CN111229208B - Lotus leaf-source biochar-loaded metal oxide low-temperature SCR (selective catalytic reduction) flue gas denitration catalyst and preparation method and application thereof - Google Patents

Lotus leaf-source biochar-loaded metal oxide low-temperature SCR (selective catalytic reduction) flue gas denitration catalyst and preparation method and application thereof Download PDF

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CN111229208B
CN111229208B CN202010168770.2A CN202010168770A CN111229208B CN 111229208 B CN111229208 B CN 111229208B CN 202010168770 A CN202010168770 A CN 202010168770A CN 111229208 B CN111229208 B CN 111229208B
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biochar
lotus leaf
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喻成龙
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Jiangxi Agricultural University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Abstract

The invention belongs to the field of environmental protection and environmental catalysis, and particularly relates to a lotus leaf source biochar loaded metal oxide low-temperature SCR flue gas denitration catalyst, and a preparation method and application thereof. The invention prepares the biochar material by anaerobic roasting after carrying out acid modification treatment on a typical agricultural waste lotus leaf, takes the acid-modified lotus leaf biochar as a carrier, and MnO is addedxAs an active component, CeOxThe low-temperature flue gas denitration catalyst based on the lotus leaf source biochar is obtained as a cocatalyst. The biochar prepared by chemical modification has higher specific surface area and can pass through MnOx、CeOxThe interaction with the lotus leaf source biochar improves the denitration activity of the catalyst; the SCR activity of the catalyst can approach 90% at 225 ℃ with ammonia as the reducing agent.

Description

Lotus leaf-source biochar-loaded metal oxide low-temperature SCR (selective catalytic reduction) flue gas denitration catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of environmental protection and environmental catalysis, and particularly relates to a lotus leaf source biochar loaded metal oxide low-temperature SCR flue gas denitration catalyst, and a preparation method and application thereof.
Background
Nitrogen Oxides (NO)x) Is one of the major atmospheric pollutants. Besides directly harming human health, the ozone generating agent is one of important precursors for generating ozone and is also an important reason for pollution such as dust haze and fine particles in areas. The nitrogen oxides are mainly derived from combustion of fossil fuels, and according to statistics, 66.7% of the emission of the nitrogen oxides in the national industry comes from power and heat production and supply industries, and is a major consumer for emission of the nitrogen oxides in China, wherein the contribution value of the nitrogen oxides in the thermal power industry is the largest, so that the power industry is a key field for controlling the emission of the nitrogen oxides in China. Among the numerous nitrogen oxide pollution control technologies, the Selective Catalytic Reduction (SCR) flue gas denitration technology is mature and effective and is widely applied to the flue gas purification process of coal-fired power plants.
The catalyst is the key of SCR flue gas denitration technology, and the current commercial SCR catalyst is mainly V2O5–WO3(MoO3)/TiO2The active temperature window of the series of catalysts is 300-400 ℃, and the SCR denitration device is generally arranged in front of the dedusting and desulfurization device due to the higher required temperature, so that the catalysts are easy to be washed and blocked by dust, and the service life is shortened. When the denitration device is arranged behind the dedusting and desulfurization device, a flue gas preheating device is required to be additionally arranged to meet the requirement of catalytic activity. In contrast, the low-temperature SCR catalyst can be operated at less than 300 ℃, so that the denitration device equipped with the low-temperature SCR catalyst can be directly installed after the dust removal and desulfurization device, resulting in better economic efficiency.
Biochar, also called as biomass charcoal, refers to a highly aromatic porous solid particulate matter produced by treating biomass raw materials (wood, grass, corn stalks, wheat straws, hulls, feces, leaves, etc.) and converting a portion of the biomass into a carbon product remaining after oil and gas. The biochar product has the characteristics of abundant pore structures, large specific surface area and more oxygen-containing active groups on the surface, and is an environment-friendly multifunctional material. Compared with other carbon materials, the biochar prepared by taking the biomass material mainly comprising agricultural wastes as the raw material has the characteristics of wide source, environmental friendliness, low cost and the like, and has a huge application prospect in the field of environmental remediation. The invention fully utilizes agricultural wastes to prepare the biochar, takes the biochar as a carrier, can load active components (manganese oxide and cerium oxide), and utilizes the interaction between the active components and the biochar to ensure that the catalyst has good low-temperature SCR activity and stability.
