CN112604696A - Denitration catalyst for purifying tail gas of marine diesel engine and preparation method thereof - Google Patents

Denitration catalyst for purifying tail gas of marine diesel engine and preparation method thereof Download PDF

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CN112604696A
CN112604696A CN202011306927.XA CN202011306927A CN112604696A CN 112604696 A CN112604696 A CN 112604696A CN 202011306927 A CN202011306927 A CN 202011306927A CN 112604696 A CN112604696 A CN 112604696A
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denitration catalyst
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mass fraction
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杨新伟
刘元琦
郭江峰
颜伟
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China Shipbuilding Power Group Co ltd
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Hudong Heavy Machinery Co Ltd
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/10—Heat treatment in the presence of water, e.g. steam
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    • B01D2251/00—Reactants
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Abstract

The invention discloses a denitration catalyst for purifying tail gas of a marine diesel engine and a preparation method thereof, wherein the chemical composition of the denitration catalyst is x Ag/Al2O3-S, wherein x is the mass fraction of the active component Ag, ranging from 0.1 wt.% to 10 wt.%. Specifically, the denitration catalyst includes Al2O3Carrier and Al supported on the carrier2O3An active component Ag on the carrier; wherein the active component Ag is in mass fractionThe number is x, and the carrier is nano microspherical Al with regular morphology2O3Carrier Al2O3S, the chemical components of the two components forming the denitration catalyst are x Ag/Al2O3-S. The catalyst can be used for selective catalytic reduction removal of nitrogen oxides (NOx) in tail gas of marine diesel engines, has the characteristics of simple preparation method, high activity, good stability and the like, and can be simultaneously applied to a selective catalytic reduction process using hydrocarbon and ammonia as reducing agents.

Description

Denitration catalyst for purifying tail gas of marine diesel engine and preparation method thereof
Technical Field
The invention belongs to the fields of atmospheric environment treatment, catalyst technology, environment-friendly ships and the like, and relates to a catalyst for selective catalytic reduction removal of nitrogen oxides (NOx) and a preparation method thereof, which can be used for tail gas purification of low-speed, medium-speed and high-speed diesel engines for ships.
Background
Nitrogen oxides (NOx) in marine diesel exhaust are one of the important constituents of atmospheric pollutants and have a more direct hazard to the health of both humans and animals. With the initial implementation of the IMO Tier III regulations and the expanding Emissions Control Area (ECA), there is an increasing pressure to research and develop suitable processes for the purification of ship exhaust. Selective Catalytic Reduction (SCR) for removing NOx is one of widely accepted methods for effectively removing NOx at present, and plays a key role in industries such as thermal power generation, automobiles, ships and the like in recent years. The process is that under the action of catalyst, proper reducing agent (ammonia gas, hydrocarbon, etc.) is selected to produce selective catalytic reaction with nitrogen oxide (NOx) at a certain temperature to produce non-toxic harmless nitrogen gas and water. The catalyst plays a very important role in the process, and the vanadium-tungsten-titanium (V-W/TiO2) system catalyst is mainly adopted at present and has the characteristics of high catalyst activity, high stability, good sulfur resistance and the like. However, the catalyst has the disadvantages that the activity is not high (below 300 ℃) in a low-temperature range, and the limited factors are more in the application of the exhaust gas treatment of a mobile source (such as a ship); and secondly, because vanadium has biotoxicity, the vanadium causes harm to the environment and the physical health of operators in the long-term continuous use process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a denitration catalyst for purifying tail gas of a marine diesel engine and a preparation method thereof, which can solve the problems.
The purpose of the invention is realized by adopting the following technical scheme:
be used for marine diesel engine tail gas clean-upThe chemical composition of the denitration catalyst is x Ag/Al2O3-S, wherein x is the mass fraction of the active component Ag, ranging from 0.1 wt.% to 10 wt.%. Specifically, the denitration catalyst includes Al2O3Carrier and Al supported on the carrier2O3An active component Ag on the carrier; wherein the mass fraction of the active component Ag is x, and the carrier is nano microspherical Al with regular morphology2O3Carrier Al2O3S, the chemical components of the two components forming the denitration catalyst are x Ag/Al2O3-S。
Preferably, Al has regular nano-microspherical morphology2O3Carrier Al2O3-S is prepared by a hydrothermal synthesis method; the active component Ag is loaded on Al by adopting a wet impregnation method2O3On a carrier.
Preferably, the mass fraction x of the active component Ag of the denitration catalyst is 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%.
A method for preparing the denitration catalyst, which comprises the following steps: firstly, Al with regular nano microspherical morphology is prepared by adopting a hydrothermal synthesis method2O3A carrier; then, an active component Ag is loaded on a fresh prepared Al by a wet impregnation method2O3On a carrier.
