CN117531518A - SCR denitration catalyst, preparation method and application thereof - Google Patents

SCR denitration catalyst, preparation method and application thereof Download PDF

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CN117531518A
CN117531518A CN202311337308.0A CN202311337308A CN117531518A CN 117531518 A CN117531518 A CN 117531518A CN 202311337308 A CN202311337308 A CN 202311337308A CN 117531518 A CN117531518 A CN 117531518A
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percent
mass
catalyst
scr denitration
preparing
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李炳宏
王晓东
刘程
王治宙
任景行
周振方
葛光荣
张全
许刚刚
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XI'AN RESEARCH INSTITUTE OF CHINA COAL RESEARCH INSTITUTE
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    • B01D—SEPARATION
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    • B01D53/8628—Processes characterised by a specific catalyst
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/58—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J23/22—Vanadium
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
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Abstract

The invention provides an SCR denitration catalyst, a preparation method and application thereof. The method comprises the steps of preparing an active component solution, preparing carrier mixed powder, preparing a catalyst precursor pellet, aging, forming, drying and calcining. The catalyst can be used for catalyzing denitration reaction of industrial tail gas. The SCR denitration catalyst disclosed by the invention is designed on the basis of a traditional vanadium-tungsten-titanium catalyst system, the forming process and the formula are correspondingly improved, a novel active component of vanadium and iron complexation is formed, the active component is more uniformly dispersed, microscopic pore channels are more developed, the strength is improved, the forming is reliable, and the forty-pore catalyst can be extruded. The effective valence state ratio and the distribution uniformity of vanadium are improved, and the addition of cerium element improves the oxygen storage capacity and the heat storage capacity of the catalyst, so that the low-temperature activity and the water resistance of the catalyst are obviously improved.

Description

SCR denitration catalyst, preparation method and application thereof
Technical Field
The invention belongs to the technical field of industrial tail gas treatment, relates to an SCR denitration catalyst, and in particular relates to an SCR denitration catalyst, a preparation method and application thereof.
Background
The requirement of ultralow content of nitrogen oxides in the flue gas of the industrial kiln needs to be met when the flue gas is discharged, however, the flue gas discharge temperature of cement kiln tail, steel kiln tail gas, ceramic kiln tail gas and the like is very low (less than 160 ℃), and the flue gas is in dust and SO (sulfur dioxide) 2 Under the condition of trace content, the ultralow emission of the nitrogen oxides in the flue gas is difficult to realize. Under the flue gas condition, the adoption of the low-temperature high-activity and water-resistant SCR denitration catalyst is an ideal solution, and the high-temperature high-activity and water resistance are key indexes for determining whether the catalyst can be industrially applied.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide an SCR denitration catalyst, a preparation method and application thereof, and solves the technical problem that the low-temperature high activity and water resistance of the SCR denitration catalyst in the prior art are to be further improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
the SCR denitration catalyst comprises the following components in percentage by mass: 65 to 80 percent of titanium dioxide, 0.1 to 1.0 percent of ferric vanadate, 0.2 to 1.5 percent of vanadium pentoxide, 0.1 to 1.0 percent of cerium oxide, 10.0 to 25.0 percent of ferric oxide, 2.0 to 10.0 percent of glass fiber and 100 percent of the sum of the mass percentages of the components; or comprises the following components in percentage by mass: the titanium dioxide is 65-80%, the ferric vanadate is 0.1-1.0%, the vanadium pentoxide is 0.2-1.5%, the ferric oxide is 10.0-25.0%, the glass fiber is 2.0-10.0%, and the sum of the mass percentages of the components is 100%.
The invention also has the following technical characteristics:
preferably, the composition comprises the following components in percentage by mass: 71.3 to 75.8 percent of titanium dioxide, 0.3 to 0.6 percent of ferric vanadate, 0.6 to 0.9 percent of vanadium pentoxide, 0.2 to 0.6 percent of cerium oxide, 15.2 to 19 percent of ferric oxide, 3.8 to 7.6 percent of glass fiber and 100 percent of the sum of the mass percentages of the components; or comprises the following components in percentage by mass: 72.6 to 76.5 percent of titanium dioxide, 0.3 to 0.6 percent of ferric vanadate, 0.4 to 0.9 percent of vanadium pentoxide, 15.3 to 19.1 percent of ferric oxide, 3.9 to 7.6 percent of glass fiber and 100 percent of the sum of the mass percentages of the components.
