CN113368893A - High-activity SCR molecular sieve catalyst and preparation method thereof - Google Patents

High-activity SCR molecular sieve catalyst and preparation method thereof Download PDF

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CN113368893A
CN113368893A CN202110603525.4A CN202110603525A CN113368893A CN 113368893 A CN113368893 A CN 113368893A CN 202110603525 A CN202110603525 A CN 202110603525A CN 113368893 A CN113368893 A CN 113368893A
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molecular sieve
cerium
copper
catalyst
drying
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姜杨
庞磊
吴章辉
刘诗逸
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Dongfeng Commercial Vehicle Co Ltd
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Abstract

The application relates to the technical field of diesel vehicle tail gas treatment, in particular to a high-activity SCR molecular sieve catalyst and a preparation method thereof. The preparation method provided by the application comprises the following steps: grinding a silicon source, an aluminum source and an alkali source, uniformly mixing to obtain a solid mixture, heating, washing, drying and calcining to obtain the zeolite molecular sieve; adding a copper salt solution and a cerium salt solution into a zeolite molecular sieve for ultrasonic dispersion to obtain a catalyst slurry; and (4) freeze-drying the catalyst slurry, and then calcining to obtain the high-activity SCR molecular sieve catalyst. The catalyst prepared by the preparation method provided by the application has a wider active temperature window, strong water and sulfur poisoning resistance, excellent low-temperature activity and excellent hydrothermal aging stability.

Description

High-activity SCR molecular sieve catalyst and preparation method thereof
Technical Field
The application relates to the technical field of diesel vehicle tail gas treatment, in particular to a high-activity SCR molecular sieve catalyst and a preparation method thereof.
Background
Nitrogen oxides contained in plant exhaust gases and motor vehicle exhaust gases are one of the main atmospheric pollutants, and the harm of nitrogen oxides to the environment is increasingly significant. Wherein, the Nitrogen Oxide (NO) of the diesel vehicle tail gasx) Pollution has become one of the most prominent problems in atmospheric pollution. Ammonia selective catalytic reduction (NH) in mobile source denitration3SCR) is one of the most applied and mature flue gas denitration technologies at present. SCR (Selective Catalytic Reduction) aims at NO in tail gas emission of diesel vehiclesxThe treatment principle of the method is that under the action of a catalyst, reducing agent ammonia or urea is sprayed in to remove NO in tail gasxReduction to N2And H2O, the catalyst has two types of noble metals and non-noble metals, and the treatment process has the advantages of no byproduct, no secondary pollution, simple device structure, high removal efficiency (up to more than 90 percent), reliable operation, convenient maintenance and the like.
Research shows that the copper-based molecular sieve catalyst is used for treating NO in the tail gas of diesel vehiclesxThe molecular sieve is a metastable material, water vapor can collapse the framework of the molecular sieve to cause the migration of active components and cause the inactivation of the catalyst, and the combustion products of sulfur in the diesel can slowly sulfate the active metal Cu, thereby reducing the activity of the catalyst.
Therefore, it is necessary to provide a copper-based molecular sieve catalyst with high activity and strong resistance to water and sulfur poisoning.
Disclosure of Invention
The embodiment of the application provides a preparation method of a high-activity SCR molecular sieve catalyst, which aims to solve the problem that a copper-based molecular sieve catalyst in the related art is weak in water and sulfur poisoning resistance.
In a first aspect, the present application provides a method for preparing a high-activity SCR molecular sieve catalyst, comprising the steps of:
step S101, preparing a zeolite molecular sieve: grinding a silicon source, an aluminum source and an alkali source, uniformly mixing to obtain a solid mixture, heating, washing, drying and calcining to obtain the zeolite molecular sieve;
step S102, adding a copper salt solution and a cerium salt solution into a zeolite molecular sieve, and performing ultrasonic dispersion to obtain catalyst slurry;
and step S103, freeze-drying the catalyst slurry, and then calcining to obtain the high-activity SCR molecular sieve catalyst.
In some embodiments, in step S101, the silicon source is any one or more of diatomite, attapulgite, sepiolite, or a mixture thereof.