Preferably, Al has regular nano-microspherical morphology2O3Carrier Al2O3The preparation process of-S comprises the following steps: s11, weighing 0.5-2.0 g of aluminum salt, 0.1-1 g of alkali metal salt and 0.1-1 g of complexing agent, and crystallizing at 100-300 ℃ for 1-5 h; s12, standing along with the furnace and cooling to room temperature after crystallization is finished; s13, washing and drying the solid sediment at the bottom of the crystallization kettle; s14, roasting the dried solid sediment in a muffle furnace at 300-700 ℃ for 1-5 hours to obtain Al2O3Nano microsphere powder.
Preferably, the aluminum salt is one or more of aluminum nitrate, aluminum isopropoxide, aluminum chloride and aluminum sulfate, the alkali metal salt is one or more of sodium chloride, sodium sulfate, potassium chloride and potassium sulfate, and the complexing agent is one or more of citric acid, sorbitol and urea.
Preferably, the active component Ag is loaded on Al2O3The process on the carrier comprises the following steps: weighing Ag precursor particles with the mass fraction of 0.1-10 wt.% for full dissolution, and loading the Ag precursor solution on Al by using a wet impregnation method2O3Roasting the nano microspheres for 1 to 5 hours at the temperature of between 300 and 700 ℃ to obtain the catalyst xAg/Al2O3-S, wherein x is the mass fraction of the active component Ag.
Preferably, the Ag precursor is one or more of silver nitrate, silver acetate and silver sulfate.
Compared with the prior art, the invention has the beneficial effects that: the catalyst can be used for selective catalytic reduction removal of nitrogen oxides (NOx) in tail gas of marine diesel engines, has the characteristics of simple preparation method, high activity, good stability and the like, and can be applied to a selective catalytic reduction process using hydrocarbon and ammonia as reducing agents.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The general scheme is as follows: the chemical composition is x Ag/Al2O3-S, wherein x is the mass fraction of the active component Ag, ranging from 0.1 wt.% to 10 wt.%; al (Al)2O3S is nano microspherical Al with regular morphology2O3And (3) a carrier. The denitration catalyst is prepared by adopting a two-step synthesis method, and is prepared by adopting a hydrothermal synthesis method to obtain the denitration catalyst with regular nano microspherical morphologyAl of (2)2O3Carrying active component Ag on the carrier by wet impregnation method to prepare Al2O3On a carrier. Nano microsphere Al2O3Carrier (Al)2O3S) the specific synthesis process comprises the following steps: 0.5-2.0 g of aluminum salt, 0.1-1 g of alkali metal salt and 0.1-1 g of complexing agent are weighed and crystallized at 100-300 ℃ for 1-5 hours. After crystallization is finished and the temperature is cooled to room temperature, washing and drying the solid sediment at the bottom of the crystallization kettle, and then roasting in a muffle furnace at 300-700 ℃ for 1-5 hours to obtain Al2O3Nano microsphere powder. Novel nano-microsphere Al2O3After the carrier is prepared, weighing Ag precursor particles with the mass fraction of 0.1-10 wt.% for full dissolution, and loading the Ag precursor solution on Al by using a wet impregnation method2O3Roasting the nano microspheres for 1 to 5 hours at the temperature of between 300 and 700 ℃ to obtain the catalyst xAg/Al2O3-S。
Example 1
1.51g of aluminum nitrate, 0.696g of potassium sulfate and 0.48g of urea were weighed and sufficiently dissolved with deionized water. The resulting mixture was transferred to a crystallization kettle and crystallized at 180 ℃ for 3 hours. After crystallization is finished and the temperature is cooled to room temperature, solid sediment at the bottom of the crystallization kettle is washed and dried, and then is roasted for 2 hours in a muffle furnace at 500 ℃ to obtain Al2O3Nano microsphere powder. Weighing 0.016g of silver nitrate particles for full dissolution, and loading 2g of freshly prepared Al by a wet impregnation method2O3On the nano microsphere powder body. The sample was calcined at 500 ℃ for 3 hours to yield a sample of 0.5 wt.% Ag/Al2O3-S。
The catalytic performance of the catalyst was evaluated using a self-made fixed bed continuous reactor. The mode of gas distribution is selected to simulate the exhaust gas of a marine diesel engine, and the composition of reaction gas is 450ppmNO +900ppmC3H8+7％O2Argon (Ar) as a reaction balance gas, the total flow rate of the reaction gas is controlled to be 350mL/min through a mass flow meter, and the mass space velocity (WHSV) is controlled to be 80,000 ml.g-1·h-1. Bed layerThe time temperature was detected using a type K thermocouple. In the performance test process, the temperature of the bed layer is programmed to be increased from 200 ℃ to 650 ℃, and the temperature increase rate is kept at 4 ℃/min. The activity test was performed after the reaction had stabilized.
