CN111921556A - Composite molecular sieve catalyst for NO decomposition and denitration, and preparation method and application thereof - Google Patents
Composite molecular sieve catalyst for NO decomposition and denitration, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a composite molecular sieve catalyst for NO decomposition and denitration, and a preparation method and application thereof, and belongs to the technical field of waste gas denitration. The catalyst comprises Fe, an auxiliary agent and HZSM-5; the auxiliary agent is at least one of Ba, Cs, Na, K, Mg, Ca, Li, Ce, Sm and La, and the molar ratio of Fe to the auxiliary agent is 1-10: 1; the Fe accounts for 0.02-10.00 wt% of the weight percent of the catalyst. The catalyst provided by the invention can provide guarantee for normal operation of ships under IMO (international mobile oxidation) saltpeter-limiting instruction in China, break monopoly of products prepared by high-end ships in Europe and America, and promote the development of China to ship building and strengthening the country.
Description
Technical Field
The invention relates to a composite molecular sieve catalyst for NO decomposition and denitration, and a preparation method and application thereof, and belongs to the technical field of waste gas denitration.
Background
Ocean transportation takes up 90% of the total amount of trade transportation, and rapid development of the ocean transportation causes the NO of ship exhaust gasxThe emission is increased sharply, and the pollution is serious and severe. For this reason, the International Maritime Organization (IMO) stipulates that NO in ship exhaust gas is carried out from 1/2016xThe discharge needs to reach the IMO Tier III standard. The mandatory implementation of the IMO convention is irreversible, and therefore experimental screening of advantageous denitrification technologies for mobile source vessel denitrification is imminent.
Currently, ammonia selective catalytic reduction (NH)3SCR) is a mature fixed source denitration technology, but ammonia is used as a reducing agent, the consumption of ammonia is high, potential safety hazards exist in transportation and storage, secondary pollution is easily caused by ammonia, and the used equipment is large in size and high in investment and operation cost. The existing NH is combined with the actual working condition of ship exhaust gas and the limitation of ship use space3The SCR technique is not suitable for denitration of diesel exhaust gas used in mobile sources such as ships. NO in marine exhaust gasx90-95% of the total amount, directly catalytically decomposing NO into N2And O2The method has the outstanding advantages of no use of reducing agent, small equipment volume, simple process, good economy, no secondary pollution and the like, and is an ideal denitration way for the ship waste gas.
The NO decomposition reaction is thermodynamically feasible (2NO → N)2+O2，△rGm86.6KJ/mol), but the activation energy of the reaction is as high as 364KJ/mol, resulting in the kinetic limitation of the reaction, and therefore the development of a highly efficient NO decomposition catalyst is the core of the denitration technology. Molecular sieve catalysts among reported NO decomposition catalysts have been considered as a potential NO decomposition denitration catalyst due to their high activity under low temperature conditions. The following publications relate to the catalytic decomposition of NO to N using molecular sieve catalysts2And O2. Since Iwamoto et al first discovered that Cu-ZSM-5 molecular sieves have NO decomposing activity in 1986, subsequent studies were mainly developed around optimizing Cu-ZSM-5 molecular sieve catalysts (catal.&Technol., 2018, 8, 4563-4575). At present, NO patent publication reports that the denitration is directly catalyzed by NO decomposition by using a molecular sieve catalyst.
However, Cu-ZSM-5 moleculesThe sieve has good activity at low temperature, but is resistant to SO2And O2The poisoning ability is poor. In one aspect, SO2Molecule and O2Molecules and NO are subjected to competitive adsorption on the active site of the Cu-ZSM-5 molecular sieve, NO adsorption is inhibited, and the NO removal rate is reduced. On the other hand, SO2Copper species of the Cu-ZSM-5 molecular sieve are prone to generate chemical reaction to generate copper sulfate salt, and permanent poisoning of the Cu-ZSM-5 molecular sieve is caused. SO far, no patent and literature is disclosed in SO2The NO decomposition denitration molecular sieve catalyst is preferably used in the atmosphere.
Disclosure of Invention
The present invention solves the above problems by preparing a novel catalyst.