Disclosure of Invention
The invention aims to provide a lotus leaf source biochar loaded metal oxide low-temperature SCR (selective catalytic reduction) flue gas denitration catalyst, and a preparation method and application thereofx。
A lotus leaf source charcoal-loaded metal oxide low-temperature SCR flue gas denitration catalyst comprises the following components: loading active component MnO on acid modified lotus leaf source biochar (LBC)xAnd a cocatalyst CeOxConstituting a catalyst MnOx-CeOx(ii) a/LBC; the MnOx-CeOxin/LBC catalysts, MnOxIs 5-20% of the mass of LBC, and CeOxThe mass of (A) is 3-10% of the mass of LBC.
A preparation method of a lotus leaf source biochar loaded metal oxide low-temperature SCR flue gas denitration catalyst comprises the following steps:
(1) pretreatment of lotus leaves:
taking lotus leaves as a raw material, drying the lotus leaves, crushing the dried lotus leaves by using a crusher, weighing a certain amount of crushed lotus leaves, soaking the biomass raw material by using a nitric acid solution, mixing the raw material with 50mL of deionized water after controlling the mass ratio of acid to the raw material in the soaking process, uniformly stirring the mixture for 2 hours, and soaking the mixture overnight;
(2) preparation of lotus leaf biochar:
drying the impregnated and filtered powder at 105 deg.C for 24h, placing in a tubular resistance furnace, and heating at 100mL/min N2Under protection, heating to a specific temperature at a certain heating rate, and activating for a period of time at a constant temperature; after the activation is finished, N is continuously introduced2Until the furnace tube is cooled to room temperature, and an active carbon primary product is obtained; then washing the sample by using boiled deionized water until the sample is neutral, and drying the washed sample at a certain temperature to obtain a finished product of the biochar carrier;
(3) loading of active components:
weighing manganese source and cerium source, dissolving in absolute ethanol, uniformly dripping into folium Nelumbinis biochar, ultrasonic treating, oven drying, and roasting under nitrogen atmosphere to obtain MnOx-CeOx(ii) a/LBC; MnO obtained by meeting the adding proportion of the manganese source and the lotus leaf biochar carrierx-CeOxMnO in/LBC catalystxIs 5 to 20% of the mass of LBC, and CeOxThe mass of (B) is 3-10% of the mass of LBC.
Wherein, in the method, the mass ratio of the acid to the raw material in the step (1) is controlled to be 0.5-5: 1.
Preferably, the mass ratio of the acid to the raw materials in the impregnation process in the step (1) is controlled to be 0.75:1, 1.5:1 and 3:1 respectively.
Wherein, in the method, the soaking time is 8-16h after the uniform stirring in the step (1) is carried out for 2 h.
Preferably, the soaking time after the uniform stirring for 2 hours in the step (1) is 12 hours, 14 hours and 16 hours respectively.
Wherein, in the above method, N in 100mL/min is described in step (2)2Under protection, the temperature is raised to a specific temperature at a certain rate of 1-5 ℃ per minute-1。
Preferably, N at 100mL/min as described in step (2)2Under protection, the temperature is raised to a specific temperature at a certain rate of 1 ℃ per minute-1、3℃·min-1、5℃·min-1。
Wherein, in the above method, N in 100mL/min is described in step (2)2Under protection, the temperature is raised to a specific temperature at a certain rate, wherein the specific temperature is 400-900 ℃.
Preferably, N at 100mL/min as described in step (2)2Under protection, the temperature is raised to a specific temperature at a certain rate, wherein the specific temperature is 600 ℃, 700 ℃ and 800 ℃.
In the method, the constant-temperature activation of the anaerobic roasting in the step (2) is carried out for a period of time, and the activation time is 1-4 h.