Further preferably, the composition comprises the following components in percentage by mass: titanium dioxide 75.7%, ferric vanadate 0.5%, vanadium pentoxide 0.9%, cerium oxide 0.7%, ferric oxide 18.9%, and glass fiber 3.8%.
Further preferably, the composition comprises the following components in percentage by mass: 71.3% of titanium dioxide, 0.6% of ferric vanadate, 0.8% of vanadium pentoxide, 0.4% of cerium oxide, 18.3% of ferric oxide and 7.1% of glass fiber.
Further preferably, the composition comprises the following components in percentage by mass: 72.1% of titanium dioxide, 0.6% of ferric vanadate, 0.8% of vanadium pentoxide, 1.0% of cerium oxide, 18.3% of ferric oxide and 7.3% of glass fiber.
The invention also provides a preparation method of the SCR denitration catalyst, which specifically comprises the following steps:
step one, preparing an active component solution:
adding ammonium metavanadate powder into water and stirring to form a suspension, adding monoethanolamine into the suspension, and continuously heating and stirring at 40-70 ℃ until ammonium metavanadate is completely dissolved to prepare an ammonium metavanadate solution; continuously introducing nitrogen into the container, adding ferrous sulfate into water under the protection of nitrogen atmosphere while stirring, and preparing ferrous sulfate solution after the ferrous sulfate is completely dissolved; adding cerium nitrate into water under the stirring condition, and preparing cerium nitrate solution after the cerium nitrate is completely dissolved;
preparing carrier mixed powder:
placing titanium dioxide in a reaction container, adding sodium stearate, lactic acid, water and ammonia water under stirring, and stirring to obtain carrier mixed powder;
step three, preparing a catalyst precursor mass:
under the stirring condition, adding the ammonium metavanadate solution, the ferrous sulfate solution and the cerium nitrate solution prepared in the first step into the carrier mixed powder prepared in the second step, and continuously stirring; then adding carboxymethyl cellulose and polyethylene oxide, adding water in the stirring process, and continuing stirring; adding glass fiber, and stirring continuously to obtain a catalyst precursor pellet;
aging and forming:
preparing a catalyst precursor material ball obtained in the step four into a pug, then carrying out moisturizing aging on the pug at room temperature, extruding the stale pug, and then forming to obtain the catalyst precursor;
step five, drying and calcining:
and (3) drying the catalyst precursor prepared in the step (IV), and placing the dried catalyst precursor in a calciner to calcine for 3-5 hours at the temperature of 400-600 ℃ to prepare the SCR denitration catalyst.
Specifically, in the fifth step, the drying process is as follows: drying at 20-40 deg.c for 5-15 days, drying at 50-80 deg.c for 2-5 days and final drying at 80-120 deg.c for 12-36 hr.
Specifically, the mass ratio of the sodium stearate, the carboxymethyl cellulose, the polyethylene oxide and the titanium dioxide is 8: (10-15): (10-15): 1000.
the application of the SCR denitration catalyst for catalyzing the denitration reaction of industrial tail gas, wherein the reaction temperature of the denitration reaction is 130-230 ℃; the industrial tail gas is mixed gas containing nitrogen oxides and ammonia, and the water content of the mixed gas is 10%.
Preferably, the reaction temperature of the denitration reaction is 130-150 ℃.
Compared with the prior art, the invention has the beneficial technical effects that:
the SCR denitration catalyst disclosed by the invention is designed on the basis of a traditional vanadium-tungsten-titanium catalyst system, the forming process and the formula are correspondingly improved, a novel active component of vanadium and iron complexation is formed, the active component is more uniformly dispersed, microscopic pore channels are more developed, the strength is improved, the forming is reliable, and forty-pore catalysts can be extruded. The effective valence state ratio and the distribution uniformity of vanadium are improved, and the addition of cerium element improves the oxygen storage capacity and the heat storage capacity of the catalyst, so that the low-temperature activity and the water resistance of the catalyst are obviously improved.