In some embodiments, in step S101, the aluminum source is any one or more of aluminum sulfate, aluminum nitrate, and aluminum chloride.
In some embodiments, in step S101, the alkali source is sodium hydroxide or potassium hydroxide. In some preferred embodiments, the alkali source is sodium hydroxide.
In some embodiments, in step S101, the silicon source is diatomaceous earth, the aluminum source is aluminum sulfate, and the alkali source is sodium hydroxide.
In some embodiments, in step S101, the mass ratio of the silicon element in the silicon source, the aluminum element in the aluminum source, and the hydroxyl in the alkali source is 3-8: 2-6: 20-30.
In some embodiments, in step S101, the heating is performed by microwave heating at 100 ℃ to 200 ℃ for 0.5h to 20 h.
In some embodiments, in step S101, the drying temperature is 60 ℃ to 200 ℃ and the drying time is 3h to 12 h.
In some embodiments, in step S101, the calcination temperature is 450 ℃ to 650 ℃, and the calcination time is 1h to 6 h.
In some embodiments, in step S102, the copper salt is copper sulfate, copper chloride or copper nitrate.
In some embodiments, in step S102, the cerium salt is cerium sulfate, cerium chloride, cerium nitrate, or cerium acetate.
In some embodiments, in step S102, the copper salt is copper sulfate and the cerium salt is cerium nitrate.
In some embodiments, in step S102, the mass ratio of the copper ions in the copper salt, the cerium ions in the cerium salt and the zeolite molecular sieve is 4-10: 1-5: 60-100.
In some embodiments, the temperature of the freeze-drying is-50 ℃ to-20 ℃ and the time of the freeze-drying is 8h to 24h in step S103.
In some embodiments, in step S103, the calcination temperature is 450-650 ℃ and the calcination time is 0.5-3 h.
In a second aspect, the application also provides a high-activity SCR molecular sieve catalyst prepared by the preparation method.
The catalyst prepared by the method takes the zeolite molecular sieve with the LTA type structure as a carrier, the main active component is Cu element, and the auxiliary active component is Ce element, so that on one hand, the Ce element can promote the dispersion and the stability of the Cu element and improve the loading capacity of the catalyst; on the other hand, valence electrons of the Ce element can be mutually converted among different valence states, the generated free oxygen and free electrons can further promote the catalytic reaction, the acidity of the catalyst is enhanced, and the low-temperature reduction performance is improved, so that the low-temperature activity window of the Cu-LTA catalyst can be further widened.
The beneficial effect that technical scheme that this application provided brought includes: the preparation method provided by the application has the advantages of wide raw material source, low cost and simple process; the catalyst prepared by the preparation method provided by the application has a wider active temperature window, strong water and sulfur poisoning resistance, excellent low-temperature activity and excellent hydrothermal aging stability, is coated on a DPF (Diesel Particulate Filter), and has the function of reducing NO in tail gasXAnd the function of filtering carbon particles.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a process for preparing a high activity SCR molecular sieve catalyst provided in an embodiment of the present application;
FIG. 2 is a scanning electron micrograph and an X-ray diffraction pattern of the zeolite molecular sieve prepared in example 1 of the present application;
FIG. 3 is a graph showing the results of activity evaluation of the catalyst obtained in example 1 of the present application and the catalyst obtained in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a preparation method of a high-activity SCR molecular sieve catalyst, which can solve the problem that a copper-based molecular sieve catalyst in the related art is weak in water and sulfur poisoning resistance.