Preferably, the constant-temperature activation of the anaerobic roasting in the step (2) is carried out for a period of time, and the activation time is 1, 2 and 3 hours.
Wherein, in the method, the ultrasonic treatment time in the step (3) is 15-120 min.
Preferably, the ultrasonic treatment time in the step (3) is 15, 30 and 60 min.
Wherein, the drying in the step (3) is drying in a drying oven, the drying temperature is 100-110 ℃, and the drying time is 6-24 h.
Wherein, in the method, the roasting temperature in the step (3) is 300-.
Preferably, the calcination temperature in the step (3) is 300, 400, 500 ℃.
In the method, the biochar source is lotus leaves, the manganese source is manganese acetate, and the cerium source is cerium nitrate.
The invention also discloses an application of the lotus leaf source biochar loaded metal oxide low-temperature SCR flue gas denitration catalyst in a low-temperature SCR flue gas denitration system.
The lotus leaf has a pore structure, and the fired biochar has good hydrophobicity but NOxThe catalytic activity of (3) is weak. After acid modification, the specific surface area is increased, and oxygen-containing functional groups and acid groups are added on the surface of the lotus leaf-source biochar, so that NO is not only treatedxDue to oxygen-containing functional groups and acidic groupsPresence, supported MnOxWith CeOxCan be uniformly dispersed on a lotus leaf biochar carrier, improves the catalytic activity of the lotus leaf biochar after being loaded, and NO is generated at the reaction temperature of 225 DEG CxThe conversion of (a) is close to 90%. However, the presence of too many oxygen-containing functional groups affects the hydrophobic properties, and therefore the acid to feedstock mass ratio during impregnation is a very important parameter, preferably 0.5-5: 1.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, firstly, the characteristics of wide sources of the prepared biochar, large specific surface area of the biochar and hydrophobicity are utilized, and the loaded active components Mn and Ce are well dispersed by an immersion method under the assistance of ultrasonic. The catalyst has better SCR performance due to the synergistic effect of Mn, Ce and the porous biochar.
The invention fully utilizes agricultural wastes to prepare the biochar, takes the biochar as a carrier, can load active components, and utilizes the interaction between the active components and the biochar to ensure that the catalyst has good low-temperature SCR activity and stability. On one hand, the problem of treatment and disposal of agricultural wastes is solved, on the other hand, waste is turned into wealth, and the method is applied to preparation of the high-activity low-temperature SCR denitration catalyst and has good economic and social values.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
The percentages in the following examples are by mass unless otherwise specified.
Example 1
(1) Pretreatment of lotus leaves:
taking lotus leaves as a raw material, drying the lotus leaves, crushing the dried lotus leaves by using a crusher, weighing a certain amount of crushed lotus leaves, carrying out impregnation treatment on a biomass raw material by using a nitric acid solution, mixing the raw material with 50mL of deionized water after controlling the mass ratio of acid to the raw material to be 1.5:1 in the impregnation process, uniformly stirring the mixture for 2 hours, and then impregnating the mixture for 14 hours;
(2) preparation of lotus leaf biochar:
drying the impregnated and filtered powder at 105 deg.C for 24h, placing in a tubular resistance furnace, and heating at 100mL/min N2Under protection, heating to 800 ℃ at a heating rate of 5 ℃/min, and activating for 2h at constant temperature; after the activation is finished, N is continuously introduced2Until the furnace tube is cooled to room temperature, and an active carbon primary product is obtained; then washing the sample by utilizing boiled deionization until the sample is neutral, and drying the washed sample at 105 ℃ to obtain a finished product of the biochar carrier;
(3) loading of active components:
weighing manganese source and cerium source, dissolving in anhydrous ethanol, uniformly dripping into folium Nelumbinis biochar, ultrasonic treating for 30min, and baking in nitrogen atmosphere to obtain MnOx-CeOx(ii) a/LBC; MnO obtained by meeting the adding proportion of the manganese source and the lotus leaf biochar carrierx-CeOxMnO in/LBC catalystxIs 10% of the mass of LBC, and CeOxThe mass of (B) is 3% of the mass of LBC.