According to the preparation method of the SCR denitration catalyst, the catalyst prepared finally has small bed resistance, large specific surface area, high mechanical strength and excellent thermal stability by adopting the proper auxiliary agent and the active component.
(III) the SCR denitration catalyst disclosed by the invention is suitable for denitration of tail gas of cement kiln, steel kiln and ceramic kiln under the condition that the flue gas temperature is lower than 160 ℃ and the water content is lower than 10%, and can be widely applied to denitration of flue gas of industrial kilns such as cement, steel, ceramic and the like with low-temperature flue gas conditions and coal-fired power plants arranged at low temperature.
Drawings
Fig. 1 is a scanning electron microscope image of an SCR denitration catalyst of the present invention.
FIG. 2 is a scanning electron microscope image of the catalyst of comparative example 1.
The technical scheme of the invention is further described below by referring to examples.
Detailed Description
In the invention, the following components are added: SCR (Selective Catalytic Reduction) refers to selective catalytic reduction.
All the raw materials used in the present invention are known in the art unless otherwise specified.
The following specific embodiments of the present invention are given according to the above technical solutions, and it should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present invention.
Example 1:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 75.7% of iron vanadate (FeVO 4 ) 0.5% of vanadium pentoxide (V) 2 O 5 ) 0.9% of cerium oxide (CeO) 2 ) 0.7% of ferric oxide (Fe) 2 O 3 ) 18.9%, 3.8% glass fiber, and a trace of other materials, with negligible mass.
In the catalyst, the titanium dioxide has stable chemical property, good dispersing capability and large surface area, and is an ideal catalyst carrier material. The glass fiber is used as a macromolecular framework material, so that the strength of the catalyst can be enhanced. Cerium is additionally added into the active component in the traditional vanadium catalyst, so that the oxygen storage capacity and the heat storage capacity of the catalyst can be improved.
In this embodiment, the preparation method of the SCR denitration catalyst specifically includes the following steps:
step one, preparing an active component solution:
adding 16g of ammonium metavanadate powder into 100mL of deionized water, stirring to form a white suspension, adding 40mL of monoethanolamine into the white suspension, and continuously heating and stirring at 60 ℃ until ammonium metavanadate is completely dissolved to prepare an ammonium metavanadate solution; continuously introducing nitrogen into the container, adding 250g of ferrous sulfate into 100mL of deionized water under the protection of nitrogen atmosphere while stirring, and preparing ferrous sulfate solution after the ferrous sulfate is completely dissolved; 5g of cerium nitrate was added to 10mL of deionized water with stirring, and after the cerium nitrate was completely dissolved, a cerium nitrate solution was prepared.
Preparing carrier mixed powder:
1000g of titanium dioxide is weighed and placed in a stirrer, 8g of sodium stearate, 10mL of lactic acid, 150mL of distilled water and 50mL of ammonia water are added under stirring, and stirring is carried out for 30min, so that milky carrier mixed powder is prepared. Wherein, sodium stearate is used as a lubricant, so that the resistance of the later extrusion molding can be reduced. Lactic acid was used as an adsorbent.
Step three, preparing a catalyst precursor mass:
under the stirring condition, adding the ammonium metavanadate solution, the ferrous sulfate solution and the cerium nitrate solution prepared in the first step into the carrier mixed powder prepared in the second step, and continuously stirring for 30min; then 10g of carboxymethyl cellulose and 10g of polyethylene oxide are added, 50mL of distilled water is added in the stirring process, and stirring is continued for 30min; 100g of glass fiber was added thereto, and stirring was continued for 30 minutes, to obtain a viscous brown catalyst precursor pellet.
The carboxymethyl cellulose and the polyethylene oxide are used as pore formers, so that the specific surface area of the catalyst carrier can be increased, the activity of the catalyst is improved, the pore structure formation of the catalyst carrier can be promoted, and the pore structure distribution of the catalyst carrier is more uniform. In addition, since carboxymethyl cellulose and polyethylene oxide have thickening and wet adhesion, they can be used as a binder, and at the same time, polyethylene oxide contributes to good dispersion of glass fibers.