The invention provides a composite molecular sieve catalyst for NO decomposition and denitration, which comprises an iron-based active component and a molecular sieve; the iron-based active component comprises Fe and an auxiliary agent, wherein the auxiliary agent is at least one of Ba, Cs, Na, K, Mg, Ca, Li, Ce, Sm and La, and the molar ratio of Fe to the auxiliary agent is 1-10: 1; the molecular sieve is HZSM-5; the Fe accounts for 0.02-10.00 wt% of the weight percent of the catalyst.
According to the invention, the auxiliary agent is preferably at least one of Ba, Na, K and Cs.
In the invention, the auxiliary agent is preferably Ba, Na, K or Cs.
The invention preferably selects the mol ratio of the Fe to the auxiliary agent as 1-8: 1.
another object of the present invention is to provide a method for preparing the above catalyst, which comprises the following steps: mixing the roasted molecular sieve with a ferric nitrate solution, stirring for 1-3h at 50-80 ℃, separating, washing the separated solid to be neutral, drying, and roasting for 0.5-3h at 400-550 ℃ in a plasma atmosphere; secondly, mixing the product obtained in the step I with a salt solution containing an auxiliary agent, stirring for 1-3h at 50-80 ℃, separating, washing the solid obtained by separation to be neutral, drying, and roasting for 0.5-3h at 400-550 ℃ in a plasma atmosphere; or mixing the roasted molecular sieve with a salt solution containing an auxiliary agent, stirring for 1-3h at 50-80 ℃, separating, washing the separated solid to be neutral, drying, and roasting for 0.5-3h at 400-550 ℃ in a plasma atmosphere; secondly, mixing the product obtained in the step I with ferric nitrate solution, stirring for 1-3h at 50-80 ℃, separating, washing the solid obtained by separation to be neutral, drying, and roasting for 0.5-3h at 400-550 ℃ in a plasma atmosphere; or mixing the roasted molecular sieve, ferric nitrate solution and salt solution containing the auxiliary agent, stirring for 1-3h at 50-80 ℃, separating, washing the separated solid to be neutral, drying, and roasting for 0.5-3h at 400-550 ℃ in a plasma atmosphere.
In the invention, the plasma atmosphere is preferably air and N2Ar, He and H2At least one of (1).
It is still another object of the present invention to provide a catalyst prepared by the above method at high SO concentration2And O2And 4, application of denitration.
The application method of the invention is preferably as follows: SO (SO)2In a concentration of 300-800ppm, O2The concentration of (A) is 5-15 vol%, the concentration of NO is 500-1500ppm, and the reaction temperature is 200-450 ℃.
The invention has the beneficial effects that:
the catalyst of the invention can directly decompose NO into N2And O2The method has the outstanding advantages of no secondary pollution, no use of reducing agents, good economy, simple process and the like, is an optimal denitration way, and is particularly suitable for denitration of tail gas of diesel engines used by mobile sources such as ships and the like.
The catalyst of the invention realizes the purpose of adding SO2Concentration 500ppm, O2In a complex atmosphere with the concentration of 10 vol.% and the NO concentration of 1000ppm and under the low-temperature condition of 350 ℃, the NO removal rate is as high as 60%, and the denitration performance of the catalyst is stable within 10 hours of reaction; in addition, the catalyst of the invention also has SO removal function2Ability, SO2The removal rate was 45%.
The catalyst provided by the invention can provide guarantee for normal operation of ships under IMO (international mobile oxidation) saltpeter-limiting instruction in China, break monopoly of products prepared by high-end ships in Europe and America, and promote the development of China to ship building and the forcing state.
Drawings
In the figure 2 of the attached drawings of the invention,
FIG. 1 is a graph showing the effect of the sequence of modification with an auxiliary and exchange of metal ions on the denitration performance of a Fe-HZSM-5 catalyst;
FIG. 2 shows SO in high concentration2And O2The stability diagram of the Cs-Fe-HZSM-5 catalyst was studied under an atmosphere.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The raw material gas used in the following comparative examples and examples was a simulated marine exhaust gas atmosphere, and the raw material gas had a NO concentration of 1000 to 1200ppm and SO2Concentration of 450-500ppm, O2Concentration 10 vol%, N2The total flow of the raw material gas is 1.0-1.1L/min for balance gas; the NO decomposition reactor is a continuous flow type fixed bed quartz reactor; the catalyst is filled in a reaction zone of the quartz reactor, the filling amount of the catalyst is 2g, the length of the corresponding reaction zone is 50-65mm, and the space velocity is 15000-20000h-1(ii) a The reaction temperature is 300-550 ℃; and detecting and evaluating the NO decomposition and denitration effects of different catalysts by using a Madu infrared flue gas analyzer.