Example 2
(1) Pretreatment of lotus leaves:
taking lotus leaves as a raw material, drying the lotus leaves, crushing the dried lotus leaves by using a crusher, weighing a certain amount of crushed lotus leaves, carrying out impregnation treatment on a biomass raw material by using a nitric acid solution, mixing the raw material with 50mL of deionized water after controlling the mass ratio of acid to the raw material to be 0.5:1 in the impregnation process, uniformly stirring the mixture for 2 hours, and then impregnating the mixture for 14 hours;
(2) preparation of lotus leaf biochar:
drying the impregnated and filtered powder at 105 deg.C for 24h, placing in a tubular resistance furnace, and heating at 100mL/min N2Under protection, heating to 800 ℃ at a heating rate of 5 ℃/min, and activating for 2h at constant temperature; after the activation is finished, N is continuously introduced2Until the furnace tube is cooled to room temperature, and an active carbon primary product is obtained; then washing with boiled deionized water until neutral, and placing the washed sample inDrying at 105 ℃ to obtain a finished product of the biochar carrier;
(3) loading of active components:
weighing manganese source and cerium source, dissolving in anhydrous ethanol, uniformly dripping into folium Nelumbinis biochar, ultrasonic treating for 30min, and baking in nitrogen atmosphere to obtain MnOx-CeOx(ii) a/LBC; MnO obtained by meeting the adding proportion of the manganese source and the lotus leaf biochar carrierx-CeOxMnO in/LBC catalystxIs 10% of the mass of LBC, and CeOxThe mass of (B) is 3% of the mass of LBC.
Example 3
(1) Pretreatment of lotus leaves:
the method comprises the steps of taking lotus leaves as a raw material, drying the lotus leaves, crushing the lotus leaves by using a crusher, weighing a certain amount of crushed lotus leaves, carrying out impregnation treatment on a biomass raw material by using a nitric acid solution, mixing the raw material with 50mL of deionized water after controlling the mass ratio of acid to the raw material to be 5:1 in the impregnation process, uniformly stirring the mixture for 2 hours, and then impregnating the mixture for 14 hours.
(2) Preparation of lotus leaf biochar:
drying the impregnated and filtered powder at 105 deg.C for 24h, placing in a tubular resistance furnace, and heating at 100mL/min N2Under protection, the temperature is raised to 800 ℃ at the temperature rise rate of 5 ℃/min, and the mixture is activated for 2 hours at constant temperature. After the activation is finished, N is continuously introduced2Until the furnace tube is cooled to room temperature, and an active carbon primary product is obtained; then washing the sample by utilizing boiled deionization until the sample is neutral, and drying the washed sample at 105 ℃ to obtain a finished product of the biochar carrier;
(3) loading of active components:
weighing manganese source and cerium source, dissolving in anhydrous ethanol, uniformly dripping into folium Nelumbinis biochar, ultrasonic treating for 30min, and baking in nitrogen atmosphere to obtain MnOx-CeOx(ii) a/LBC; MnO obtained by meeting the adding proportion of the manganese source and the lotus leaf biochar carrierx-CeOxMnO in/LBC catalystxIs 10% of the mass of LBC, and CeOxThe mass of (B) is 3% of the mass of LBC.
