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CN109647501B - Hierarchical porous Fe-beta molecular sieve catalyst and preparation method and application thereof - Google Patents

Hierarchical porous Fe-beta molecular sieve catalyst and preparation method and application thereof Download PDF

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CN109647501B
CN109647501B CN201910049389.1A CN201910049389A CN109647501B CN 109647501 B CN109647501 B CN 109647501B CN 201910049389 A CN201910049389 A CN 201910049389A CN 109647501 B CN109647501 B CN 109647501B
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CN109647501A (en
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贺泓
朱娜
单文坡
连志华
张燕
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Hefei Zhongke Hongyi Environmental Protection Technology Co ltd
Ningbo Beilun Zhongke Haixi Industrial Technology Innovation Center
Institute of Urban Environment of CAS
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Ningbo Urban Environment Observation And Research Station-Nueors Chinese Academy Of Sciences
Institute of Urban Environment of CAS
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

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Abstract

本发明涉及一种多级孔Fe‑β分子筛催化剂及其制备方法和用途；所述制备方法采用有机胺水溶液水热处理β分子筛得到多级孔β分子筛，随后通过离子交换得到多级孔Fe‑β分子筛催化剂，将本发明所制备的催化剂用作氨气选择性催化还原氮氧化物时，其相对于单纯采用离子交换法制备得到的Fe‑β分子筛催化剂在150‑225℃的温度范围内的催化活性明显提高，在225℃的氮氧化物转化率即可达到78％，且其抗C3H6中毒的性能也明显提高。

Figure 201910049389

The invention relates to a multi-level porous Fe-β molecular sieve catalyst, a preparation method and application thereof; the preparation method adopts the hydrothermal treatment of an organic amine aqueous solution to obtain a beta molecular sieve, and then obtains a multi-level porous Fe-β molecular sieve by ion exchange. Molecular sieve catalyst, when the catalyst prepared by the present invention is used as the selective catalytic reduction of nitrogen oxides by ammonia gas, its catalysis in the temperature range of 150-225 ° C is compared with that of the Fe-β molecular sieve catalyst prepared by simply adopting the ion exchange method. The activity is obviously improved, the nitrogen oxide conversion rate at 225°C can reach 78%, and its anti-C 3 H 6 poisoning performance is also significantly improved.

Figure 201910049389

Description

Hierarchical porous Fe-beta molecular sieve catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalytic materials, in particular to a hierarchical pore Fe-beta molecular sieve catalyst and a preparation method and application thereof.
Background
NO in the atmospherexMainly, the emission of exhaust gas from industrial processes related to combustion and exhaust gas from motor vehicles, ships and the like is an important cause of environmental pollution such as acid rain, photochemical smog, haze and the like. At present, NOxThe main method of removal is NOxStorage reduction and ammonia selective catalytic reduction. Among them, the selective catalytic reduction method of ammonia gas has the advantages of high removal efficiency, low cost, etc., and is receiving wide attention. The key to the research of the ammonia selective catalytic reduction method is the catalyst. Among the molecular sieve catalysts, the modified molecular sieve catalyst is considered to be a catalyst for ammonia selective catalytic reduction with practical application prospect due to excellent activity and selectivity, wide activity window and high-temperature thermal stability. Cu-based and Fe-based molecular sieve catalysts are the most studied systems at present. The Cu-based molecular sieve has excellent low-temperature performance, but the high-temperature activity and the sulfur resistance of the Cu-based molecular sieve are required to be further improved, the activity of Fe-based molecular sieve catalysts (Fe-beta molecular sieve catalysts and Fe-ZSM-5 molecular sieve catalysts) is mainly concentrated in a middle-high temperature region of 300-plus-500 ℃, and NO is removed in a middle-low temperature region of 200-plus-300 DEG CxThe efficiency of (2) is not ideal.
