CN111744494A - Flat plate type CO and SO2And NOxSynchronous removal catalyst and preparation method thereof - Google Patents

Flat plate type CO and SO2And NOxSynchronous removal catalyst and preparation method thereof Download PDF

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CN111744494A
CN111744494A CN202010527741.0A CN202010527741A CN111744494A CN 111744494 A CN111744494 A CN 111744494A CN 202010527741 A CN202010527741 A CN 202010527741A CN 111744494 A CN111744494 A CN 111744494A
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曲艳超
陈晨
陆强
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Beijing Huadian Guangda Environment Co ltd
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Abstract

The embodiment of the invention provides a flat-plate type CO and SO2And NOxA synchronous removal catalyst and a preparation method thereof. The catalyst carrier is gamma-Al2O3Nanotube with La as active component0.8Sr0.2CoxMo1‑ xO3Perovskite, preparing a flat catalyst by adopting a roll-in coating process, and pre-vulcanizing the catalyst before use to prepare the final catalyst. The catalyst is prepared from gamma-Al2O3The nanotube is used as a carrier, so that the uniform distribution of active components is facilitated, the specific surface area of the catalyst can be greatly increased, and the catalyst has good catalytic activity and anti-poisoning performance within the temperature range of 300-450 ℃; la0.8Sr0.2CoxMo1‑xO3The perovskite structure can realize CO and SO2And NOxSynchronously removing the three pollutants; the catalyst is pre-vulcanized to reduce SO to CO2Has good catalytic activity and contains O2And H2The real smoke of O has good reaction activity and selectivity; and by adding the forming auxiliary agent, the preparation process is optimized, the prepared catalyst has the advantages of reduced pressure, long service life, reduced investment and operation cost, and good economic benefit.

Description

Flat plate type CO and SO2And NOxSynchronous removal catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of environmental protection and denitration catalysis, and particularly relates to a flat plate type CO and SO2And NOxThe catalyst is synchronously removed, and the synchronous removal of CO, nitrogen and sulfur pollutants can be realized. The invention also provides the flat-plate type CO and SO2And NOxA preparation method of synchronously removing a catalyst.
Background
Sulfur dioxide (SO)2) And Nitrogen Oxides (NO)x) Is an important atmospheric pollutant, can cause acid rain, photochemical smog, ozone layer damage and the like, and causes great harm to the environment and human health. Coal is one of the most important energy sources in China, namely SO discharged by coal-fired power plants2And NOxAccounting for more than 90% of the total discharge. At present, limestone and gypsum wet desulphurization (FGD) is widely adopted as a desulphurization process in coal-fired power plants, Selective Catalytic Reduction (SCR) is mostly adopted as a denitration process, and two independent devices have ideal desulphurization efficiency and denitration efficiency, but if two devices are used for combined desulphurization and denitration, the defects of large floor area, complex system, high investment and operation cost and the like exist.
The flue gas usually contains a certain amount of carbon monoxide (CO), SO the CO existing in the flue gas is used as a reducing agent to reduce SO2And NOxReduction to elemental sulfur and N2Not only can realize CO and SO2And NOxThe method has the advantages of synchronous removal of the three pollutants, no need of adding an additional reducing agent, simple process, low operation cost and wide application prospect. But CO reduces SO2And NOxThe reaction of (a) needs to be carried out in the presence of a catalyst, and therefore the development of a catalyst with high activity, selectivity and stability is the core of the process. Chinese patent document CN102049257A discloses CO simultaneous reduction of SO2And NO as catalyst, in TiO2-Al2O3The composite oxide is used as carrier, the transition metal oxide is used as active component, after said catalyst is presulfurized, under the condition of low temp. and high air speed 98% SO can be obtained2Conversion and near 100% NO conversion, but the remaining CO in the flue gas is not further treated and is still vented to the atmosphere. Chinese patent document CN103464154A also discloses a method for simultaneously catalyzing and reducing NO and SO by CO2The catalyst of (1), the catalyst being prepared from gamma-Al2O3Is used as a carrier and carries metal oxide. The catalyst can effectively reduce SO2And NO, but can not remove residual CO, so that the CO emission of tail gas exceeds the standard. In view of the above technical problems of the existing catalysts, it is urgently needed to develop a catalyst capable of realizing CO and SO2And NOxHigh efficiency and synchronous removal of catalyst.