The activity evaluation results showed 0.5 wt.% Ag/Al2O3The conversion rate of the-S to the nitrogen oxide reaches more than 90 percent when the temperature range is 440-600 ℃.
Example 2
1.51g of aluminum nitrate, 0.696g of potassium sulfate and 0.48g of urea were weighed and sufficiently dissolved with deionized water. The resulting mixture was transferred to a crystallization kettle and crystallized at 180 ℃ for 3 hours. After crystallization is finished and the temperature is cooled to room temperature, solid sediment at the bottom of the crystallization kettle is washed and dried, and then is roasted for 2 hours in a muffle furnace at 500 ℃ to obtain Al2O3Nano microsphere powder. Weighing 0.063g of silver nitrate particles, fully dissolving, and loading 2g of freshly prepared Al by wet impregnation method2O3On the nano microsphere powder body. The sample was calcined at 500 ℃ for 3 hours to give a sample of 2 wt.% Ag/Al2O3-S。
The catalyst was evaluated in the same manner as in example 1. The activity evaluation results showed 2 wt.% Ag/Al2O3The conversion rate of S to nitrogen oxide reaches more than 90% when the temperature range is 420-570 ℃.
Example 3
1.51g of aluminum nitrate, 0.696g of potassium sulfate and 0.48g of urea were weighed and sufficiently dissolved with deionized water. The obtained mixture is transferred to a crystallization kettle and crystallized for 3 hours at 180 ℃. After crystallization is finished and the temperature is cooled to room temperature, solid sediment at the bottom of the crystallization kettle is washed and dried, and then is roasted for 2 hours in a muffle furnace at 500 ℃ to obtain Al2O3Nano microsphere powder. Weighing 0.126g of silver nitrate particles, fully dissolving, and loading 2g of freshly prepared Al by a wet impregnation method2O3On the nano microsphere powder body. The sample was calcined at 500 ℃ for 3 hours to give a sample of 4 wt.% Ag/Al2O3-S。
The catalyst was evaluated in the same manner as in example 1. Results of Activity evaluationIndicating 2 wt.% Ag/Al2O3The conversion rate of S to nitrogen oxide reaches more than 90% when the temperature is 410-560 ℃.
Example 4
1.51g of aluminum nitrate, 1.2g of sodium sulfate and 0.70g of urea were weighed and sufficiently dissolved with deionized water. The resulting mixture was transferred to a crystallization kettle and crystallized at 180 ℃ for 3 hours. After crystallization is finished and the temperature is cooled to room temperature, solid sediment at the bottom of the crystallization kettle is washed and dried, and then is roasted for 2 hours in a muffle furnace at 500 ℃ to obtain Al2O3Nano microsphere powder. Weighing 0.063g of silver nitrate particles, fully dissolving, and loading 2g of freshly prepared Al by wet impregnation method2O3On the nano microsphere powder body. The sample was calcined at 500 ℃ for 3 hours to give a sample of 2 wt.% Ag/Al2O3-S。
The catalyst was evaluated in the same manner as in example 1. The activity evaluation results showed 2 wt.% Ag/Al2O3The conversion rate of S to nitrogen oxide reaches more than 90% when the temperature is 430-570 ℃.
Example 5
2.13g of aluminum isopropoxide, 0.696g of potassium sulfate and 0.48g of urea were weighed and sufficiently dissolved with deionized water. The resulting mixture was transferred to a crystallization kettle and crystallized at 180 ℃ for 3 hours. After crystallization is finished and the temperature is cooled to room temperature, solid sediment at the bottom of the crystallization kettle is washed and dried, and then is roasted for 2 hours in a muffle furnace at 500 ℃ to obtain Al2O3Nano microsphere powder. Weighing 0.063g of silver nitrate particles, fully dissolving, and loading 2g of freshly prepared Al by wet impregnation method2O3On the nano microsphere powder body. The sample was calcined at 500 ℃ for 3 hours to give a sample of 2 wt.% Ag/Al2O3-S。
The catalyst was evaluated in the same manner as in example 1. The activity evaluation results showed 2 wt.% Ag/Al2O3The conversion rate of S to nitrogen oxide reaches more than 90% when the temperature range is 450-560 ℃.