CN107029781A discloses a selective reduction catalyst of iron and cerium modified beta molecular sieve, a preparation method and an application thereof, a template-free synthesized beta zeolite molecular sieve with low silica-alumina ratio is used as a catalyst matrix component, Fe and Ce ions are introduced in a liquid ion exchange-impregnation mode, and the weight percentage of Fe element is 0.5-8.0 percent and the weight percentage of Ce element is 0.5-6.0 percent based on the total weight of the powdery catalyst modified by ion exchange-impregnation; beta zeolite molecular sieve silicon-aluminium ratio (mol ratio nSiO)2/nAl2O3) In the range of 7.8 to 20, for treating a gas containing NOxA gas stream; catalysis of the catalyst obtained in this schemeThe activity temperature window is narrow, the maximum value of the conversion rate of nitrogen oxides is reached at 250 ℃, then the activity begins to decline, and the preparation process of the catalyst is complex and the cost is high.
CN105314647A discloses a silicon-aluminum beta or silicon-iron beta molecular sieve, a catalyst for purifying automobile exhaust prepared from the molecular sieve, and a preparation method and application of the molecular sieve and the catalyst; the method for preparing the ferrosilicon beta molecular sieve comprises the following steps of (1) preparing sol: mixing template agent, alkali and water, adding iron source and silicon source, and stirring at 25-45 deg.C; (2) taking the sol obtained in the step (1), adding 0.1-5 wt% (relative to SiO in silicon source)2Weight) seed crystal is added into a pressure kettle, stirred and crystallized for 2 to 6 days at the temperature of 135-; (4) and (3) calcining the product obtained in the step (3) at high temperature to obtain the ferrosilicon beta molecular sieve, wherein the preparation method of the scheme is complex and has high cost, and the prepared catalyst has poor low-temperature activity.
CN102513145A discloses NO in acrylonitrile oxidation tail gasxA purified Fe molecular sieve SCR catalyst and a preparation method thereof; it uses commercial ZSM-5 molecular sieve, Y-type molecular sieve, ferrierite or beta molecular sieve as carrier, and adopts impregnation method or ion exchange method to introduce Fe whose mass fraction is 0.3-10.0%3+Is used as an active component, and 0.5-8.0 percent of M (lanthanum La or cobalt Co) is introduced as a modification component; the Fe-beta molecular sieve catalyst obtained by the scheme has poor activity below 250 ℃, and the catalyst has complex preparation process and high cost.
Although the above documents provide some preparation methods of Fe- β molecular sieve catalysts, there are still problems of complex catalyst preparation process, high cost, poor low-temperature activity of the catalyst or narrow temperature window, so it is of great significance to develop a simple preparation method to improve the low-temperature activity of the catalyst.
Disclosure of Invention
The invention aims to provide a hierarchical pore Fe-beta molecular sieve catalyst and a preparation method and application thereof; the preparation method adopts organic amine aqueous solution to carry out hydrothermal treatment on the beta molecular sieve to obtain the hierarchical pore beta molecular sieve, and then the hierarchical pore beta molecular sieve is obtained through ion exchangeWhen the catalyst is used as a catalyst for catalyzing ammonia selective catalytic reduction of nitrogen oxides in a multi-level pore Fe-beta molecular sieve catalyst, compared with the Fe-beta molecular sieve catalyst prepared by a simple ion exchange method, the catalytic activity of the catalyst in the temperature range of 150-225 ℃ is obviously improved, the conversion rate of the nitrogen oxides at 225 ℃ can reach 78%, and the C resistance of the catalyst is C-resistant3H6The poisoning performance is also significantly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a hierarchical pore Fe- β molecular sieve catalyst, the method comprising the steps of:
(1) treating the beta molecular sieve by using an organic amine aqueous solution to obtain a hierarchical pore beta molecular sieve;
(2) and (2) loading Fe on the hierarchical pore beta molecular sieve obtained in the step (1) through ion exchange to obtain the hierarchical pore Fe-beta molecular sieve catalyst.