Disclosure of Invention
The invention provides a flat plate type CO and SO for solving the technical problem that residual CO cannot be synchronously treated in the existing synchronous desulfurization and denitrification process2And NOxSynchronous removal catalyst for reducing SO from CO and preparation method thereof2And NOxThe reaction has high activity and can oxidize CO into CO2Also has high activity, and can efficiently realize CO and SO2And NOxAnd (4) synchronously removing.
To solve the above technical problems, embodiments of the present invention provide a flat plate type CO, SO2And NOxThe catalyst is synchronously removed and is of a flat plate structure, and the components of the catalyst comprise 5-20% of La by mass0.8Sr0.2CoxMo1-xO3And 80-95% of gamma-Al2O3Nanotubes, said catalyst being presulfided.
Preferably, the La0.8Sr0.2CoxMo1-xO3The perovskite structure is obtained, wherein x is 0.5-0.7.
Preferably, the gamma-Al2O3The length of the nanotube is 250-300 nm, and the outer diameter is 18-20 nm.
The inventionThe embodiment also provides the flat-plate type CO and SO2And NOxThe preparation method of the synchronous removal catalyst comprises the following steps:
step 1, catalyst carrier preparation, namely, under the condition of stirring, AlCl is added3The solution is slowly dripped into NaOH solution to obtain transparent NaAlO2A solution; adding hydrogen peroxide solution into hexadecyl trimethyl ammonium bromide solution at 45 ℃, stirring uniformly, and then adding NaAlO2Slowly dripping the solution into hexadecyl trimethyl ammonium bromide solution, stirring uniformly, and then adding 30% of H2O2A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, then carrying out reaction at 120 ℃ for 12h, washing and filtering the product, drying the product in the air at 80-120 ℃ for 12-24 h, and roasting the product in the air at 500-550 ℃ for 4-24 h to obtain the gamma-Al2O3A nanotube;
step 2, catalyst mud preparation, namely according to La0.8Sr0.2CoxMo1-xO3Sequentially adding lanthanum nitrate, strontium nitrate, cobalt nitrate and ammonium heptamolybdate into deionized water according to the mass proportion of lanthanum, strontium, cobalt and molybdenum elements, adding citric acid after completely dissolving, and stirring for 1-2 h at 40-60 ℃; adding the obtained solution into the gamma-Al prepared in the step 12O3Uniformly stirring the nano tubes, adding montmorillonite, glass fiber, polyethylene oxide and carboxymethyl cellulose, and aging for 24-48 h under a closed condition to prepare catalyst mud;
and 3, preparing a flat-plate catalyst, comprising the following steps:
step 31, forming a flat-plate catalyst, namely extruding the catalyst mud material prepared in the step 2 by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, rolling, coating, folding and shearing, drying the catalyst mud material in the air at 105-120 ℃ for 5-10 min, and roasting the catalyst mud material in the air at 750-800 ℃ for 4-8 h to prepare the flat-plate catalyst;
step 32, presulfurizing the catalyst, namely, the flat-plate catalyst prepared in the step 31 is prepared by CO and SO2、O2And N2The pre-sulfiding gas composition is at 200 deg.CTreating for 1-4 h; then cut off SO2Heating the gas to 300-400 ℃ and keeping the temperature for 1-4 h; finally, heating to 600-700 ℃ and introducing SO2Keeping the gas for 2-6 h to prepare the prevulcanized flat plate type La0.8Sr0.2CoxMo1-xO3/γ-Al2O3The catalyst is the flat-plate type CO or SO2And NOxAnd synchronously removing the catalyst.