Example 4
(1) Pretreatment of lotus leaves:
taking lotus leaves as a raw material, drying the lotus leaves, crushing the dried lotus leaves by using a crusher, weighing a certain amount of crushed lotus leaves, carrying out impregnation treatment on a biomass raw material by using a nitric acid solution, mixing the raw material with 50mL of deionized water after controlling the mass ratio of acid to the raw material to be 1.5:1 in the impregnation process, uniformly stirring the mixture for 2 hours, and then impregnating the mixture for 14 hours;
(2) preparation of lotus leaf biochar:
drying the impregnated and filtered powder at 105 deg.C for 24h, placing in a tubular resistance furnace, and heating at 100mL/min N2Under protection, the temperature is raised to 800 ℃ at the temperature rise rate of 5 ℃/min, and the mixture is activated for 2 hours at constant temperature. After the activation is finished, N is continuously introduced2Until the furnace tube is cooled to room temperature, and the primary product of the activated carbon is obtained. Then washing the sample by utilizing boiled deionization until the sample is neutral, and drying the washed sample at 105 ℃ to obtain a finished product of the biochar carrier;
(3) loading of active components:
weighing manganese source and cerium source, dissolving in anhydrous ethanol, uniformly dripping into folium Nelumbinis biochar, ultrasonic treating for 30min, and baking in nitrogen atmosphere to obtain MnOx-CeOx(ii) a/LBC; MnO obtained by meeting the adding proportion of the manganese source and the lotus leaf biochar carrierx-CeOxMnO in/LBC catalystxIs 10% of the mass of LBC, and CeOxThe mass of (B) is 8% of the mass of LBC.
Comparative example 1
(1) Pretreatment of lotus leaves:
taking lotus leaves as a raw material, drying the lotus leaves, crushing the dried lotus leaves by using a crusher, weighing a certain amount of crushed lotus leaves, carrying out impregnation treatment on a biomass raw material by using a nitric acid solution, mixing the raw material with 50mL of deionized water after controlling the mass ratio of acid to the raw material to be 1.5:1 in the impregnation process, uniformly stirring the mixture for 2 hours, and then impregnating the mixture for 14 hours;
(2) preparation of lotus leaf biochar:
drying the impregnated and filtered powder at 105 deg.C for 24h, placing in a tubular resistance furnace, and heating at 100mL/min N2Under protection, heating to 800 ℃ at a heating rate of 5 ℃/min, and activating for 2h at constant temperature; after the activation is finished, N is continuously introduced2Until the furnace tube is cooled to room temperature, and an active carbon primary product is obtained; then washing the sample by using boiled deionized water until the sample is neutral, and drying the washed sample at 105 ℃ to obtain a finished product of the biochar carrier;
(3) loading of active components:
weighing manganese source by adopting an ultrasonic-assisted immersion method, dissolving the manganese source in absolute ethyl alcohol, uniformly dropwise adding the manganese source into the lotus leaf biochar, carrying out ultrasonic treatment for 30min, and roasting the dried powder in nitrogen atmosphere to obtain MnOx(ii) a/LBC; MnO obtained by meeting the adding proportion of the manganese source and the lotus leaf biochar carrierxMnO in/LBC catalystxIs 10% of the mass of LBC; namely 10% MnOx/LBC。
Comparative example 2
(1) Pretreatment of lotus leaves:
taking lotus leaves as a raw material, drying the lotus leaves, crushing the dried lotus leaves by using a crusher, weighing a certain amount of crushed lotus leaves, soaking the biomass raw material by using a nitric acid solution, mixing acid and 50mL of deionized water according to a mass ratio of 1.5:1 in the soaking process, uniformly stirring for 2h, and soaking for 14 h;
(2) preparation of lotus leaf biochar:
drying the impregnated and filtered powder at 105 deg.C for 24h, placing in a tubular resistance furnace, and heating at 100mL/min N2Under protection, heating to 800 ℃ at a heating rate of 5 ℃/min, and activating for 2h at constant temperature; after the activation is finished, N is continuously introduced2Until the furnace tube is cooled to room temperature, and an active carbon primary product is obtained; then washing the sample by using deionized water under the condition of boiling until the sample is neutral, and drying the washed sample at the temperature of 105 ℃ to obtain a finished product of the biochar carrier, namely 0% MnOx/LBC。
Comparative example 3
(1) Pretreatment of rice straws:
taking rice straws as a raw material, drying the rice straws, crushing the dried rice straws by using a crusher, weighing a certain amount of crushed lotus leaves, soaking the biomass raw material by using a nitric acid solution, mixing the raw material with 50mL of deionized water after controlling the mass ratio of acid to the raw material to be 3:1 in the soaking process, uniformly stirring the mixture for 2 hours, and soaking the mixture for 14 hours;
(2) preparation of rice straw biochar (RBC):
drying the impregnated and filtered powder at 105 deg.C for 24h, placing in a tubular resistance furnace, and heating at 100mL/min N2Under protection, heating to 800 ℃ at a heating rate of 5 ℃/min, and activating for 2h at constant temperature; after the activation is finished, N is continuously introduced2Until the furnace tube is cooled to room temperature, and an active carbon primary product is obtained; then washing the sample by using boiled deionized water until the sample is neutral, and drying the washed sample at 105 ℃ to obtain a finished product of the biochar carrier;
(3) loading of active components:
weighing manganese source and cerium source, dissolving in anhydrous ethanol, adding into rice straw charcoal, performing ultrasonic treatment for 30min, and baking in nitrogen atmosphere to obtain CeOx-MnOx/RBC; the manganese source and the straw biochar carrier are added in a proportion meeting the requirement of the obtained CeOx-MnOxMnO in RBC catalystxIs 10% of the mass of LBC, CeOx-MnOxCeO in RBC catalystxThe mass of (b) is 3% of the mass of RBC.