According to the invention, the pore structure in the beta molecular sieve is increased by adopting a method of hydrothermally treating the beta molecular sieve by using an organic amine aqueous solution, the prepared hierarchical pore beta molecular sieve contains pore structures with different scales, and the hierarchical pore beta molecular sieve has excellent hydrothermal stability of a microporous molecular sieve crystal and excellent diffusion and transmission performance of a mesoporous material, on one hand, the structure increases the diffusion rate of reactant molecules in pores, and on the other hand, more ion exchange sites are provided for Fe on the surface of the beta molecular sieve, so that more reaction active sites are provided for catalytic reaction, and the activity of the catalytic reaction is improved; compared with the Fe-beta molecular sieve catalyst prepared by a simple ion exchange method, the multi-level pore Fe-beta molecular sieve catalyst prepared by the preparation method of the multi-level pore Fe-beta molecular sieve catalyst has the advantages that the specific surface area is increased, the Fe loading capacity is increased under the same ion exchange condition, and the catalytic activity is obviously improved within the temperature range of 150-225 ℃.
Preferably, the silica-alumina ratio of the beta molecular sieve in the step (1) is 10-50, such as 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45 or 50, etc., preferably 20-30, preferably 25.
Preferably, the organic amine in the aqueous organic amine solution includes any one or a mixture of at least two of tetraethylammonium hydroxide, triethylamine, diethanolamine, or di-n-propylamine, and the mixture illustratively includes a mixture of tetraethylammonium hydroxide and triethylamine, a mixture of diethanolamine and di-n-propylamine, or a mixture of triethylamine and diethanolamine, and the like, preferably tetraethylammonium hydroxide.
The method adopts organic amine as a template agent of the beta molecular sieve, can dissolve part of the beta molecular sieve in the hydrothermal treatment process, and takes the organic amine as the template agent to carry out recrystallization to form a micropore-mesopore (macropore) hierarchical pore structure.
Preferably, the concentration of the organic amine in the organic amine aqueous solution is 0.1 to 1mol/L, such as 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L, etc., preferably 0.3 mol/L.
Preferably, the method for treating beta molecular sieve by using the organic amine aqueous solution in the step (1) comprises the following steps:
(a) mixing the beta molecular sieve with an organic amine aqueous solution, and stirring;
(b) carrying out hydrothermal treatment on the product obtained in the step (a);
(c) and (c) filtering, washing, drying and roasting the product obtained in the step (b) to obtain the hierarchical pore beta molecular sieve.
Preferably, the ratio of the mass of the beta molecular sieve in step (a) to the volume of the aqueous organic amine solution is 0.033 to 0.1g/mL, such as 0.033g/mL, 0.04g/mL, 0.05g/mL, 0.06g/mL, 0.07g/mL, 0.08g/mL, 0.09g/mL, or 0.1g/mL, and the like.
Preferably, the temperature of the hydrothermal treatment in step (b) is 120-.
Preferably, the hydrothermal treatment time of the step (b) is 24-168 h; for example 24h, 36h, 48h, 60h, 72h, 84h, 96h, 108h, 120h, 132h, 144h or 168h, etc., preferably 72 h.
The method adopts hydrothermal treatment to dissolve and recrystallize the beta molecular sieve, thereby forming a hierarchical pore structure.
Preferably, the temperature of the calcination in step (c) is 450-600 deg.C, such as 450 deg.C, 480 deg.C, 500 deg.C, 550 deg.C, 570 deg.C or 600 deg.C, etc., preferably 550 deg.C.
Preferably, the calcination time in step (c) is 3-10h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc., preferably 5 h.
Preferably, the temperature rise rate of the calcination in step (c) is 1-5 deg.C/min, such as 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, or 5 deg.C/min, etc., preferably 2 deg.C/min.
Preferably, the ion exchange method of step (2) comprises the following steps:
(a') mixing the hierarchical pore beta molecular sieve prepared in the step (1) with an iron salt aqueous solution, and stirring for ion exchange;
(b ') filtering, washing, drying and roasting the product obtained in the step (a') to obtain the hierarchical porous Fe-beta molecular sieve catalyst.