Preferably, in step 1, the AlCl is3The concentration of the solution is 0.5mol/L, the concentration of the NaOH solution is 4mol/L, and AlCl3And NaOH in a molar ratio of 1: 2.
As the optimization of the step 1, the concentration of the hexadecyl trimethyl ammonium bromide solution is 0.3 mol/L.
As a preference of step 2, the amount of the substance of citric acid added to the deionized water is equal to the total amount of the metal ion substance added.
Preferably, in the step 2, the length of the glass fiber is 4-6 mm.
Preferably, in step 2, the polyacrylamide is anionic and has a molecular weight of 200 to 400 ten thousand.
Preferably, in step 32, CO and SO in the pre-sulfiding gas2、O2And N2The volume ratio of each component is respectively 10%, 2%, 5% and 83%.
The technical scheme of the embodiment of the invention provides a novel gamma-Al2O3Nanotube as carrier, La0.8Sr0.2CoxMo1-xO3Perovskite is an active component, and the catalyst can synchronously remove CO and SO in flue gas through presulfurizing the treated catalyst2And NOxThe beneficial effects are as follows:
1.γ-Al2O3the nanotube is used as a carrier, so that the uniform distribution of active components is facilitated, the specific surface area of the catalyst can be greatly increased, and the activity of the catalyst is effectively improved; meanwhile, gamma-Al is properly selected2O3The length and the outer diameter of the nano tube can ensure that the nano tube has larger specific surface as a carrierAnd the mechanical strength of the catalyst is not reduced; thirdly, gamma-Al2O3The unique tubular cavity structure of the nanotube can lead most active components to be fixed inside the pipeline, and the gamma-Al2O3The nanotube pipeline can effectively isolate solid toxic substances such as alkali metal, heavy metal and the like outside the pipeline, thereby avoiding the inactivation of active components due to the influence of the toxic substances in the flue gas and improving the anti-poisoning performance of the catalyst;
2.La0.8Sr0.2CoxMo1-xO3perovskite structure to SO2And NOxHas good reducibility and selectivity, simultaneously has good catalytic oxidation performance on CO, and can convert SO2Reduction to elemental sulfur, NOx to N2Oxidation of CO to CO2The synchronous removal of the three pollutants is realized;
3. after the catalyst is subjected to pre-vulcanization treatment, the metal-sulfur bond in the Co-Mo-S structure can also reduce SO to CO2Has good catalytic activity; and part of La is generated after prevulcanization2O2S, the substance has double active centers, not only has the active center which reacts with CO to form intermediate product COS, but also promotes COS and SO2The active center of the reaction is adopted, no COS is generated in the product, and the selectivity of the reaction is very high;
4. the catalyst is presulfided and then contains O2And H2The real smoke of O has good reaction activity and selectivity, and the catalyst has excellent anti-oxygen poisoning performance;
5. by adding various inorganic and organic forming aids, the preparation process is optimized, the flat-plate catalyst with high mechanical property is prepared, the pressure drop is low, the service life is long, the investment and the operation cost are reduced, and the economic benefit is good.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
Aiming at the existing problems, the invention provides a flat-plate type CO and SO2And NOxSynchronous removal of catalystThe catalyst can realize CO and SO with high efficiency2And NOxAnd (4) synchronously removing.
In order to realize the technical scheme, the embodiment of the invention provides a flat-plate CO and SO2And NOxThe catalyst is synchronously removed and is of a flat plate structure, and the components of the catalyst comprise 5-20% of La by mass0.8Sr0.2CoxMo1-xO3And 80-95% of gamma-Al2O3Nanotubes and catalyst are presulfurized. As a more preferred embodiment, La0.8Sr0.2CoxMo1-xO3The structure is a perovskite structure, wherein x is 0.5-0.7; gamma-Al2O3The length of the nanotube can be controlled to be 250-300 nm selectively, the outer diameter size is controlled to be 18-20 nm, and gamma-Al can be ensured2O3The nanotube as catalyst carrier has relatively great specific surface area and no reduction in the mechanical strength of the catalyst.