Fig. 1 is a schematic flow chart of a preparation method of a high-activity SCR molecular sieve catalyst provided in an embodiment of the present application, and referring to fig. 1, the preparation method of the high-activity SCR molecular sieve catalyst provided in the embodiment of the present application includes the following steps:
step S101, preparing a zeolite molecular sieve: grinding a silicon source, an aluminum source and an alkali source, uniformly mixing to obtain a solid mixture, heating the solid mixture by microwave for 0.5-20 h at 100-200 ℃, then centrifugally washing the solid mixture for 3 times by using deionized water at the speed of 4000-8000 r/min, wherein the centrifugal time is 5-10 min each time, drying the solid mixture for 3-12 h at 60-200 ℃ after washing, and calcining the solid mixture for 1-6 h at 450-650 ℃ after drying to obtain the LTA (Linda A) -type zeolite molecular sieve; the alkali-resistant silicon-aluminum mixed material comprises a silicon source, an alkali source and a base, wherein the silicon source is any one or a mixture of more of diatomite, attapulgite and sepiolite, the aluminum source is any one or a mixture of more of aluminum sulfate, aluminum nitrate and aluminum chloride, the alkali source is sodium hydroxide or potassium hydroxide, and the mass ratio of silicon elements in the silicon source, aluminum elements in the aluminum source and hydroxyl groups in the alkali source is 3-8: 2-6: 20-30;
step S102, adding a copper salt solution and a cerium salt solution into a zeolite molecular sieve, and ultrasonically mixing and dispersing for 0.5-2 h at the power of 30-80 kHZ to obtain catalyst slurry; wherein the copper salt is copper sulfate, copper chloride or copper nitrate, and the cerium salt is cerous sulfate, cerous chloride, cerous nitrate or cerous acetate; the mass ratio of copper ions in the copper salt to cerium ions in the cerium salt to the zeolite molecular sieve is 4-10: 1-5: 60-100;
and S103, freeze-drying the catalyst slurry for 8 to 24 hours at the temperature of between 50 ℃ below zero and 20 ℃ below zero, and calcining the catalyst slurry for 0.5 to 3 hours at the temperature of between 450 and 650 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Diatomaceous earth is made of amorphous SiO2Composition and containing a small amount of Fe2O3、CaO、MgO、Al2O3And organic impurities, diatomaceous earth is generally light yellow or light gray in color, soft, porous and light.
Attapulgite is a crystalline hydrated magnesium aluminum silicate mineral, has unique layer chain structure characteristic, and has lattice displacement in its structure, and the crystal contains variable amount of Na+、Ca2+、Fe3+、Al3+The crystals are needle-shaped, fibrous or fibrous aggregates. The attapulgite has unique dispersion, high temperature resistance, good colloid properties of salt and alkali resistance, high adsorption and decolorization capacity, certain plasticity and binding power, and ideal chemical molecular formula of the attapulgite is Mg5Si8O20(OH)2(OH2)4·4H2And O. The attapulgite is produced in sedimentary rock and weathering crust in the form of soil and dense block, and has white, off-white, grey green or weak silk luster. The soil is fine and smooth, has a greasy feeling, is light and crisp, has shell-shaped or ragged fracture and strong water absorption.
Sepiolite is a fibrous hydrous magnesium silicate, usually white, light grey, light yellow in colorHas equal color and strong adsorption capacity, and has a chemical formula of Si12Mg8O30(OH)4(OH2)4·8H2O。
The catalyst prepared by the method takes the zeolite molecular sieve with the LTA type structure as a carrier, the main active component is Cu element, and the auxiliary active component is Ce element, so that on one hand, the Ce element can promote the dispersion and the stability of the Cu element and improve the loading capacity of the catalyst; on the other hand, valence electrons of the Ce element can be mutually converted among different valence states, the generated free oxygen and free electrons can further promote the catalytic reaction, the acidity of the catalyst is enhanced, and the low-temperature reduction performance is improved, so that the low-temperature activity window of the Cu-LTA catalyst can be further widened.
The preparation method provided by the application has the advantages of wide raw material source, low cost and simple process; the catalyst prepared by the preparation method provided by the application has a wider active temperature window, strong water-resistant and sulfur poisoning-resistant performance, excellent low-temperature activity and hydrothermal aging stability, and can reduce NO in tail gas when coated on DPFXAnd the function of filtering carbon particles.
The high activity SCR molecular sieve catalyst and the preparation method thereof provided by the present application are described in detail below with reference to examples and comparative examples.