Preferably, the iron salt in the iron salt aqueous solution of step (a') includes any one or a mixture of at least two of ferrous chloride, ferrous sulfate, ferric nitrate or ferrocene, and the mixture exemplarily includes a mixture of ferrous chloride and ferrous sulfate, a mixture of ferric nitrate and ferrous sulfate, or ferrocene, a mixture of ferrous chloride and ferric nitrate, and the like.
Preferably, the concentration of the aqueous iron salt solution of step (a') is 0.01-0.25mol/L, such as 0.01mol/L, 0.03mol/L, 0.05mol/L, 0.08mol/L, 0.13mol/L, 0.15mol/L, 0.17mol/L, 0.2mol/L, 0.22mol/L or 0.25mol/L, etc., preferably 0.05 mol/L.
Preferably, the ratio of the mass of the hierarchical pore beta molecular sieve to the volume of the aqueous solution of the iron salt in step (a') is 0.004-0.0067g/mL, such as 0.004g/mL, 0.005g/mL, 0.006g/mL, 0.0067g/mL or the like, preferably 0.005 g/mL.
Preferably, the temperature at which the stirring for ion exchange in step (a') is carried out is between room temperature and 90 ℃, preferably between 60 and 80 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, and more preferably 80 ℃.
Preferably, the stirring of step (a') is performed for 5-48h, such as 5h, 7h, 10h, 15h, 18h, 24h, 28h, 32h, 36h, 40h, 44h or 48h, etc., preferably 24 h.
Preferably, the temperature of the calcination in step (b') is 400-.
Preferably, the calcination time in step (b') is 3-10h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc., preferably 3 h.
Preferably, the temperature rise rate of the calcination in step (b') is 1-10 deg.C/min, such as 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min or 10 deg.C/min, preferably 5 deg.C/min.
As a preferable technical scheme, the preparation method of the hierarchical porous Fe-beta molecular sieve catalyst comprises the following steps:
(1') mixing a beta molecular sieve with the silicon-aluminum ratio of 10-50 and an aqueous solution of tetraethylammonium hydroxide with the concentration of 0.1-1mol/L according to the proportion of 0.033-0.1 g/mL;
(2 ') hydrothermal treatment of the product obtained in step (1') at a temperature of 120 ℃ and 150 ℃ for 24-168 h;
(3 ') filtering, washing and drying the product obtained in the step (2'), and then roasting at the temperature of 450 ℃ and 600 ℃ for 3-10h to obtain the hierarchical pore beta molecular sieve;
(4 ') mixing the hierarchical pore beta molecular sieve prepared in the step (3') with a ferric salt aqueous solution with the concentration of 0.01-0.25mol/L according to the proportion of 0.004-0.0067g/mL, and stirring at the temperature of 60-80 ℃ for ion exchange for 5-48 h;
(5 ') filtering, washing and drying the product obtained in the step (4'), and finally roasting at the temperature of 400 ℃ and 600 ℃ for 3-10h to obtain the hierarchical porous Fe-beta molecular sieve catalyst.
In a second aspect, the invention provides a hierarchical pore Fe-beta molecular sieve catalyst prepared by the preparation method of the first aspect.
Compared with the Fe-beta molecular sieve catalyst prepared by only adopting an ion exchange method, the low-temperature activity of the multi-stage porous Fe-beta molecular sieve catalyst is obviously improved within the temperature range of 150-225 ℃, the selectivity of the multi-stage porous Fe-beta molecular sieve catalyst to nitrogen within the temperature range of 150-550 ℃ is 100 percent, and the multi-stage porous Fe-beta molecular sieve catalyst resists C3H6The poisoning performance is also significantly improved.
In a third aspect, the present invention provides the use of a hierarchical pore Fe- β molecular sieve catalyst as described in the second aspect as a catalyst for the selective catalytic reduction of nitrogen oxides with ammonia.