Aging and forming:
putting the catalyst precursor dough prepared in the step four into a vacuum pugging machine for repeated pugging to prepare pug with compact material and compact surface and without cracking; and (3) tightly wrapping the pug with a plastic film, carrying out moisture preservation and aging for 24 hours at room temperature, and then extruding the stale pug by adopting an extruder and then forming to obtain the 40-hole honeycomb catalyst precursor.
Step five, drying and calcining:
putting the catalyst precursor prepared in the step four into a drying box, drying for 10 days at the temperature of 30 ℃, drying for 4 days at the temperature of 60 ℃, and drying for 24 hours at the temperature of 100 ℃; and (3) placing the dried catalyst precursor in a calciner, and calcining for 4 hours at the temperature of 500 ℃ to obtain the SCR denitration catalyst.
Example 2:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 76.2% of iron vanadate (FeVO 4 ) 0.5% of vanadium pentoxide (V) 2 O 5 ) 0.9% of ferric oxide (Fe) 2 O 3 ) 19.1%, 3.9% glass fiber, and a trace of other materials, with negligible mass.
In this example, the preparation method of the SCR denitration catalyst is basically the same as that of example 1, except that: in the first step, cerium nitrate is adjusted. In this example, no cerium nitrate was added.
Example 3:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 75.8%, iron vanadate (FeVO 4 ) 0.5% of vanadium pentoxide (V) 2 O 5 ) 0.9% of cerium oxide (CeO) 2 ) 0.6% of ferric oxide (Fe) 2 O 3 ) 19.0 percent, 3.8 percent of glass fiber,in addition, the material also contains trace other materials, and the quality is negligible.
In this example, the preparation method of the SCR denitration catalyst is basically the same as that of example 1, except that: in the first step, the quality of cerium nitrate is different. In this example, the mass of cerium nitrate was 8g.
Example 4:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 72.8% of iron vanadate (FeVO 4 ) 0.6% of vanadium pentoxide (V) 2 O 5 ) 0.8% of ferric oxide (Fe) 2 O 3 ) 18.4%, 7.2% glass fiber, and a trace of other materials, with negligible mass.
In this example, the preparation method of the SCR denitration catalyst is basically the same as that of example 1, except that: in the first step, ammonium metavanadate is different in quality, and cerium nitrate is adjusted. In this example, the mass of ammonium metavanadate was 32g, and cerium nitrate was not added.
In the third step, the quality of the carboxymethyl cellulose and the quality of the polyethylene oxide are different. In this example, the mass of carboxymethyl cellulose was 15g, and the mass of polyethylene oxide was 15g.
Example 5:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 71.3% of iron vanadate (FeVO 4 ) 0.6% of vanadium pentoxide (V) 2 O 5 ) 0.8%, cerium oxide (CeO) 2 ) 0.4% of ferric oxide (Fe) 2 O 3 ) 18.3%, 7.1% glass fiber, and a trace of other materials, with negligible mass.
In this example, the preparation method of the SCR denitration catalyst is basically the same as that of example 1, except that: in the first step, the ammonium metavanadate has different quality. In this example, the mass of ammonium metavanadate was 32g.
In the third step, the quality of the carboxymethyl cellulose and the quality of the polyethylene oxide are different. In this example, the mass of carboxymethyl cellulose was 15g, and the mass of polyethylene oxide was 15g.
Example 6:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 72.1% of iron vanadate (FeVO 4 ) 0.6% of vanadium pentoxide (V) 2 O 5 ) 0.8%, cerium oxide (CeO) 2 ) 1.0% of ferric oxide (Fe) 2 O 3 ) 18.3%, 7.3% glass fiber, and a trace of other materials, with negligible mass.
In this example, the preparation method of the SCR denitration catalyst is basically the same as that of example 1, except that: in the first step, the ammonium metavanadate has different quality. In this example, the mass of ammonium metavanadate was 32g.
In the second step, the quality of cerium nitrate is different. In this example, the mass of cerium nitrate was 12g.
In the third step, the quality of the carboxymethyl cellulose and the quality of the polyethylene oxide are different. In this example, the mass of carboxymethyl cellulose was 15g, and the mass of polyethylene oxide was 15g.