In order to better realize the technical scheme, the invention also provides the flat-plate CO and SO2And NOxThe preparation method of the synchronous removal catalyst comprises the following steps:
s1, catalyst carrier preparation, namely, under the stirring condition, preparing AlCl3The solution is slowly dripped into NaOH solution to obtain transparent NaAlO2A solution; adding hydrogen peroxide solution into hexadecyl trimethyl ammonium bromide solution at 45 ℃, stirring uniformly, and then adding NaAlO2Slowly dripping the solution into hexadecyl trimethyl ammonium bromide solution, stirring uniformly, and then adding 30% of H2O2A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, then carrying out reaction at 120 ℃ for 12h, washing and filtering the product, drying the product in the air at 80-120 ℃ for 12-24 h, and roasting the product in the air at 500-550 ℃ for 4-24 h to obtain the gamma-Al2O3A nanotube;
s2, preparing catalyst mud, namely preparing catalyst mud according to La0.8Sr0.2CoxMo1-xO3The ratio of the amounts of lanthanum, strontium, cobalt and molybdenum elements in the material lanthanum nitrate, strontium nitrate, cobalt nitrate and heptamolybdic acid respectivelySequentially adding ammonium into deionized water, adding citric acid after completely dissolving, and stirring for 1-2 h at 40-60 ℃; adding the obtained solution into the gamma-Al prepared in the step 12O3Uniformly stirring the nano tubes, adding montmorillonite, glass fiber, polyethylene oxide and carboxymethyl cellulose, and aging for 24-48 h under a closed condition to prepare catalyst mud;
s3, preparing a flat-plate catalyst, comprising the following steps:
s31, forming a flat-plate catalyst, namely extruding the catalyst mud material prepared in the step S2 by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, rolling, coating, folding and shearing, drying the catalyst mud material in the air at 105-120 ℃ for 5-10 min, and roasting the catalyst mud material in the air at 750-800 ℃ for 4-8 h to prepare the flat-plate catalyst;
s32, presulfurizing the catalyst, namely, preparing the flat-plate catalyst prepared in the step S31 from CO and SO2、O2And N2Treating the pre-vulcanized gas at 200 ℃ for 1-4 h; then cut off SO2Heating the gas to 300-400 ℃ and keeping the temperature for 1-4 h; finally, heating to 600-700 ℃ and introducing SO2Keeping the gas for 2-6 h to prepare the prevulcanized flat plate type La0.8Sr0.2CoxMo1-xO3/γ-Al2O3The catalyst is the flat-plate type CO or SO2And NOxAnd synchronously removing the catalyst.
As a more preferred embodiment:
in step S1, AlCl3The concentration of the solution is 0.5mol/L, the concentration of the NaOH solution is 4mol/L, and AlCl3The molar ratio of NaOH to NaOH is 1: 2; the concentration of the hexadecyl trimethyl ammonium bromide solution is 0.3 mol/L;
in step S2, the amount of the substance of citric acid added to the deionized water is equal to the total amount of the metal ion substance added; the length of the glass fiber is 4-6 mm; the polyacrylamide is anionic, and the molecular weight is 200-400 ten thousand.
In step S32, CO and SO in the presulfurization gas2、O2And N2The volume ratio of each component is respectively10%, 2%, 5% and 83%.
The technical solution of the present invention is specifically described below by specific examples:
example 1
Flat plate type CO and SO2And NOxThe preparation method comprises the following specific steps:
(1)γ-Al2O3nanotube support preparation
6.544kg of AlCl were dissolved in 98L of deionized water324.5L of deionized water was dissolved in 3.922kg of NaOH, and then the prepared AlCl was mixed with stirring3The solution is slowly dripped into NaOH solution to obtain transparent NaAlO2A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 40 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO2Stirring the solution evenly, and adding 30% of H2O2A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, and then carrying out reaction at 120 ℃ for 12 h; washing the obtained product with water, filtering, drying in air at 80 deg.C for 24h, calcining in air at 500 deg.C for 24h, and collecting 2417g of gamma-Al2O3A nanotube support.