Preferably, the hierarchical porous Fe-beta molecular sieve catalyst is used as a catalyst for selective catalytic reduction of nitrogen oxides in the mobile source tail gas and/or the fixed source flue gas by ammonia gas.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) compared with the Fe-beta molecular sieve catalyst prepared by a simple ion exchange method, the Fe-beta molecular sieve catalyst prepared by the preparation method of the hierarchical pore Fe-beta molecular sieve catalyst has larger BET specific surface area, and the Fe loading capacity is obviously improved;
(2) compared with the Fe-beta molecular sieve catalyst prepared by a simple ion exchange method, the Fe-beta molecular sieve catalyst prepared by the preparation method of the multi-level pore Fe-beta molecular sieve catalyst has obviously improved catalytic activity within the temperature range of 150 ℃ and 225 ℃, and the conversion rate of nitrogen oxides at 225 ℃ can reach 78%;
(3) compared with the Fe-beta molecular sieve catalyst prepared by a simple ion exchange method, the multi-stage pore Fe-beta molecular sieve catalyst has the anti-C property3H6The poisoning performance is also obviously improved;
(4) the preparation method of the hierarchical porous Fe-beta molecular sieve catalyst is simple, low in cost and easy for industrial application.
Drawings
FIG. 1 is a graph comparing the activity of catalysts prepared in example 1 of the present invention and comparative example 1 for catalyzing ammonia gas to reduce nitrogen oxides;
FIG. 2 is a graph comparing the selectivity of catalysts prepared in example 1 of the present invention and comparative example 1 for nitrogen in the process of catalyzing ammonia gas to reduce nitrogen oxides;
FIG. 3 shows that the catalysts prepared in example 1 and comparative example 1 of the present invention do not contain C in the reaction gas3H6And contain C3H6Activity comparison of catalytic ammonia reduction of nitrogen oxides under the conditions of (1).
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
(1) Mixing a beta molecular sieve with the silicon-aluminum ratio of 25 with 60mL of tetraethylammonium hydroxide aqueous solution with the concentration of 0.3mol/L according to the proportion of 0.05g/mL, and stirring for 1 h;
(2) carrying out hydrothermal treatment on the product of the step (1) at the temperature of 140 ℃ for 72 h;
(3) filtering the product obtained in the step (2), washing the product to be neutral, drying the product at 100 ℃ for 12h, and roasting the product at 550 ℃ for 5h to obtain the hierarchical pore beta molecular sieve;
(4) mixing the hierarchical pore beta molecular sieve prepared in the step (3) with 200mL of ferrous chloride aqueous solution with the concentration of 0.05mol/L according to the proportion of 0.005g/mL, and stirring at 80 ℃ for ion exchange for 24 hours;
(5) and (3) filtering the product obtained in the step (4), washing with water to be neutral, drying at 100 ℃ for 12h, and finally roasting at 500 ℃ for 5h to obtain the hierarchical porous Fe-beta molecular sieve catalyst, wherein the hierarchical porous Fe-beta molecular sieve catalyst is marked as hierarchical porous Fe-beta.
The structural data and the Fe content of the hierarchical porous Fe-beta molecular sieve catalyst prepared in the embodiment are shown in Table 1; the activity diagrams of the hierarchical porous Fe-beta molecular sieve catalyst for catalyzing ammonia gas to reduce nitrogen oxides are shown in figures 1 and 3, the selectivity of the hierarchical porous Fe-beta molecular sieve catalyst for catalyzing ammonia gas to reduce nitrogen oxides is shown in figure 2, and the conversion rate of nitrogen oxides of the hierarchical porous Fe-beta molecular sieve catalyst obtained in the embodiment at 225 ℃ is shown in table 2.
Example 2
This example differs from example 1 in that: replacing the silicon-aluminum ratio of the beta molecular sieve from 25 to 50, and replacing 0.3mol/L tetraethylammonium hydroxide aqueous solution with 0.5mol/L triethylamine aqueous solution with the same volume; replacing the temperature of the hydrothermal treatment in the step (2) with 150 ℃, and replacing the time of the hydrothermal treatment with 48 h; replacing the roasting temperature in the step (3) with 600 ℃; replacing the 0.05mol/L ferrous chloride aqueous solution with 0.05mol/L ferrous sulfate aqueous solution with the same volume; the temperature of the ion exchange in step (4) was replaced with 60 ℃ and other conditions were exactly the same as in example 1.
