO2And the removal efficiency of NO is obviously higher with the increase of the concentration of potassium hydrogen Persulfate (PMS), but when the concentration of PMS is increased to 0.03mol/L, the denitration reaction is inhibited, and the denitration efficiency begins to decrease. The results were: when the concentration of PMS is 0.03mol/L, SO in the flue gas2The removal efficiency of the catalyst and NO is the best, and the removal efficiency is respectively 99 percent and 94 percent。
The embodiment of the invention provides a catalyst for simultaneously desulfurizing and denitrifying boiler flue gas, and a preparation method and an application method thereof. Meanwhile, the catalyst has good magnetism, is easy to recycle, has small dosage and can greatly reduce the cost.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The composite catalyst for simultaneously desulfurizing and denitrifying boiler flue gas is characterized by comprising copper ferrite nanoparticles and graphene oxide loaded on the copper ferrite nanoparticles.
2. The composite catalyst for simultaneous desulfurization and denitrification of boiler flue gas according to claim 1, wherein the loading amount of the graphene oxide is 0.1-10% of the weight of the copper ferrite nanoparticles.
3. The composite catalyst for simultaneously desulfurizing and denitrating boiler flue gas according to claim 1 or 2, wherein the molar ratio of Cu to Fe in the copper ferrite is 1:0.5 to 3.
4. The preparation method of the composite catalyst for simultaneous desulfurization and denitrification of boiler flue gas according to any one of claims 1 to 3, characterized by comprising the following steps:
dissolving ferric nitrate and cupric nitrate in absolute ethyl alcohol to obtain a mixed solution, and dissolving graphene oxide in absolute ethyl alcohol to obtain a graphene oxide dispersion liquid;
and mixing the mixed solution with the graphene oxide dispersion liquid, adjusting the pH value, and performing hydro-thermal treatment to obtain the composite catalyst for simultaneously desulfurizing and denitrifying the boiler flue gas.
5. The preparation method of the composite catalyst for simultaneous desulfurization and denitrification of boiler flue gas according to claim 4, wherein the molar ratio of copper nitrate to iron nitrate in the mixed solution is 1: 0.5-3, wherein the dosage ratio of the copper nitrate to the absolute ethyl alcohol is 1-1.5 kg: 60L;
in the graphene oxide dispersion liquid, the dosage ratio of graphene oxide to absolute ethyl alcohol is 0.1-0.5 kg: 60L.
6. The preparation method of the composite catalyst for simultaneous desulfurization and denitrification of boiler flue gas according to claim 4 or 5, characterized in that NaOH is used for adjusting the pH to 10-12.
7. The preparation method of the composite catalyst for simultaneous desulfurization and denitrification of boiler flue gas according to claim 6, wherein the temperature of the hydrothermal treatment is 170-190 ℃ and the time is 18-22 h.
8. The method for simultaneously desulfurizing and denitrifying boiler flue gas by using the composite catalyst of any one of claims 1 to 3 is characterized by comprising the following steps:
mixing a catalyst and a potassium hydrogen persulfate solution to obtain a mixed solution; after the pH value of the mixed solution is adjusted, mixed flue gas is introduced under the heating condition.
9. The method for simultaneously desulfurizing and denitrating boiler flue gas by using the composite catalyst according to claim 8, wherein the concentration of the catalyst in the mixed solution is 0.05-0.1 g/L; the concentration of the potassium hydrogen persulfate solution is 0.02-0.05 mol/L.
10. The method for simultaneously desulfurizing and denitrating boiler flue gas by using the composite catalyst according to claim 8 or 9, wherein the pH of the mixed solution is adjusted to 2-7, and the heating temperature is 35-90 ℃.
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