Example 7:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 76.5% of iron vanadate (FeVO 4 ) 0.3% of vanadium pentoxide (V) 2 O 5 ) 0.4% of ferric oxide (Fe) 2 O 3 ) 15.3%, 7.6% glass fiber, and trace amounts of other materials, with negligible mass.
In this example, the preparation method of the SCR denitration catalyst is basically the same as that of example 1, except that: and step one, the quality of ferrous sulfate and ammonium metavanadate are different, and cerium nitrate is adjusted. In this example, the mass of ferrous sulfate was 200g, the mass of ammonium metavanadate was 10g, and cerium nitrate was not added.
Example 8:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 75.8%, iron vanadate (FeVO 4 ) 0.3% of vanadium pentoxide (V) 2 O 5 ) 0.6% of cerium oxide (CeO) 2 ) 0.2% of ferric oxide (Fe) 2 O 3 ) 15.2%, 7.6% glass fiber, and trace amounts of other materials, with negligible mass.
In this example, the preparation method of the SCR denitration catalyst is basically the same as that of example 1, except that: in the first step, the quality of ferrous sulfate and cerium nitrate are different. In this example, the mass of ferrous sulfate was 200g, and the mass of cerium nitrate was 3g.
Example 9:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 73.0% of iron vanadate (FeVO 4 ) 0.4% of vanadium pentoxide (V) 2 O 5 ) 0.6% of cerium oxide (CeO) 2 ) 0.2% of ferric oxide (Fe) 2 O 3 ) 18.3%, 7.3% glass fiber, and a trace of other materials, with negligible mass.
In this example, the preparation method of the SCR denitration catalyst is basically the same as that of example 1, except that: in the first step, the quality of cerium nitrate is different. In this example, the mass of cerium nitrate was 3g.
Example 10:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 72.6% of iron vanadate (FeVO 4 ) 0.5% of vanadium pentoxide (V) 2 O 5 ) 0.8% of ferric oxide (Fe) 2 O 3 ) 18.2% and 7.3% glass fiber, and further contains a trace amount of other materials, with negligible mass.
In this example, the preparation method of the SCR denitration catalyst is basically the same as that of example 1, except that: and step one, ammonium metavanadate is different in quality and cerium nitrate is adjusted. In this example, ammonium metavanadate was 28g by mass, and cerium nitrate was not added.
Example 11:
the embodiment provides an SCR denitration catalyst, which comprises the following components in percentage by mass: titanium dioxide (TiO) 2 ) 72.8% of iron vanadate (FeVO 4 ) 0.5% of vanadium pentoxide (V) 2 O 5 ) 0.7%, cerium oxide (CeO) 2 ) 0.4% of ferric oxide (Fe) 2 O 3 ) 18.2% and 7.2% glass fiber, and further contains a trace amount of other materials, with negligible mass.
In this example, the preparation method of the SCR denitration catalyst is basically the same as that of example 1, except that: in the first step, the ammonium metavanadate has different quality. In this example, the mass of ammonium metavanadate was 25g.
Comparative example 1:
the comparative example shows a commercial product V-Mo/TiO for a 40-pore honeycomb catalyst 2 The main components of the catalyst are vanadium and molybdenum doped titanium dioxide. The appearance of the product is 3cm multiplied by 3cm honeycomb block.
Performance test:
the catalyst prepared in the above example and the sample of the comparative example were subjected to denitration performance test in an activity test system, the test gas was a mixed gas containing nitrogen oxide and ammonia, the water content of the mixed gas was 10%, and the ammonia nitrogen ratio of the mixed gas was 1:1, oxygen concentration of 8%, nitrogen oxide concentration of 300ppm, space velocity of 3000h -1 . The test results are shown in Table 1.
Table 1, sample denitration efficiency statistics Table
From examples 1 to 11 and comparative example 1, the following can be concluded:
(A) At a reaction temperature of 130 ℃, the denitration efficiency is ordered from small to large as follows: comparative example 1< example 7< example 8< example 2< example 10< example 4< example 11=example 5< example 3< example 9< example 1=example 6; among them, the denitration efficiency of example 1 and example 6 can reach 78%.