The nitrogen oxide conversion of the hierarchical porous Fe-beta molecular sieve catalyst obtained in this example at 225 ℃ is shown in Table 2.
Example 3
This example differs from example 1 in that: replacing 0.3mol/L tetraethylammonium hydroxide aqueous solution with 0.5mol/L diethanolamine aqueous solution with the same volume; replacing the temperature of the hydrothermal treatment in the step (2) with 120 ℃, and replacing the time of the hydrothermal treatment in the step (2) with 120 h; replacing the roasting time in the step (3) with 8 hours; replacing the 0.05mol/L ferrous chloride aqueous solution in the step (4) with 0.1mol/L ferric nitrate aqueous solution with the same volume; the ion exchange temperature in step (4) was replaced with 70 ℃ and other conditions were exactly the same as in example 1.
The nitrogen oxide conversion of the hierarchical porous Fe-beta molecular sieve catalyst obtained in this example at 225 ℃ is shown in Table 2.
Example 4
This example differs from example 1 in that: replacing 0.3mol/L tetraethylammonium hydroxide aqueous solution with an equal volume of 0.8mol/L di-n-propylamine aqueous solution; replacing the 0.05mol/L ferrous chloride aqueous solution in the step (4) with an equal volume of 0.1mol/L ferrocene aqueous solution; replacing the ion exchange temperature of the step (4) with room temperature, and replacing the roasting temperature of the step (5) with 450 ℃.
The nitrogen oxide conversion of the hierarchical porous Fe-beta molecular sieve catalyst obtained in this example at 225 ℃ is shown in Table 2.
Comparative example 1
This comparative example used only step (4) and step (5) of example 1, and the hierarchical pore beta molecular sieve in step (4) was replaced with an equal mass of beta molecular sieve in step (1) of example 1 that was not hydrothermally treated with an aqueous organic amine solution; otherwise, the catalyst was labeled as Fe-beta, exactly as in example 1.
The structural data and Fe content of the Fe-beta catalyst obtained in the comparative example are shown in Table 1; the activity diagrams of the catalyst for ammonia gas to reduce nitrogen oxides are shown in figure 1 and figure 3; the selectivity graph of the catalyst for ammonia gas to reduce nitrogen oxides is shown in figure 2; the conversion of nitrogen oxides at 225 ℃ of the Fe-beta catalyst obtained in this comparative example is shown in Table 2.
The activity evaluation method of the catalysts prepared in examples 1 to 4 and comparative example 1 is to take catalyst particles of 40 to 60 meshes to perform an experiment for catalyzing ammonia gas to reduce nitrogen oxides on a fixed bed reactor.
Does not contain C3H6The experimental inlet composition was: [ NO ]]＝[NH3]＝500ppm，[O2]＝5％，N2As the balance Gas, the total flow rate of the Gas is 500mL/min, and the space velocity (GHSV) of the Gas is 200000h-1The reaction temperature is 150-550 ℃.
Containing C3H6The experimental inlet composition was: [ NO ]]＝[NH3]＝500ppm，[C3H6]＝500ppm，[O2]＝5％，N2As balance gas, the total flow of the gas is 500mL/min, and the space velocity of the gas is 200000h-1The reaction temperature is 150-550 ℃; catalyst obtained in example 1 in the presence of C3H6The test result under the test conditions of (1) is marked as hierarchical pore Fe-beta + C3H6Comparative example 1 the catalyst obtained in the presence of C3H6The test result under the test conditions of (1) is labeled as Fe-beta + C3H6。
The analysis method comprises the following steps: NO and NH3And by-product N2O、NO2The content of (D) was measured by means of an infrared gas analyzer (Nicolet Antaris IGS).