Example 1:
the embodiment 1 of the application provides a preparation method of a high-activity SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing diatomite, aluminum sulfate and sodium hydroxide according to the following silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 5:3:25 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture at 150 ℃ for 2 hours by using microwaves, then centrifugally washing the solid mixture for 3 times by using deionized water at a rotating speed of 6000rpm, drying the solid mixture at 80 ℃ for 8 hours after washing, and calcining the solid mixture at 450 ℃ for 2 hours after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper sulfate solution and a cerium nitrate solution into the zeolite molecular sieve in a mass ratio of 6:2:80, and ultrasonically mixing and dispersing for 1h at the power of 35kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of minus 45 ℃ for freeze drying for 12 hours, and then calcining for 2 hours at 550 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
The ICP test results show that the catalyst prepared in example 1 contains the catalytically active elements copper and cerium at the same time, with the mass content of copper being 3% and the mass content of cerium being 1%.
Referring to fig. 2, fig. 2a is a scanning electron micrograph of the zeolitic molecular sieve obtained in example 1, and fig. 2b is an X-ray diffraction pattern of the zeolitic molecular sieve obtained in example 1, and it can be seen from fig. 2 that the zeolitic molecular sieve obtained in example 1 is of LTA type.
Comparative example 1:
the Cu-ZSM-5 molecular sieve catalyst prepared in the comparative example 1 of the application comprises the following preparation processes: weighing 300g H-ZSM-5 powder, calcining at 550 ℃ for 4h, and then cooling to room temperature; adding H-ZSM-5 powder into a copper nitrate solution, rotationally drying the powder at 80 ℃ to be powdery, and calcining the powder at 550 ℃ for 2 hours to obtain the Cu-ZSM-5 molecular sieve catalyst, wherein the mass ratio of copper ions in the copper nitrate solution to the H-ZSM-5 powder is 6: 80.
The catalysts prepared in example 1 and comparative example 1 were subjected to activity evaluation by the following method: weighing 50g of the high-activity SCR molecular sieve catalyst prepared in the embodiment 1, adding the weighed high-activity SCR molecular sieve catalyst into 150mL of deionized water, and mixing to obtain slurry A; weighing 50g of the Cu-ZSM-5 molecular sieve catalyst prepared in the comparative example 1, adding the catalyst into 150mL of deionized water, and mixing to obtain slurry B; respectively coating the slurry A and the slurry B on 400 cells/in of the hole number2Sample A and sample B were obtained on a cordierite honeycomb ceramic substrate having a volume of 0.18L, and the coating amounts of slurry A and slurry B were 220 g.L-1Then, respectively drying the sample A and the sample B at 100 ℃ for 2h, then roasting at 500 ℃ for 2h to obtain a copper-based catalyst A and a copper-based catalyst B, respectively putting the copper-based catalyst A and the copper-based catalyst B into a fixed bed activity evaluation device for simulation test, wherein the simulated tail gas comprises 1000ppm NO and 1100ppm NH3、5％O2And 10% of H2O, the reaction space velocity is 30000h-1。
Experimental test results referring to fig. 3, in fig. 3, Cu/Ce LTA aging means hydrothermal aging of the catalyst prepared in example 1 at 700 ℃ for 12 hours, Cu/Ce LTA fresh means the catalyst prepared in example 1, comparative-fresh means the catalyst prepared in comparative example 1, and comparative-aging means hydrothermal aging of the catalyst prepared in comparative example 1 at 700 ℃ for 12 hours, and it can be seen that the catalyst prepared in example 1 has superior hydrothermal stability to the catalyst prepared in comparative example 1 by comparing the conversion rates of the catalyst of example 1 and the catalyst of comparative example 1 before and after hydrothermal aging at 700 ℃ for 12 hours.