At a reaction temperature of 150 ℃, the denitration efficiency is ordered from small to large as follows: comparative example 1< example 7< example 8< example 2< example 10< example 11< example 3< example 6< example 9< example 5< example 4< example 1; among them, the denitration efficiencies of examples 1, 3, 4, 5, 6 and 9 were 80% or more, and the highest denitration efficiency of example 1 was 85%.
At a reaction temperature of 170 ℃, the denitration efficiency is ordered from small to large as follows: comparative example 1< example 8< example 7=example 10< example 2< example 11< example 6=example 9< example 3< example 4< example 5< example 1, wherein the denitration efficiency of example 1, example 3, example 4, example 5, example 6 and example 9 is 85% or more, and the highest denitration efficiency of example 1 can reach 94%.
At a reaction temperature of 190 ℃, the denitration efficiency is ordered from small to large as follows: comparative example 1< example 7=example 10< example 2< example 11< example 8< example 9< example 4=example 1< example 3=example 5< example 6, wherein the denitration efficiency of example 1, example 3, example 4, example 5, example 6 and example is 90% or more, and the highest denitration efficiency of example 6 can reach 96%.
From the above comparison, the denitration efficiency of examples 1 to 11 is higher than that of comparative example 1 at a reaction temperature of 130 to 190 ℃, indicating that the catalyst of the present invention is more suitable for use in an environment having a temperature of 190℃or less, particularly 130 to 150℃than the catalyst of the prior art.
(B) At a reaction temperature of 210 ℃, the denitration efficiency is ordered from small to large as follows: example 8< example 11< example 9< example 10< example 2< example 4< comparative example 1< example 7< example 1< example 6< example 3< example 5.
At a reaction temperature of 230 ℃, the denitration efficiency is ordered from small to large as follows: example 9< example 8< example 11< example 10< example 1< example 7< example 4< example 6< example 2< comparative example 1< example 3< example 5.
As can be seen from the above comparison, the denitration efficiencies of example 7, example 1, example 6, example 3 and example 5 were all greater than those of comparative example 1 at a reaction temperature of 210℃and example 5 was the most effective. The denitration efficiency of example 3 and example 5 was greater than that of comparative example 1 at a reaction temperature of 230 c, with example 5 being the most effective denitration.
(C) From the above analysis, it was found that examples 7, 1, 6, 3 and 5 all had good denitration effects, and that examples 1 and 6 showed the best denitration effects at 130 to 190℃and example 5 showed the best denitration effects at 210 to 230 ℃. The best overall effect is example 5, which is a best example of the present invention, with denitration effect at each temperature of 130 to 230 ℃ being better than comparative example 1.
(D) As can be seen from fig. 1 and fig. 2, compared with comparative example 1, the catalyst of example 1 has smaller particles, more irregular surface, larger specific surface area, more abundant pore channels and more microporous structure, and these characteristics indicate that the catalyst of the present invention has strong ammonia adsorption capacity and fast catalytic reaction rate; the large pore canal is rich, so that the enrichment of ammonium bisulfate on the surface of the catalyst has little influence on the catalytic performance.

Claims (10)

1. The SCR denitration catalyst is characterized by comprising the following components in percentage by mass: 65 to 80 percent of titanium dioxide, 0.1 to 1.0 percent of ferric vanadate, 0.2 to 1.5 percent of vanadium pentoxide, 0.1 to 1.0 percent of cerium oxide, 10.0 to 25.0 percent of ferric oxide, 2.0 to 10.0 percent of glass fiber and 100 percent of the sum of the mass percentages of the components;
or comprises the following components in percentage by mass: the titanium dioxide is 65-80%, the ferric vanadate is 0.1-1.0%, the vanadium pentoxide is 0.2-1.5%, the ferric oxide is 10.0-25.0%, the glass fiber is 2.0-10.0%, and the sum of the mass percentages of the components is 100%.
2. The SCR denitration catalyst according to claim 1, characterized by being composed of the following components in mass percent: 71.3 to 75.8 percent of titanium dioxide, 0.3 to 0.6 percent of ferric vanadate, 0.6 to 0.9 percent of vanadium pentoxide, 0.2 to 0.6 percent of cerium oxide, 15.2 to 19 percent of ferric oxide, 3.8 to 7.6 percent of glass fiber and 100 percent of the sum of the mass percentages of the components;
or comprises the following components in percentage by mass: 72.6 to 76.5 percent of titanium dioxide, 0.3 to 0.6 percent of ferric vanadate, 0.4 to 0.9 percent of vanadium pentoxide, 15.3 to 19.1 percent of ferric oxide, 3.9 to 7.6 percent of glass fiber and 100 percent of the sum of the mass percentages of the components.