FIG. 1 is a graph comparing the activity of catalysts prepared in example 1 of the present invention and comparative example 1 for catalyzing ammonia gas to reduce nitrogen oxides; as can be seen from the graph, the activity of the hierarchical porous Fe-beta prepared by the preparation method of the present invention at low temperature is significantly improved compared to that of comparative example 1 under the same reaction conditions.
FIG. 2 is a graph comparing the selectivity of catalysts prepared in example 1 of the present invention and comparative example 1 for nitrogen in the process of catalyzing ammonia gas to reduce nitrogen oxides; it can be seen from the figure that the nitrogen selectivity of the multi-stage pore Fe- β prepared in example 1 in the whole reaction process reaches 100%, which indicates that the catalyst is suitable for purifying nitrogen oxides in tail gas of fixed sources and mobile sources, especially nitrogen oxides at low temperature, and indicates that the method for improving the low-temperature performance of the catalyst by introducing the multi-stage pore β molecular sieve is feasible.
FIG. 3 shows that the catalysts prepared in example 1 and comparative example 1 of the present invention do not contain C in the reaction gas3H6And contain C3H6A graph comparing the activity of catalytic ammonia reduction of nitrogen oxides under the conditions of (1); as can be seen from the graph, the multi-stage porous Fe-beta obtained by the preparation method of the present invention has C resistance under the same reaction conditions as compared to Fe-beta of comparative example 13H6The poisoning ability is greatly improved.
The structural data and Fe content of the catalysts prepared in example 1 and comparative example 1 are shown in table 1;
TABLE 1
Figure BDA0001950246920000111
It can be seen from table 1 that the hierarchical pore Fe- β has a larger external specific surface area than Fe- β, which indicates that hierarchical pores are introduced on the β molecular sieve by the organic amine aqueous solution treatment, and the Fe content on the hierarchical pore Fe- β is higher when ion exchange is performed under the same conditions, which indicates that the introduced hierarchical pores provide more ion exchange sites, which is also the reason for the improved activity.
The reaction gas does not contain C3H6The nitrogen oxide conversion at 225 ℃ of the catalysts obtained in examples 1 to 4 and comparative example 1 is shown in Table 2。
TABLE 2
Figure BDA0001950246920000112
Figure BDA0001950246920000121
It can be seen from comparison of examples 1-4 with comparative example 1 that the low-temperature activity of the catalyst after treatment with the aqueous solution of organic amine is significantly improved, which indicates that the hierarchical pore structure formed on the beta molecular sieve by treatment with the aqueous solution of organic amine is indeed beneficial to improving the catalytic activity of the catalyst.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (32)

1. A preparation method of a hierarchical pore Fe-beta molecular sieve catalyst for selective catalytic reduction of nitrogen oxides by ammonia gas is characterized by comprising the following steps:
(1) treating a beta molecular sieve with the silicon-aluminum ratio of 10-50 by using an organic amine aqueous solution to obtain a hierarchical pore beta molecular sieve; the organic amine in the organic amine aqueous solution comprises any one or a mixture of at least two of tetraethyl ammonium hydroxide, triethylamine, diethanolamine and di-n-propylamine, and the concentration of the organic amine in the organic amine aqueous solution is 0.1-1 mol/L; the treatment specifically comprises the following steps:
(a) mixing the beta molecular sieve with the organic amine aqueous solution according to the volume ratio of 0.033-0.1g/mL, and stirring;
(b) carrying out hydrothermal treatment on the product obtained in the step (a) at the temperature of 120-150 ℃;
(c) filtering, washing, drying and roasting the product obtained in the step (b) to obtain the hierarchical pore beta molecular sieve;
(2) loading Fe on the hierarchical pore beta molecular sieve obtained in the step (1) through ion exchange to obtain the hierarchical pore Fe-beta molecular sieve catalyst, which specifically comprises the following steps:
(a') mixing the hierarchical pore beta molecular sieve prepared in the step (1) with an iron salt aqueous solution, and stirring for ion exchange; the ferric salt in the ferric salt aqueous solution comprises any one or a mixture of at least two of ferrous chloride, ferrous sulfate, ferric nitrate and ferrocene;
(b ') filtering, washing, drying and roasting the product obtained in the step (a') to obtain the hierarchical porous Fe-beta molecular sieve catalyst.