(2) Preparation of catalyst mud
131.98g of La (NO) were weighed out3)36H2O, 16.13g of Sr (NO)3)256.55g of Co (NO)3)26H2O and 32.94g of (NH)4)6Mo7O24Dissolving in 1.24L water, adding 146.4g citric acid, and stirring at 40 deg.C for 1 hr; the prepared solution was added to 1900g of gamma-Al2O3And adding montmorillonite, 4mm glass fiber, polyethylene oxide and carboxymethyl cellulose into the carrier, and aging for 24 hours under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Extruding the prepared catalyst mud material by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, rolling, coating, creasing and shearing, drying for 5min at 105 ℃ in air, and roasting for 4h at 750 ℃ in air to obtain 5% La0.8Sr0.2Co0.51Mo0.49O3/95％γ-Al2O3A flat catalyst with the components in percentage by mass;
the prepared flat-plate catalyst is prepared by mixing 10 percent by volume of CO and 2 percent by volume of SO25% of O2And 83% of N2Treating the pre-vulcanized gas for 1h at 200 ℃; then cutting off SO2Heating the gas to 300 ℃, and keeping the temperature for 1 h; finally heating to 600 ℃, and introducing SO2Keeping the gas for 2 hours to obtain the presulfurized flat catalyst.
The prepared catalyst component is La with the mass percentage of 5 percent0.8Sr0.2Co0.51Mo0.49O3/95％γ-Al2O3。
Example 2
Another flat plate type CO and SO2And NOxThe preparation method comprises the following specific steps:
(1)γ-Al2O3nanotube support preparation
7.853kg of AlCl were dissolved in 117.6L of deionized water, respectively329.4L of deionized water was dissolved in 4.706kg of NaOH, and the prepared AlCl was stirred3The solution is slowly dripped into NaOH solution to obtain transparent NaAlO2A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 40 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO2Stirring the solution evenly, and adding 30% of H2O2A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, and then carrying out reaction at 120 ℃ for 12 h; washing the obtained product with water, filtering, drying in air at 120 deg.C for 12 hr, calcining in air at 550 deg.C for 4 hr, and collecting 2897g of gamma-Al2O3A nanotube support.
(2) Preparation of catalyst mud
827.90g of La (NO) was taken3)36H2O, 101.16g of Sr (NO)3)2479.93g of Co (NO)3)26H2O and 130.72g of (NH)4)6Mo7O24Dissolving in 1.85L water, adding 918.38g citric acid, and stirring at 60 deg.C for 2 hr; 2400g of gamma-Al were added to the prepared solution2O3And adding montmorillonite, 6mm glass fiber, polyethylene oxide and carboxymethyl cellulose into the carrier, and aging for 48 hours under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Extruding the prepared catalyst mud material by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, rolling, coating, creasing and shearing, drying the catalyst mud material in the air at 120 ℃ for 10min, and roasting the catalyst mud material in the air at 800 ℃ for 8h to obtain 20% La0.8Sr0.2Co0.69Mo0.31O3/80％γ-Al2O3A flat catalyst with the components in percentage by mass;
the prepared flat-plate catalyst is prepared by mixing 10 percent by volume of CO and 2 percent by volume of SO25% of O2And 83% of N2Treating the pre-vulcanized gas for 4 hours at 200 ℃; then cutting off SO2Heating the gas to 400 ℃, and keeping the temperature for 4 hours; finally heating to 700 ℃, and introducing SO2Keeping the gas for 6 hours to obtain the presulfurized flat catalyst.