Example 6
1.51g of aluminum nitrate, 0.696 was weighedPotassium sulfate, 0.48g urea, and fully dissolved with deionized water. The resulting mixture was transferred to a crystallization kettle and crystallized at 180 ℃ for 3 hours. After crystallization is finished and the temperature is cooled to room temperature, solid sediment at the bottom of the crystallization kettle is washed and dried, and then is roasted for 2 hours in a muffle furnace at 500 ℃ to obtain Al2O3Nano microsphere powder. Weighing 0.063g of silver nitrate particles, fully dissolving, and loading 2g of freshly prepared Al by wet impregnation method2O3On the nano microsphere powder body. The sample was calcined at 700 ℃ for 3 hours to give a sample of 2 wt.% Ag/Al2O3-S。
The catalyst was evaluated in the same manner as in example 1. The activity evaluation results showed 2 wt.% Ag/Al2O3The conversion rate of S to nitrogen oxide reaches more than 90% when the temperature is 425 ℃ and 570 ℃.
Example 7:
1.51g of aluminum nitrate, 0.696g of potassium sulfate and 0.48g of urea were weighed and sufficiently dissolved with deionized water. The resulting mixture was transferred to a crystallization kettle and crystallized at 180 ℃ for 3 hours. After crystallization is finished and the temperature is cooled to room temperature, solid sediment at the bottom of the crystallization kettle is washed and dried, and then is roasted for 2 hours in a muffle furnace at 500 ℃ to obtain Al2O3Nano microsphere powder. Weighing 0.062g of silver acetate particles, fully dissolving, and loading 2g of freshly prepared Al by a wet impregnation method2O3On the nano microsphere powder body. The sample was calcined at 500 ℃ for 3 hours to give a sample of 2 wt.% Ag/Al2O3-S。
The catalyst was evaluated in the same manner as in example 1. The activity evaluation results showed 2 wt.% Ag/Al2O3The conversion rate of S to nitrogen oxide reaches more than 90% when the temperature is 410-570 ℃.
The catalyst can be used for selective catalytic reduction removal (SCR) of nitrogen oxides (NOx) in tail gas of a marine low-speed, medium-speed and high-speed diesel engine, the reducing agent is one or more of urea or unburned Hydrocarbons (HC), the power of the diesel engine covers 200-50000 kW, and marine oil covers light oil, marine fuel oil, heavy oil and the like.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (9)

1. A denitration catalyst for purifying tail gas of a marine diesel engine is characterized by comprising Al2O3Carrier and Al supported on the carrier2O3An active component Ag on the carrier; wherein the mass fraction of the active component Ag is x, and the carrier is nano microspherical Al with regular morphology2O3Carrier Al2O3S, the chemical components of the two components forming the denitration catalyst are x Ag/Al2O3-S。
2. The denitration catalyst according to claim 1, characterized in that: wherein x is the mass fraction x of the active component Ag and ranges from 0.1 wt.% to 10 wt.%.
3. The denitration catalyst according to claim 1, characterized in that: al with regular nano microspherical morphology2O3Carrier Al2O3-S is prepared by a hydrothermal synthesis method; the active component Ag is loaded on Al by adopting a wet impregnation method2O3On a carrier.
4. The denitration catalyst according to claim 2, characterized in that: the denitration catalyst comprises an active component Ag with a mass fraction x of 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% and 10 wt%.
5. A method of preparing the denitration catalyst of claim 1, comprising: firstly, Al with regular nano microspherical morphology is prepared by adopting a hydrothermal synthesis method2O3A carrier; then, an active component Ag is loaded on a fresh prepared Al by a wet impregnation method2O3On a carrier.
6. The method of claim 5, wherein the Al has regular nano-micro spherical morphology2O3Carrier Al2O3The preparation process of-S comprises the following steps:
s11, weighing 0.5-2.0 g of aluminum salt, 0.1-1 g of alkali metal salt and 0.1-1 g of complexing agent, and crystallizing at 100-300 ℃ for 1-5 h;
s12, standing along with the furnace and cooling to room temperature after crystallization is finished;
s13, washing and drying the solid sediment at the bottom of the crystallization kettle;
s14, roasting the dried solid sediment in a muffle furnace at 300-700 ℃ for 1-5 hours to obtain Al2O3Nano microsphere powder.
7. The method of claim 6, wherein: the aluminum salt is one or more of aluminum nitrate, aluminum isopropoxide, aluminum chloride and aluminum sulfate, the alkali metal salt is one or more of sodium chloride, sodium sulfate, potassium chloride and potassium sulfate, and the used complexing agent is one or more of citric acid, sorbitol and urea.
8. The production method according to claim 5, wherein Ag, an active ingredient, is supported on Al2O3The process on the carrier comprises the following steps: weighing Ag precursor particles with the mass fraction of 0.1-10 wt.% for full dissolution, and loading the Ag precursor solution on Al by using a wet impregnation method2O3Roasting the nano microspheres for 1 to 5 hours at the temperature of between 300 and 700 ℃ to obtain the catalyst xAg/Al2O3-S, wherein x is activeThe mass fraction of the component Ag.
9. The method of claim 8, wherein: the Ag precursor is one or more of silver nitrate, silver acetate and silver sulfate.
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