Comparative example 1
The NO decomposition reactor was packed with Fe/HZSM-5 catalyst and the results are shown in Table 1.
Example 1
A preparation method of Fe-Ba/HZSM-5 catalyst comprises the following steps:
mixing the roasted molecular sieve with a barium nitrate solution, stirring for 2 hours at 70 ℃, separating, washing the separated solid to be neutral, drying for 3 hours at 120 ℃, and roasting for 3 hours at 500 ℃ in an air plasma atmosphere;
secondly, mixing the product obtained in the step I with ferric nitrate solution, stirring for 2 hours at 70 ℃, separating, washing the solid obtained by separation to be neutral, drying for 3 hours at 120 ℃, and then roasting for 3 hours at 500 ℃ in air plasma atmosphere to obtain the Fe-Ba/HZSM-5 catalyst, wherein: the molar ratio of Fe to Ba is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was packed with Fe-Ba/HZSM-5 catalyst, and the results are shown in Table 1.
Example 2
A preparation method of an Fe-Na-HZSM-5 catalyst is different from that of the example 1 in that: mixing the roasted molecular sieve with a sodium nitrate solution to obtain the Fe-Na-HZSM-5 catalyst, wherein: the molar ratio of Fe to Na is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was packed with Fe-Na-HZSM-5 catalyst, and the results are shown in Table 1.
Example 3
A preparation method of a Fe-K-HZSM-5 catalyst is different from that of the example 1 in that: mixing the roasted molecular sieve with a potassium nitrate solution to obtain the Fe-K-HZSM-5 catalyst, wherein: the molar ratio of Fe to K is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was packed with Fe-K-HZSM-5 catalyst and the results are shown in Table 1.
Example 4
A preparation method of an Fe-Cs-HZSM-5 catalyst is different from that of the example 1 in that: mixing the roasted molecular sieve with a cesium nitrate solution to obtain the Fe-Cs-HZSM-5 catalyst, wherein: the molar ratio of Fe to Cs is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was packed with Fe-Cs-HZSM-5 catalyst and the results are shown in Table 1.
Example 5
A preparation method of a Ba-Fe-HZSM-5 catalyst comprises the following steps:
mixing the roasted molecular sieve with a ferric nitrate solution, stirring for 2 hours at 70 ℃, separating, washing the separated solid to be neutral, drying for 3 hours at 120 ℃, and roasting for 3 hours at 500 ℃ in an air plasma atmosphere;
secondly, mixing the product obtained in the step I with a barium nitrate solution, stirring for 2 hours at 70 ℃, separating, washing the solid obtained by separation to be neutral, drying for 3 hours at 120 ℃, and then roasting for 3 hours at 500 ℃ in an air plasma atmosphere to obtain the Ba-Fe-HZSM-5 catalyst, wherein: the molar ratio of Fe to Ba is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was filled with Ba-Fe-HZSM-5 catalyst modified with Ba as an auxiliary agent, and the results are shown in table 1.
Example 6
A preparation method of a Na-Fe-HZSM-5 catalyst is different from that of the example 5 in that: mixing the product obtained in the step I with a sodium nitrate solution to obtain the Na-Fe-HZSM-5 catalyst, wherein: the molar ratio of Fe to Na is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was packed with Na-Fe-HZSM-5 catalyst, and the results are shown in Table 1.
Example 7
A preparation method of a K-Fe-HZSM-5 catalyst is different from that of the example 5 in that: mixing the product obtained in the step I with a potassium nitrate solution to obtain the K-Fe-HZSM-5 catalyst, wherein: the molar ratio of Fe to K is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was packed with K-Fe-HZSM-5 catalyst and the results are shown in Table 1.
Example 8
A preparation method of a Cs-Fe-HZSM-5 catalyst is different from that of the embodiment 5 in that: mixing the product obtained in the step I with a cesium nitrate solution to obtain a Cs-Fe-HZSM-5 catalyst, wherein: the molar ratio of Fe to Cs is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was packed with Cs-Fe-HZSM-5 catalyst and the results are shown in Table 1.