2. The method of claim 1, wherein the beta molecular sieve of step (1) has a silica to alumina ratio of 20 to 30.
3. The method of claim 2, wherein the beta molecular sieve of step (1) has a silica to alumina ratio of 25.
4. The method according to claim 1, wherein the organic amine in the aqueous organic amine solution in the step (1) is tetraethylammonium hydroxide.
5. The method according to claim 1, wherein the concentration of the organic amine in the aqueous organic amine solution in the step (1) is 0.3 mol/L.
6. The method of claim 1, wherein the hydrothermal treatment in step (b) is performed at a temperature of 140 ℃.
7. The method of claim 1, wherein the hydrothermal treatment time of step (b) is 24-168 hours.
8. The method of claim 7, wherein the hydrothermal treatment of step (b) is carried out for a period of 72 hours.
9. The method as claimed in claim 1, wherein the temperature of the calcination in the step (c) is 450-600 ℃.
10. The method of claim 9, wherein the temperature of the firing of step (c) is 550 ℃.
11. The method of claim 1, wherein the calcination time in step (c) is 3 to 10 hours.
12. The method of claim 11, wherein the calcination in step (c) is carried out for a period of 5 hours.
13. The method of claim 1, wherein the firing of step (c) is carried out at a temperature increase rate of 1 to 5 ℃/min.
14. The method of claim 13, wherein the firing of step (c) is carried out at a ramp rate of 2 ℃/min.
15. The method of claim 1, wherein the concentration of the aqueous solution of the iron salt in step (a') is 0.01 to 0.25 mol/L.
16. The method of claim 15, wherein the concentration of the aqueous iron salt solution of step (a') is 0.05 mol/L.
17. The method of claim 1, wherein the ratio of the mass of the hierarchical pore beta molecular sieve to the volume of the aqueous solution of the iron salt in step (a') is from 0.004g/mL to 0.0067 g/mL.
18. The method of claim 17, wherein the ratio of the mass of the hierarchical pore beta molecular sieve to the volume of the aqueous solution of the iron salt in step (a') is 0.005 g/mL.
19. The process of claim 1, wherein the temperature at which the ion exchange is carried out with stirring in step (a') is from room temperature to 90 ℃.
20. The process of claim 19, wherein the temperature at which the agitation for ion exchange in step (a') is from 60 ℃ to 80 ℃.
21. The process of claim 20, wherein the temperature at which the agitation for ion exchange in step (a') is 80 ℃.
22. The process of claim 1, wherein the stirring of step (a') is carried out for an ion exchange time of 5 to 48 hours.
23. The process of claim 22, wherein the agitation in step (a') is carried out for an ion exchange time of 24 hours.
24. The method as claimed in claim 1, wherein the temperature of the calcination in the step (b') is 400-600 ℃.
25. The method of claim 24, wherein said firing of step (b') is at a temperature of 500 ℃.
26. The method of claim 1, wherein the calcination time in step (b') is 3 to 10 hours.
27. The method of claim 26, wherein said calcining of step (b') occurs for a period of 3 hours.
28. The method of claim 1, wherein the firing of step (b') is carried out at a temperature increase rate of 1 to 10 ℃/min.
29. The method of claim 28, wherein said firing of step (b') is at a ramp rate of 5 ℃/min.
30. The hierarchical pore Fe-beta molecular sieve catalyst prepared by the preparation method of any one of claims 1 to 29.
31. Use of the hierarchical pore Fe-beta molecular sieve catalyst of claim 30 as a catalyst for ammonia selective catalytic reduction of nitrogen oxides.
32. The use of claim 31, wherein the hierarchical pore Fe- β molecular sieve catalyst is used as a catalyst for ammonia selective catalytic reduction of nitrogen oxides in mobile source tail gases and/or stationary source flue gases.
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