3. The SCR denitration catalyst according to claim 2, characterized by being composed of the following components in mass percent: titanium dioxide 75.7%, ferric vanadate 0.5%, vanadium pentoxide 0.9%, cerium oxide 0.7%, ferric oxide 18.9%, and glass fiber 3.8%.
4. The SCR denitration catalyst according to claim 2, characterized by being composed of the following components in mass percent: 71.3% of titanium dioxide, 0.6% of ferric vanadate, 0.8% of vanadium pentoxide, 0.4% of cerium oxide, 18.3% of ferric oxide and 7.1% of glass fiber.
5. The SCR denitration catalyst according to claim 2, characterized by being composed of the following components in mass percent: 72.1% of titanium dioxide, 0.6% of ferric vanadate, 0.8% of vanadium pentoxide, 1.0% of cerium oxide, 18.3% of ferric oxide and 7.3% of glass fiber.
6. A method for preparing an SCR denitration catalyst according to any one of claims 1 to 5, characterized in that the method comprises the steps of:
step one, preparing an active component solution:
adding ammonium metavanadate powder into water and stirring to form a suspension, adding monoethanolamine into the suspension, and continuously heating and stirring at 40-70 ℃ until ammonium metavanadate is completely dissolved to prepare an ammonium metavanadate solution; continuously introducing nitrogen into the container, adding ferrous sulfate into water under the protection of nitrogen atmosphere while stirring, and preparing ferrous sulfate solution after the ferrous sulfate is completely dissolved; adding cerium nitrate into water under the stirring condition, and preparing cerium nitrate solution after the cerium nitrate is completely dissolved;
preparing carrier mixed powder:
placing titanium dioxide in a reaction container, adding sodium stearate, lactic acid, water and ammonia water under stirring, and stirring to obtain carrier mixed powder;
step three, preparing a catalyst precursor mass:
under the stirring condition, adding the ammonium metavanadate solution, the ferrous sulfate solution and the cerium nitrate solution prepared in the first step into the carrier mixed powder prepared in the second step, and continuously stirring; then adding carboxymethyl cellulose and polyethylene oxide, adding water in the stirring process, and continuing stirring; adding glass fiber, and stirring continuously to obtain a catalyst precursor pellet;
aging and forming:
preparing a catalyst precursor material ball obtained in the step four into a pug, then carrying out moisturizing aging on the pug at room temperature, extruding the stale pug, and then forming to obtain the catalyst precursor;
step five, drying and calcining:
and (3) drying the catalyst precursor prepared in the step (IV), and placing the dried catalyst precursor in a calciner to calcine for 3-5 hours at the temperature of 400-600 ℃ to prepare the SCR denitration catalyst.
7. The method for preparing an SCR denitration catalyst according to claim 6, wherein in the fifth step, the drying process is as follows: drying at 20-40 deg.c for 5-15 days, drying at 50-80 deg.c for 2-5 days and final drying at 80-120 deg.c for 12-36 hr.
8. The method for preparing the SCR denitration catalyst as claimed in claim 6, wherein the mass ratio of sodium stearate, carboxymethyl cellulose, polyethylene oxide and titanium dioxide is 8: (10-15): (10-15): 1000.
9. the use of the SCR denitration catalyst according to any one of claims 1 to 5 for catalyzing a denitration reaction of industrial exhaust gas, wherein the denitration reaction has a reaction temperature of 130 to 230 ℃; the industrial tail gas is mixed gas containing nitrogen oxides and ammonia, and the water content of the mixed gas is 10%.
10. The use according to claim 8, wherein the denitration reaction is carried out at a reaction temperature of 130 to 150 ℃.
CN202311337308.0A 2023-10-16 2023-10-16 SCR denitration catalyst, preparation method and application thereof Pending CN117531518A (en)

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