The prepared catalyst component is 20 percent of La by mass0.8Sr0.2Co0.69Mo0.31O3/80％γ-Al2O3。
Example 3
Another flat plate type CO and SO2And NOxThe preparation method comprises the following specific steps:
(1)γ-Al2O3nanotube support preparation
9.162kg of AlCl were dissolved in 137.3L of deionized water334.3L of deionized water was dissolved in 5.490kg of NaOH, and then the prepared AlCl was stirred3The solution is slowly dripped into NaOH solution to obtain transparent NaAlO2A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 40 ℃, adding a proper amount of hydrogen peroxide solutionThen NaAlO is slowly dripped2Stirring the solution evenly, and adding 30% of H2O2A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, and then carrying out reaction at 120 ℃ for 12 h; washing the obtained product with water, filtering, drying in air at 110 deg.C for 15h, calcining in air at 525 deg.C for 5h, and collecting 3421g of gamma-Al2O3A nanotube support.
(2) Preparation of catalyst mud
404.60g of La (NO) was taken3)36H2O, 49.44g of Sr (NO)3)2203.95g of Co (NO)3)26H2O and 82.43g of (NH)4)6Mo7O24Dissolving in 2.15L water, adding 448.82g citric acid, and stirring at 50 deg.C for 1.5 hr; the prepared solution was added with 2700g of gamma-Al2O3And adding montmorillonite, 5mm glass fiber, polyethylene oxide and carboxymethyl cellulose into the carrier, and aging for 36h under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Extruding the prepared catalyst mud material by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, rolling, coating, creasing and shearing, drying the catalyst mud material in the air at 110 ℃ for 7min, and roasting the catalyst mud material in the air at 800 ℃ for 4h to obtain 10% La0.8Sr0.2Co0.6Mo0.4O3/90％γ-Al2O3A flat catalyst with the components in percentage by mass;
the prepared flat-plate catalyst is prepared by mixing 10 percent by volume of CO and 2 percent by volume of SO25% of O2And 83% of N2Treating the pre-vulcanized gas at 200 ℃ for 2.5 h; then cutting off SO2Heating the gas to 400 ℃, and keeping the temperature for 1.5 h; finally heating to 650 ℃, and introducing SO2Keeping the gas for 4.5h to obtain the presulfurized flat catalyst.
The prepared catalyst component is La with the mass percentage of 10 percent0.8Sr0.2Co0.6Mo0.4O3/90％γ-Al2O3。
Example 4
Another flat plate type CO and SO2And NOxThe preparation method comprises the following specific steps:
(1)γ-Al2O3nanotube support preparation
10.471kg of AlCl were dissolved in 156.9L of deionized water339.2L of deionized water was dissolved in 6.274kg of NaOH, and the prepared AlCl was stirred3The solution is slowly dripped into NaOH solution to obtain transparent NaAlO2A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 40 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO2Stirring the solution evenly, and adding 30% of H2O2A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, and then carrying out reaction at 120 ℃ for 12 h; washing the obtained product with water, filtering, drying in air at 105 deg.C for 18h, calcining in air at 520 deg.C for 6.5h, and collecting 3917g of gamma-Al2O3A nanotube support.
(2) Preparation of catalyst mud
803.30g of La (NO) was taken3)36H2O, 98.15g Sr (NO)3)2384.69g of Co (NO)3)26H2O and 175.93g of (NH)4)6Mo7O24Dissolving in 2.85L water, adding 891.10g citric acid, and stirring at 55 deg.C for 1.5 h; 3400g of gamma-Al is added to the prepared solution2O3And adding montmorillonite, 4mm glass fiber, polyethylene oxide and carboxymethyl cellulose into the carrier, and aging for 30h under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Extruding the prepared catalyst mud material by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, rolling, coating, creasing and shearing, drying at 115 ℃ in air for 6min, and roasting at 780 ℃ in air for 5.5h to obtain 15% La0.8Sr0.2Co0.57Mo0.43O3/85％γ-Al2O3A flat catalyst with the components in percentage by mass;
the prepared flat-plate catalyst is prepared by mixing 10 percent by volume of CO and 2 percent by volume of SO25% of O2And 83% of N2Treating the pre-vulcanized gas for 3.5 hours at 200 ℃; then cutting off SO2Heating the gas to 350 ℃, and keeping the temperature for 3.5 hours; finally heating to 680 ℃, and introducing SO2Keeping the gas for 3.5h to obtain the presulfurized flat catalyst.