Example 2:
the embodiment 2 of the application provides a preparation method of a high-activity SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing attapulgite, aluminum sulfate and sodium hydroxide according to the ratio of silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 4:5:22 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture at 120 ℃ for 3 hours by using microwaves, then centrifugally washing the solid mixture for 3 times by using deionized water at a rotating speed of 5000rpm, drying the solid mixture at 90 ℃ for 6 hours after washing, and calcining the solid mixture at 500 ℃ for 2.5 hours after drying to obtain the zeolite molecular sieve with the LTA-type structure;
step S102, according to copper ions: cerium ion: adding a copper nitrate solution and a cerium acetate solution into the zeolite molecular sieve in a mass ratio of 7:3:65, and ultrasonically mixing and dispersing for 1.5 hours at the power of 40kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of minus 30 ℃ for freeze drying for 10 hours, and then calcining for 2 hours at the temperature of 500 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 3:
the application embodiment 3 provides a preparation method of a high-activity SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing diatomite, attapulgite, aluminum sulfate and sodium hydroxide according to the following silicon elements: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 4:5.5:24 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture at 160 ℃ for 2 hours by using microwaves, then centrifugally washing the solid mixture for 3 times by using deionized water at the rotating speed of 7000rpm, drying the solid mixture at 85 ℃ for 8 hours after washing, and calcining the solid mixture at 550 ℃ for 2 hours after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper chloride solution and a cerium nitrate solution into the zeolite molecular sieve in a mass ratio of 8:2:90, and ultrasonically mixing and dispersing for 1h at the power of 35kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of-40 ℃ for freeze drying for 15h, and then calcining at 600 ℃ for 2.5h to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 4:
the embodiment 4 of the application provides a preparation method of a high-activity SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing sepiolite, aluminum chloride and sodium hydroxide according to silicon elements: aluminum element: grinding and uniformly mixing hydroxyl groups in a mass ratio of 4.5:3.5:25 to obtain a solid mixture, putting the solid mixture into a reaction kettle, heating the solid mixture at 100 ℃ for 3 hours by using microwaves, then centrifugally washing the solid mixture for 3 times by using deionized water at a rotating speed of 6500rpm, drying the solid mixture at 100 ℃ for 6 hours after washing, and calcining the solid mixture at 500 ℃ for 3 hours after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper sulfate solution and a cerium chloride solution into the zeolite molecular sieve according to the mass ratio of 5:3.5:68, and ultrasonically mixing and dispersing for 1h at the power of 50kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of-30 ℃ for freeze drying for 18h, and then calcining for 2h at the temperature of 500 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 5:
embodiment 5 of the present application provides a preparation method of a high-activity SCR molecular sieve catalyst, which includes the following steps:
step S101, mixing diatomite, sepiolite, aluminum sulfate, aluminum chloride and sodium hydroxide according to the silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 4:5:28 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture by microwave at 180 ℃ for 2h, then centrifugally washing the solid mixture by deionized water at 6000rpm for 3 times, drying the solid mixture at 80 ℃ for 8h after washing, and calcining the solid mixture at 500 ℃ for 2h after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper sulfate solution and a cerium acetate solution into the zeolite molecular sieve in a mass ratio of 5:3:85, and ultrasonically mixing and dispersing for 1h at the power of 50kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of minus 30 ℃ for freeze drying for 12 hours, and then calcining for 2 hours at the temperature of 550 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 6:
embodiment 6 of the present application provides a preparation method of a high-activity SCR molecular sieve catalyst, which includes the following steps:
step S101, mixing diatomite, attapulgite, sepiolite, aluminum sulfate and sodium hydroxide according to the silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 4:3:25 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture at 185 ℃ for 3 hours by using microwaves, then centrifugally washing the solid mixture for 3 times by using deionized water at a rotating speed of 6000rpm, drying the solid mixture at 80 ℃ for 8 hours after washing, and calcining the solid mixture at 600 ℃ for 2 hours after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper nitrate solution and a cerium chloride solution into the zeolite molecular sieve in a mass ratio of 8:4:75, and ultrasonically mixing and dispersing for 1h at the power of 60kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of 45 ℃ below zero for freeze drying for 12 hours, and then calcining for 2 hours at the temperature of 600 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 7:
embodiment 7 of the present application provides a preparation method of a high-activity SCR molecular sieve catalyst, which includes the following steps:
step S101, mixing attapulgite, sepiolite, aluminum sulfate and sodium hydroxide according to the silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 4:3:25 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture by microwave at 120 ℃ for 2 hours, then centrifugally washing the solid mixture by deionized water at a rotating speed of 6000rpm for 3 times, drying the solid mixture at 70 ℃ for 8 hours after washing, and calcining the solid mixture at 500 ℃ for 2 hours after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper chloride solution and a cerium chloride solution into the zeolite molecular sieve in a mass ratio of 7:3:85, and ultrasonically mixing and dispersing for 1h at the power of 55kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of-30 ℃ for freeze drying for 12 hours, and then calcining for 2 hours at the temperature of 500 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 8:
the embodiment 8 of the application provides a preparation method of a high-activity SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing diatomite, aluminum sulfate, aluminum nitrate and sodium hydroxide according to the following silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 4:3:21 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture at 170 ℃ for 2 hours by using microwaves, then centrifugally washing the solid mixture for 3 times by using deionized water at a rotating speed of 6000rpm, drying the solid mixture at 100 ℃ for 9 hours after washing, and calcining the solid mixture at 550 ℃ for 2 hours after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper sulfate solution and a cerium nitrate solution into the zeolite molecular sieve in a mass ratio of 6:2:80, and ultrasonically mixing and dispersing for 1h at the power of 35kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of minus 30 ℃ for freeze drying for 20 hours, and then calcining for 1.5 hours at the temperature of 600 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 9:
embodiment 9 of the present application provides a preparation method of a high-activity SCR molecular sieve catalyst, which includes the following steps:
step S101, mixing diatomite, aluminum nitrate, aluminum chloride and potassium hydroxide according to the following silicon element: aluminum element: grinding and uniformly mixing hydroxyl groups in a mass ratio of 4:5:25 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture by microwave at 180 ℃ for 1h, then centrifugally washing the solid mixture by deionized water at 6500rpm for 3 times, drying the solid mixture at 75 ℃ for 10h after washing, and calcining the dried solid mixture at 550 ℃ for 3h after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper nitrate solution and a cerium chloride solution into the zeolite molecular sieve according to the mass ratio of 6:3:65, and ultrasonically mixing and dispersing for 1.5 hours at the power of 60kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of 35 ℃ below zero for freeze drying for 16h, and then calcining at 500 ℃ for 2.5h to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 10:
the embodiment 10 of the application provides a preparation method of a high-activity SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing diatomite, aluminum sulfate, aluminum nitrate, aluminum chloride and sodium hydroxide according to the ratio of silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 4:5:22 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture at 160 ℃ for 4 hours by using microwaves, then centrifugally washing the solid mixture for 3 times by using deionized water at the rotating speed of 7000rpm, drying the solid mixture at 95 ℃ for 6 hours after washing, and calcining the solid mixture at 520 ℃ for 4 hours after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper sulfate solution and a cerium sulfate solution into the zeolite molecular sieve in a mass ratio of 7:3:70, and ultrasonically mixing and dispersing for 1h at the power of 55kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of-30 ℃ for freeze drying for 18h, and then calcining at 500 ℃ for 2.5h to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 11:
embodiment 11 of the present application provides a method for preparing a high-activity SCR molecular sieve catalyst, which includes the following steps:
step S101, mixing sepiolite, attapulgite, aluminum sulfate and sodium hydroxide according to the silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 6:5:28 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture by microwave at 110 ℃ for 5 hours, then centrifugally washing the solid mixture by deionized water at a rotating speed of 7000rpm for 3 times, drying the solid mixture at 120 ℃ for 4 hours after washing, and calcining the solid mixture at 500 ℃ for 2 hours after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper chloride solution and a cerium sulfate solution into the zeolite molecular sieve in a mass ratio of 5:2:70, and ultrasonically mixing and dispersing for 1h at the power of 55kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of-40 ℃ for freeze drying for 15h, and then calcining at 550 ℃ for 2h to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 12:
embodiment 12 of the present application provides a method for preparing a high-activity SCR molecular sieve catalyst, which includes the following steps:
step S101, mixing diatomite, sepiolite, aluminum nitrate, aluminum chloride and potassium hydroxide according to the silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 4:4:21 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture at 120 ℃ for 6 hours by using microwaves, then centrifugally washing the solid mixture for 3 times by using deionized water at a rotating speed of 6000rpm, drying the solid mixture at 90 ℃ for 6 hours after washing is finished, and calcining the solid mixture at 640 ℃ for 2 hours after drying is finished to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a nitric acid solution and a cerium nitrate solution into the zeolite molecular sieve in a mass ratio of 5:3:80, and ultrasonically mixing and dispersing for 1.5 hours at the power of 40kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of 45 ℃ below zero for freeze drying for 12 hours, and then calcining for 2 hours at the temperature of 600 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 13:
embodiment 13 of the present application provides a method for preparing a high-activity SCR molecular sieve catalyst, comprising the following steps:
step S101, mixing sepiolite, aluminum sulfate and sodium hydroxide according to the silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 3.5:5.5:22 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture by microwave at 120 ℃ for 5 hours, then centrifugally washing the solid mixture by deionized water at a rotating speed of 6000rpm for 3 times, drying the solid mixture at 78 ℃ for 8 hours after washing, and calcining the solid mixture at 635 ℃ for 2 hours after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper chloride solution and a cerium nitrate solution into the zeolite molecular sieve in a mass ratio of 9:4:90, and ultrasonically mixing and dispersing for 1h at the power of 55kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of minus 45 ℃ for freeze drying for 12 hours, and then calcining for 2 hours at 550 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 14:
an embodiment 14 of the present application provides a preparation method of a high-activity SCR molecular sieve catalyst, including the following steps:
step S101, mixing attapulgite, aluminum sulfate and sodium hydroxide according to the ratio of silicon element: aluminum element: grinding and uniformly mixing hydroxyl groups in a mass ratio of 6.5:3.5:22 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture at 160 ℃ for 1.5h by using microwaves, then centrifugally washing the solid mixture for 3 times by using deionized water at a rotating speed of 6000rpm, drying the solid mixture at 115 ℃ for 8h after washing, and calcining the solid mixture at 550 ℃ for 2h after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper nitrate solution and a cerium nitrate solution into the zeolite molecular sieve in a mass ratio of 5:1.5:64, and ultrasonically mixing and dispersing for 1h at the power of 45kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of-40 ℃ for freeze drying for 12 hours, and then calcining for 2 hours at 480 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 15:
an embodiment 15 of the present application provides a preparation method of a high-activity SCR molecular sieve catalyst, including the following steps:
step S101, mixing sepiolite, attapulgite, aluminum nitrate, aluminum chloride and sodium hydroxide according to the silicon element: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 6:3:26 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture at 160 ℃ for 2 hours by using microwaves, then centrifugally washing the solid mixture for 3 times by using deionized water at a rotating speed of 6000rpm, drying the solid mixture at 150 ℃ for 4 hours after washing, and calcining the solid mixture at 530 ℃ for 2 hours after drying to obtain the LTA-type zeolite molecular sieve;
step S102, according to copper ions: cerium ion: adding a copper sulfate solution and a cerium acetate solution into the zeolite molecular sieve in a mass ratio of 8:5:75, and ultrasonically mixing and dispersing for 1h at the power of 45kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of 35 ℃ below zero for freeze drying for 12 hours, and then calcining for 2.5 hours at the temperature of 600 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
Example 16:
the embodiment 16 of the present application provides a preparation method of a high-activity SCR molecular sieve catalyst, which includes the following steps:
step S101, mixing diatomite, attapulgite, aluminum nitrate, aluminum sulfate and sodium hydroxide according to the ratio of silicon elements: aluminum element: grinding and uniformly mixing hydroxyl in a mass ratio of 6:4:27 to obtain a solid mixture, placing the solid mixture in a reaction kettle, heating the solid mixture by microwave for 5 hours at 120 ℃, then centrifugally washing the solid mixture for 3 times by using deionized water at a rotating speed of 4500rpm, drying the solid mixture for 12 hours at 100 ℃ after washing is finished, and calcining the solid mixture for 2 hours at 640 ℃ after drying is finished to obtain the zeolite molecular sieve with the LTA type structure;
step S102, according to copper ions: cerium ion: adding a copper sulfate solution and a cerium acetate solution into the zeolite molecular sieve according to the mass ratio of 7:2.5:85, and ultrasonically mixing and dispersing for 1h at the power of 55kHZ to obtain catalyst slurry;
and step S103, placing the catalyst slurry in an environment with the temperature of-40 ℃ for freeze drying for 12 hours, and then calcining for 2 hours at the temperature of 500 ℃ to obtain the high-activity SCR molecular sieve catalyst doped with copper and cerium.