And (4) conclusion: compared with the comparative example 1, the (1) auxiliary agent modified Fe/HZSM-5 catalyst can be obtained, and the NO removal rate is obviously improved; (2) the Fe/HZSM-5 catalyst modified by different additives has great influence on the NO removal effect, and Ba and Cs additives are preferred; (3) in the preparation process of the catalyst, the NO removal rate of the catalyst is obviously influenced by the ion exchange sequence, and the NO removal rate of the Cs-Fe-HZSM-5 catalyst is obviously superior to that of the Fe-Cs-HZSM-5 catalyst. In addition, the catalyst can obviously promote SO besides the removal effect on NO2Removal of at SO2The concentration of the oxygen and the oxygen is 450-500ppm2The denitration performance of the Cs-Fe-HZSM-5 catalyst is stable under the complex atmosphere with the concentration of 10 vol%, which shows that the sulfur resistance of the catalyst is good.
Example 9
A preparation method of a Cs/Fe/HZSM-5 catalyst comprises the following steps:
mixing the roasted molecular sieve, an iron nitrate solution and a cesium nitrate solution, stirring for 2 hours at 70 ℃, separating, washing the separated solid to be neutral, drying for 3 hours at 120 ℃, and roasting for 3 hours at 500 ℃ in an air plasma atmosphere to obtain the Cs/Fe/HZSM-5 catalyst, wherein: the molar ratio of Fe to Cs is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was packed with Cs/Fe/HZSM-5 catalyst modified with Cs as a promoter with the results shown in table 1.
Example 10
A preparation method of a Cs/Fe/HZSM-5 catalyst is different from that of the embodiment 9 in that: calcining in He plasma atmosphere to obtain the Cs/Fe/HZSM-5 catalyst, wherein: the molar ratio of Fe to Cs is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was packed with Cs/Fe/HZSM-5 catalyst modified with Cs as a promoter with the results shown in table 1.
Example 11
A preparation method of a Cs/Fe/HZSM-5 catalyst is different from that of the embodiment 9 in that: at H2Roasting in plasma atmosphere to obtain the Cs/Fe/HZSM-5 catalyst, wherein: the molar ratio of Fe to Cs is 2: 1, Fe represents 0.30 wt.% of the catalyst weight percent.
The NO decomposition reactor was packed with Cs/Fe/HZSM-5 catalyst modified with Cs as a promoter with the results shown in table 1.
And (4) conclusion: the preparation method of the catalyst has influence on the denitration performance of the catalyst, and the step-by-step exchange method is superior to the common exchange method; the catalyst calcined in He plasma atmosphere works best.
Example 12
A preparation method of a Cs-Fe-HZSM-5 catalyst is different from that of the embodiment 8 in that: obtaining the Cs-Fe-HZSM-5 catalyst, wherein: the molar ratio of Fe to Cs is 4: 1, Fe represents 0.60 wt.% of the catalyst weight percent.
The NO decomposition reactor was filled with Cs-Fe-HZSM-5 catalyst modified with Cs as an auxiliary agent, and the results are shown in table 1.
Example 13
A preparation method of a Cs-Fe-HZSM-5 catalyst is different from that of the embodiment 8 in that: obtaining the Cs-Fe-HZSM-5 catalyst, wherein: the molar ratio of Fe to Cs is 1: 1, Fe represents 0.15 wt.% of the catalyst weight percent.
The NO decomposition reactor was filled with Cs-Fe-HZSM-5 catalyst modified with Cs as an auxiliary agent, and the results are shown in table 1.
Example 14
A preparation method of a Cs-Fe-HZSM-5 catalyst is different from that of the embodiment 8 in that: obtaining the Cs-Fe-HZSM-5 catalyst, wherein: the molar ratio of Fe to Cs is 6: 1, Fe represents 0.90 wt.% of the catalyst weight percent.
The NO decomposition reactor was filled with Cs-Fe-HZSM-5 catalyst modified with Cs as an auxiliary agent, and the results are shown in table 1.