Activity evaluation test
The catalysts prepared in the examples and the comparative examples are put in a quartz tube fixed bed reactor for activity evaluation under simulated flue gas conditions, and NH is used3As a reducing agent, under typical flue gas conditions: NO and O2The volume fractions of the components are respectively 0.06 percent and 2.5 percent, the ammonia-nitrogen ratio is 1:1, Ar is balance gas, and the space velocity is 45000h-1. The gas analysis was performed using German Degraph 350 (NO-NO)2-NOxFlue gas analyzer), the results are shown in table 1:
table 1 results of activity evaluation of examples and comparative examples
Figure BDA0002408391590000081
Figure BDA0002408391590000091
As can be seen from table 1, the catalyst prepared in example 1 exhibited a certain SCR activity in a low temperature range, and the activity of the catalyst prepared in example was significantly superior to the denitration activity of the catalyst prepared in comparative example 1. Example 1 the corresponding catalyst has the best SCR activity and NO at a reaction temperature of 225 deg.CxThe conversion of (a) is close to 90%. The difference between the example 1 and the comparative example 3 is only that the biomass raw material is used, and the comparative example 3 uses rice straw for preparing the biochar, and the result shows that the SCR activity of the comparative example 3 is obviously lower than that of the example 1, which shows that the type of the biochar raw material has an important influence on the SCR activity of the catalyst. Examples 1, 2 and 3 are only the difference in acid to feed ratio during impregnation, and it can be seen from the above table that in the range of 0.5 to 5:1, the catalyst activity effect increases first and then decreases as the acid to feed ratio increases.
Test for antitoxic Effect
The catalysts prepared in the examples and the comparative examples are placed in a quartz tube fixed bed reactor for sulfur resistance test under simulated flue gas conditions, the reaction temperature is 225 ℃, and NH is used3As a reducing agent, under typical flue gas conditions: NO and O2Are 0.06% and 2.5%, respectively, and SO2The volume fraction of (A) is 0.02%, the ammonia-nitrogen ratio is 1:1, Ar is balance gas, and the space velocity is 45000h-1. The gas analysis was performed using German Degraph 350 (NO-NO)2-NOxFlue gas analyzer), the results are shown in table 2:
table 2 results of the sulfur poisoning resistance test of example 1
Figure BDA0002408391590000092
As can be seen from Table 2, the catalyst of example 1 corresponds toShowing stronger anti-sulfur capability. The difference between the example 1 and the comparative example 3 is only that the biomass raw material is different, the comparative example 3 uses rice straws for preparing the biochar, and the result shows that the sulfur water poisoning resistance of the comparative example 3 is obviously lower than that of the example 1, which shows that the type of the biochar raw material also has an important influence on the poisoning resistance of the catalyst. Example 1 differs from comparative example 1 only in the kind of the supported metal oxide, and the active component of the catalyst in comparative example 1 is only MnOxWhile example 1 contains MnOxAnd CeOxAs can be seen from the poisoning resistance test, the sulfur water poisoning resistance of example 1 is significantly higher than that of the comparative example. This means that MnO is loadedxAnd CeOxThe anti-poisoning performance of the lotus leaf source biochar catalyst is better than that of singly loaded MnOxThe catalyst of (1).