In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
In this application, "plurality" means at least two, e.g., two, three, etc., unless specifically stated otherwise.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A preparation method of a high-activity SCR molecular sieve catalyst is characterized by comprising the following steps:
s101, grinding a silicon source, an aluminum source and an alkali source, uniformly mixing to obtain a solid mixture, heating, washing, drying and calcining to obtain the zeolite molecular sieve;
s102, adding a copper salt solution and a cerium salt solution into a zeolite molecular sieve, and performing ultrasonic dispersion to obtain catalyst slurry;
s103, freeze-drying the catalyst slurry, and then calcining to obtain the high-activity SCR molecular sieve catalyst.
2. The method for preparing the high-activity SCR molecular sieve catalyst according to claim 1, wherein in step S101, the silicon source is any one or more of diatomite, attapulgite and sepiolite; the aluminum source is any one or a mixture of aluminum sulfate, aluminum nitrate and aluminum chloride; the alkali source is sodium hydroxide or potassium hydroxide.
3. The method of claim 1, wherein in step S101, the silicon source is diatomite, the aluminum source is aluminum sulfate, and the alkali source is sodium hydroxide.
4. The preparation method of the high-activity SCR molecular sieve catalyst as recited in claim 1, wherein in step S101, the mass ratio of the silicon element in the silicon source, the aluminum element in the aluminum source and the hydroxyl group in the alkali source is 3-8: 2-6: 20-30.
5. The preparation method of the high-activity SCR molecular sieve catalyst according to claim 1, wherein in step S101, the heating is performed by microwave heating at 100-200 ℃ for 0.5-20 h; the drying temperature is 60-200 ℃, and the drying time is 3-12 h; the calcining temperature is 450-650 ℃, and the calcining time is 1-6 h.
6. The method of claim 1, wherein in step S102, the copper salt is copper sulfate, copper chloride or copper nitrate; the cerium salt is cerium sulfate, cerium chloride, cerium nitrate or cerium acetate.
7. The method of claim 1, wherein in step S102, the copper salt is copper sulfate and the cerium salt is cerium nitrate.
8. The preparation method of the high-activity SCR molecular sieve catalyst according to claim 1, wherein in step S102, the mass ratio of the copper ions in the copper salt to the cerium ions in the cerium salt to the zeolite molecular sieve is 4-10: 1-5: 60-100.
9. The method for preparing the high-activity SCR molecular sieve catalyst according to claim 1, wherein the temperature of the freeze-drying is-50 ℃ to-20 ℃ and the time of the freeze-drying is 8h to 24h in step S103.
10. A high activity SCR molecular sieve catalyst, characterized by being produced by the production method according to any one of claims 1 to 9.
CN202110603525.4A 2021-05-31 2021-05-31 High-activity SCR molecular sieve catalyst and preparation method thereof Pending CN113368893A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102614875A (en) * 2011-01-26 2012-08-01 福特环球技术公司 LNT and SCR catalysts for combined LNT-SCR applications
CN103964462A (en) * 2014-05-19 2014-08-06 吉林大学 Method for quickly synthesizing zeolite molecular sieve by microwave solid-phase method
CN110479359A (en) * 2019-08-27 2019-11-22 无锡威孚环保催化剂有限公司 Low silica-alumina ratio high stability cupric molecular sieve catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102614875A (en) * 2011-01-26 2012-08-01 福特环球技术公司 LNT and SCR catalysts for combined LNT-SCR applications
CN103964462A (en) * 2014-05-19 2014-08-06 吉林大学 Method for quickly synthesizing zeolite molecular sieve by microwave solid-phase method
CN110479359A (en) * 2019-08-27 2019-11-22 无锡威孚环保催化剂有限公司 Low silica-alumina ratio high stability cupric molecular sieve catalyst and preparation method thereof

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