Example 15
A preparation method of a Cs-Fe-HZSM-5 catalyst is different from that of the embodiment 8 in that: obtaining the Cs-Fe-HZSM-5 catalyst, wherein: the molar ratio of Fe to Cs is 8: 1, Fe comprises 1.20 wt.% of the catalyst weight percent.
The NO decomposition reactor was filled with Cs-Fe-HZSM-5 catalyst modified with Cs as an auxiliary agent, and the results are shown in table 1.
TABLE 1
| NO conversion (%) | Optimum denitration temperature (. degree.C.) | |
| Comparative example 1 | 35.2 | 400 |
| Example 1 | 57.8 | 400 |
| Example 2 | 50.2 | 400 |
| Example 3 | 53.2 | 400 |
| Example 4 | 43.6 | 400 |
| Example 5 | 55.2 | 400 |
| Example 6 | 57.3 | 400 |
| Example 7 | 54.3 | 400 |
| Example 8 | 57.3 | 350 |
| Example 9 | 48.6 | 350 |
| Example 10 | 54.5 | 350 |
| Example 11 | 50.3 | 350 |
| Example 12 | 59.7 | 350 |
| Example 13 | 48.0 | 350 |
| Example 14 | 63.1 | 350 |
| Example 15 | 62.5 | 350 |
Claims (8)
1. The composite molecular sieve catalyst for NO decomposition and denitration is characterized in that: the catalyst comprises an iron-based active component and a molecular sieve;
the iron-based active component comprises Fe and an auxiliary agent, wherein the auxiliary agent is at least one of Ba, Cs, Na, K, Mg, Ca, Li, Ce, Sm and La, and the molar ratio of Fe to the auxiliary agent is 1-10: 1;
the molecular sieve is HZSM-5;
the Fe accounts for 0.02-10.00 wt% of the weight percent of the catalyst.
2. The composite molecular sieve catalyst for NO decomposition denitration according to claim 1, characterized in that: the auxiliary agent is at least one of Ba, Na, K and Cs.
3. The composite molecular sieve catalyst for NO decomposition denitration according to claim 2, characterized in that: the auxiliary agent is Ba, Na, K or Cs.
4. The composite molecular sieve catalyst for NO decomposition denitration according to claim 3, characterized in that: the molar ratio of Fe to the auxiliary agent is 1-8: 1.
5. a process for preparing the catalyst of claim 1, 2, 3 or 4, characterized in that: the preparation method comprises the following steps:
mixing the roasted molecular sieve with a ferric nitrate solution, stirring for 1-3h at 50-80 ℃, separating, washing the separated solid to be neutral, drying, and roasting for 0.5-3h at 400-550 ℃ in a plasma atmosphere;
secondly, mixing the product obtained in the step I with a salt solution containing an auxiliary agent, stirring for 1-3h at 50-80 ℃, separating, washing the solid obtained by separation to be neutral, drying, and roasting for 0.5-3h at 400-550 ℃ in a plasma atmosphere;
or mixing the roasted molecular sieve with a salt solution containing an auxiliary agent, stirring for 1-3h at 50-80 ℃, separating, washing the separated solid to be neutral, drying, and roasting for 0.5-3h at 400-550 ℃ in a plasma atmosphere;
secondly, mixing the product obtained in the step I with ferric nitrate solution, stirring for 1-3h at 50-80 ℃, separating, washing the solid obtained by separation to be neutral, drying, and roasting for 0.5-3h at 400-550 ℃ in a plasma atmosphere;
or mixing the roasted molecular sieve, ferric nitrate solution and salt solution containing the auxiliary agent, stirring for 1-3h at 50-80 ℃, separating, washing the separated solid to be neutral, drying, and roasting for 0.5-3h at 400-550 ℃ in a plasma atmosphere.
6. The method of claim 5, wherein: the plasma atmosphere is airGas, N2Ar, He and H2At least one of (1).
7. The catalyst of claim 1, 2, 3 or 4 in high SO concentrations2And O2And 4, application of denitration.
8. Use according to claim 7, characterized in that: the application method comprises the following steps: SO (SO)2In a concentration of 300-800ppm, O2The concentration of (A) is 5-15 vol%, the concentration of NO is 500-1500ppm, and the reaction temperature is 200-450 ℃.
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| CN111921556B (en) | 2023-08-22 |
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