The prepared catalyst component is 15 percent of La by mass0.8Sr0.2Co0.57Mo0.43O3/85％γ-Al2O3。
The catalysts prepared in the previous examples 1 to 4 were subjected to CO and SO at 300 ℃ and 400 ℃ respectively2And NOxSynchronous removal test, the test working condition is: CO concentration 500mg/m3NO concentration 420mg/m3，SO2The concentration is 450mg/m3，O2Volume ratio of 5%, H2The volume ratio of O is 5 percent, and the space velocity is 4500h-1. The efficiency data from the removal test are given in the following table:
TABLE 1.300 ℃ CO, SO2And NOxSynchronous stripping efficiency
Figure BDA0002534173990000091
TABLE 2 CO, SO at 450 deg.C2And NOxSynchronous stripping efficiency
Figure BDA0002534173990000092
Figure BDA0002534173990000101
As can be seen from the above tables 1 and 2, the catalyst provided by the embodiments of the invention has good catalytic activity and oxidation poisoning resistance within the temperature range of 300-450 ℃, and can realize CO and SO2And NOxHigh-efficiency synchronous removal.
It should be understood that the above-mentioned embodiments are only for illustrating the technical concept and features of the present invention, and are not intended to be exhaustive or to limit the scope of the present invention, for providing those skilled in the art with understanding the present invention and implementing the same. Modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is set forth in the following claims.

Claims (10)

1. Flat plate type CO and SO2And NOxThe synchronous removal catalyst is characterized by being of a flat plate structure, and the catalyst comprises 5-20% by mass of La0.8Sr0.2CoxMo1-xO3And 80-95% of gamma-Al2O3Nanotubes, said catalyst being presulfided.
2. The catalyst of claim 1, wherein the La is0.8Sr0.2CoxMo1-xO3The perovskite structure is obtained, wherein x is 0.5-0.7.
3. The catalyst of claim 1, wherein the γ -Al is2O3The length of the nanotube is 250-300 nm, and the outer diameter is 18-20 nm.
4. Flat CO, SO plate according to any of claims 1 to 32And NOxThe preparation method of the synchronous removal catalyst is characterized by comprising the following steps:
step 1. catalyst support preparation, comprising:
under the condition of stirring, adding AlCl3The solution is slowly dripped into NaOH solution to obtain transparent NaAlO2A solution; adding hydrogen peroxide solution into hexadecyl trimethyl ammonium bromide solution at 45 ℃, stirring uniformly, and then adding NaAlO2Slowly dripping the solution into hexadecyl trimethyl ammonium bromide solution, stirring uniformly, and then adding 30% of H2O2A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, then carrying out reaction at 120 ℃ for 12h, washing and filtering the product, drying the product in the air at 80-120 ℃ for 12-24 h, and roasting the product in the air at 500-550 ℃ for 4-24 h to obtain the gamma-Al2O3A nanotube;
step 2, catalyst mud preparation, comprising:
according to La0.8Sr0.2CoxMo1-xO3Sequentially adding lanthanum nitrate, strontium nitrate, cobalt nitrate and ammonium heptamolybdate into deionized water according to the mass proportion of lanthanum, strontium, cobalt and molybdenum elements, adding citric acid after completely dissolving, and stirring for 1-2 h at 40-60 ℃; adding the obtained solution into the gamma-Al prepared in the step 12O3Uniformly stirring the nano tubes, adding montmorillonite, glass fiber, polyethylene oxide and carboxymethyl cellulose, and aging for 24-48 h under a closed condition to prepare catalyst mud;
and 3, preparing a flat-plate catalyst, comprising the following steps:
step 31, forming the flat-plate catalyst, which comprises the following steps:
extruding the catalyst mud material prepared in the step 2 by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, rolling, coating, folding and shearing, drying the catalyst mud material in the air at 105-120 ℃ for 5-10 min, and roasting the catalyst mud material in the air at 750-800 ℃ for 4-8 h to prepare a flat plate type catalyst;
step 32. catalyst presulfiding, comprising:
the flat-plate catalyst prepared in the step 31 is prepared from CO and SO2、O2And N2Treating the pre-vulcanized gas at 200 ℃ for 1-4 h; then cut off SO2Heating the gas to 300-400 ℃ and keeping the temperature for 1-4 h; finally, heating to 600-700 ℃ and introducing SO2Keeping the gas for 2-6 h to prepare the prevulcanized flat plate type La0.8Sr0.2CoxMo1-xO3/γ-Al2O3The catalyst is the flat-plate type CO or SO2And NOxAnd synchronously removing the catalyst.