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.

Claims (9)

1. The low-temperature SCR flue gas denitration catalyst with metal oxide loaded on lotus leaf-source biochar is characterized in that active component MnO is loaded on acid-modified lotus leaf-source biochar LBCxAnd a cocatalyst CeOxConstituting a catalyst MnOx-CeOx(ii) a/LBC; the MnOx-CeOxin/LBC catalysts, MnOxIs 5-20% of the LBC mass, CeOxThe mass of (A) is 3-10% of that of LBC; the preparation method of the low-temperature SCR flue gas denitration catalyst comprises the following steps:
(1) pretreatment of lotus leaves:
taking lotus leaves as a raw material, drying the lotus leaves, then crushing the lotus leaves by using a crusher, weighing the crushed lotus leaves, carrying out impregnation treatment on the biomass raw material by using a nitric acid solution, controlling the mass ratio of acid to the raw material in the impregnation process, mixing the raw material with 50mL of deionized water, uniformly stirring the mixture for 2 hours, and then impregnating the mixture overnight;
(2) preparation of lotus leaf biochar:
drying the impregnated and filtered powder at 105 deg.C for 24h, placing in a tubular resistance furnace, and heating at 100mL/min N2Under protection, heating and activating at constant temperature; after the activation is finished, N is continuously introduced2Until the furnace tube is cooled to room temperature, and an active carbon primary product is obtained; then washing the product with boiled deionized water until the product is neutral, and drying the washed sample to obtain a finished product of the biochar carrier;
(3) loading of active components:
weighing manganese source and cerium source, dissolving in absolute ethanol, uniformly dripping into folium Nelumbinis biochar, ultrasonic treating, oven drying, and roasting under nitrogen atmosphere to obtain MnOx-CeOx/LBC。
2. The low-temperature SCR flue gas denitration catalyst of the lotus leaf-derived biochar-supported metal oxide as recited in claim 1, wherein the mass ratio of acid to raw materials in the impregnation process in step (1) is controlled to be 0.5-5: 1.
3. The low-temperature SCR flue gas denitration catalyst of the lotus leaf-derived biochar-supported metal oxide as recited in claim 1, wherein the dipping time after the stirring uniformly for 2 hours in step (1) is 8-16 hours.
4. The preparation method of the lotus leaf-derived biochar-supported metal oxide low-temperature SCR flue gas denitration catalyst as claimed in claim 1, wherein N in 100mL/min in step (2) is N2Under protection, heating at a rate of 1-5 ℃ per minute-1(ii) a And (3) activating at a constant temperature of 400-900 ℃ for 1-4 h.
5. The preparation method of the lotus leaf-derived biochar-supported metal oxide low-temperature SCR flue gas denitration catalyst according to claim 1, wherein the washed sample is dried in the step (2), and the drying temperature is 90-110 ℃.
6. The preparation method of the lotus leaf-derived biochar-supported metal oxide low-temperature SCR flue gas denitration catalyst as claimed in claim 1, wherein the ultrasonic treatment time in step (3) is 15-120 min.
7. The preparation method of the lotus leaf-derived biochar-supported metal oxide low-temperature SCR flue gas denitration catalyst according to claim 1, wherein the drying in the step (3) is drying in a drying oven, the drying temperature is 100-110 ℃, the drying time is 6-24 hours, the roasting temperature is 300-500 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 1-4 hours.
8. The preparation method of the lotus leaf-source biochar-supported metal oxide low-temperature SCR flue gas denitration catalyst as claimed in claim 1, wherein the manganese source in step (3) is manganese acetate, and the cerium source is cerium nitrate.
9. The lotus leaf-source biochar-supported metal oxide low-temperature SCR flue gas denitration catalyst as set forth in any one of claims 1 to 3 is applied to a low-temperature SCR flue gas denitration system.
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