5. The method of claim 4, wherein the AlCl is adopted in the step 13The concentration of the solution is 0.5mol/L, the concentration of the NaOH solution is 4mol/L, and AlCl3And NaOH in a molar ratio of 1: 2.
6. The method according to claim 4, wherein the concentration of the cetyltrimethylammonium bromide solution in the step 1 is 0.3 mol/L.
7. The method according to claim 4, wherein the amount of the citric acid added to the deionized water in the step 2 is equal to the total amount of the metal ion species added.
8. The preparation method according to claim 4, wherein the length of the glass fiber in the step 2 is 4-6 mm.
9. The method according to claim 4, wherein the polyacrylamide in step 2 is anionic and has a molecular weight of 200 to 400 ten thousand.
10. The method of claim 4, wherein the pre-sulfiding gas in step 32 is CO, SO2、O2And N2The volume ratio of each component is respectively 10%, 2%, 5% and 83%.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471589A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane
CN115518661A (en) * 2021-06-25 2022-12-27 中国石油化工股份有限公司 Sulfur-tolerant shift catalyst, preparation method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60132628A (en) * 1983-11-24 1985-07-15 ハインリツヒ　フリユーブス Removal of sox and nox from exhaust gas
CN106268296A (en) * 2016-08-03 2017-01-04 中南大学 A kind of flue gas processing method of the lanthanio perovskite composite oxide catalysis reduction simultaneous SO_2 and NO removal of doping
CN108355665A (en) * 2018-02-06 2018-08-03 北京石油化工学院 Energy simultaneous SO_2 and NO removal has spinel structure catalyst and its preparation method and application
CN108722431A (en) * 2018-05-15 2018-11-02 昆明理工大学 A kind of A doping type double-perovskite catalyst and the preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60132628A (en) * 1983-11-24 1985-07-15 ハインリツヒ　フリユーブス Removal of sox and nox from exhaust gas
CN106268296A (en) * 2016-08-03 2017-01-04 中南大学 A kind of flue gas processing method of the lanthanio perovskite composite oxide catalysis reduction simultaneous SO_2 and NO removal of doping
CN108355665A (en) * 2018-02-06 2018-08-03 北京石油化工学院 Energy simultaneous SO_2 and NO removal has spinel structure catalyst and its preparation method and application
CN108722431A (en) * 2018-05-15 2018-11-02 昆明理工大学 A kind of A doping type double-perovskite catalyst and the preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
秦毅红等: "La_xSr_(1-x)FeO_3催化剂的制备及其催化还原SO_2性能的研究", 《分子催化》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471589A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane
CN115518661A (en) * 2021-06-25 2022-12-27 中国石油化工股份有限公司 Sulfur-tolerant shift catalyst, preparation method and application
CN115518661B (en) * 2021-06-25 2023-12-05 中国石油化工股份有限公司 Sulfur-tolerant shift catalyst, preparation method and application

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