CN117753395A

CN117753395A - Catalyst carrier and preparation method thereof, denitration catalyst and preparation method thereof

Info

Publication number: CN117753395A
Application number: CN202311728707.XA
Authority: CN
Inventors: 姚建年; 徐永; 张婷; 彭成华
Original assignee: Beijing Haishunde Titanium Catalyst Co ltd; Tan Kah Kee Innovation Laboratory
Current assignee: Beijing Haishunde Titanium Catalyst Co ltd; Tan Kah Kee Innovation Laboratory
Priority date: 2023-12-14
Filing date: 2023-12-14
Publication date: 2024-03-26

Abstract

The application discloses a catalyst carrier and a preparation method thereof, a denitration catalyst and a preparation method thereof. The preparation method of the catalyst carrier comprises the following steps: providing a first mixed solution and a titanium source solution, wherein the first mixed solution comprises an aluminum source, a silicon source and water, and the first mixed solution and the titanium source solution are mixed to obtain a second mixed solution; heating the second mixed solution to obtain a first solid; grinding the first solid to obtain a first solid powder; and mixing the first solid powder with a forming agent and water to obtain a carrier precursor mixture, and forming and calcining the carrier precursor mixture to obtain the catalyst carrier. The preparation method of the catalyst carrier ensures that enough Ti sites favorable for SCR reaction are reserved on the catalyst carrier while the catalyst carrier has higher mechanical strength, so that the denitration catalyst comprising the catalyst carrier has higher catalytic activity while having higher wear resistance and mechanical strength.

Description

Catalyst carrier and preparation method thereof, denitration catalyst and preparation method thereof

Technical Field

The application relates to the technical field of flue gas denitration, in particular to a catalyst carrier and a preparation method thereof, a denitration catalyst and a preparation method thereof.

Background

The generated energy and the coal burning amount in the thermal power industry of China are in a trend of increasing continuously, and the generated nitrogen oxides cause a series of problems such as acid rain, photochemical smog, PM2.5, greenhouse effect and the like, so that serious threat is caused to the health of human bodies. Therefore, the control and management of nitrogen oxide pollution has been a research hotspot in the international field.

At present, the flue gas denitration technology with highest efficiency, maturity and most widely application is the selective catalytic reduction technology (abbreviated as NH ₃ -SCR), which has become the first choice technology for flue gas denitration in China.

The selective catalytic reduction technology of ammonia mainly adopts a denitration catalyst for catalytic reduction, and the denitration catalyst needs to be molded when in use so that the denitration catalyst has certain granularity, strength and porosity, thereby meeting the pressure drop, compressive strength and stability of the denitration catalyst after filling. The formed denitration catalyst is usually arranged in the denitration device, and the denitration device is arranged in front of the desulfurization and dust removal device, so that the flue gas temperature is higher, and the denitration catalyst is easily lost and collapsed due to long-time exposure of the denitration catalyst to high-temperature flue gas components due to weak mechanical strength of a carrier of the existing denitration catalyst, thereby influencing the service life of the denitration catalyst.

Therefore, there is a need for a catalyst support having high mechanical strength.

Disclosure of Invention

In view of the above, the present application provides a catalyst carrier and a preparation method thereof, a denitration catalyst and a preparation method thereof, and aims to solve the problem that the existing catalyst carrier has poor mechanical strength.

The embodiment of the application is realized in such a way that a preparation method of the catalyst carrier comprises the following steps:

providing a first mixed solution and a titanium source solution, wherein the first mixed solution comprises an aluminum source, a silicon source and water, and the first mixed solution and the titanium source solution are mixed to obtain a second mixed solution;

heating the second mixed solution to obtain a first solid;

grinding the first solid to obtain first solid powder;

and mixing the first solid powder with a forming agent and water to obtain a carrier precursor mixture, and forming and calcining the carrier precursor mixture to obtain the catalyst carrier.

Optionally, in some embodiments, the molar ratio of the aluminum source to the silicon source is 1 (0.1-10), preferably the molar ratio of the aluminum source to the silicon source is 1 (1-3); and/or

The molar ratio of the aluminum source to the titanium source is 1 (20-32); and/or

The mass ratio of the molding agent to the first solid powder is 1 (78-94).

Optionally, in some embodiments, the aluminum source comprises one or more of aluminum oxide, aluminum nitrate, aluminum chloride, aluminum sulfate; and/or

The silicon source comprises one or more of silicon dioxide, silicon chloride and tetraethoxysilane; and/or

The titanium source comprises one or more of titanyl sulfate, tetrabutyl titanate, titanium dioxide, titanium sulfate, titanium chloride and titanyl sulfate; and/or

The forming agent comprises one or more of sodium carboxymethyl cellulose, hydroxypropyl cellulose, sesbania powder and polyethylene oxide.

Optionally, in some embodiments, the heating is at a temperature in the range of 55 to 100 ℃ for a time in the range of 6 to 8 hours; and/or

The particle size of the first solid powder is 40-80 meshes; and/or

The calcination temperature is 300-600 ℃, and the calcination time is 3-6 h.

Optionally, in some embodiments, a lubricant is also added to the carrier precursor mixture, wherein,

the lubricant comprises glycerol; and/or

The mass ratio of the molding agent to the lubricant is 1 (1-4).

Correspondingly, the embodiment also provides a catalyst carrier prepared by the preparation method, wherein the catalyst carrier comprises metal oxide modified TiO ₂ Wherein the metal oxide comprises Al ₂ O ₃ And SiO ₂ 。

Optionally, in some embodiments, the TiO ₂ 、Al ₂ O ₃ And SiO ₂ The mass ratio of (1) is (60-90): (0.4-10): (0.6-12), preferably, the TiO ₂ 、Al ₂ O ₃ And SiO ₂ The mass ratio of (80-90): (1-4): (2-8); and/or

In the catalyst carrier, the Al ₂ O ₃ And SiO ₂ Linking and/or bonding and/or adsorbing to TiO ₂ Is a surface of the substrate.

Correspondingly, the embodiment of the application also provides a preparation method of the denitration catalyst, which comprises the following steps:

adding an active component source into the second mixed solution, and heating to obtain a second solid;

grinding the second solid to obtain second solid powder;

and mixing the second solid powder with a forming agent and water to obtain a catalyst precursor mixture, and forming and calcining the catalyst precursor mixture to obtain the denitration catalyst.

The mass ratio of the molding agent to the first solid powder is 1 (78-94); and/or

The molar ratio of the active component source to the titanium source is in the range of 1 (9.3-16.4), preferably the molar ratio of the active component source to the titanium source is in the range of 1 (9.5-11.3); and/or

And the pH value of the system after the active component source is added into the second mixed solution is 0.8-5.5.

Optionally, in some embodiments, the active ingredient source comprises an active agent source and a co-agent source, wherein,

the active agent source comprises a vanadium source; and/or

The co-agent source includes one or more of a tungsten source, a molybdenum source, a zirconium source, and a cerium source.

Optionally, in some embodiments, the vanadium source comprises ammonium metavanadate; and/or

The tungsten source comprises one or more of ammonium tungstate and ammonium metatungstate; and/or

The molybdenum source comprises one or more of molybdenum oxide, ammonium heptamolybdate, and molybdenum sulfate; and/or

The zirconium source comprises one or more of zirconium dioxide, zirconium nitrate and zirconium chloride; and/or

The cerium source comprises one or more of cerium sulfate, cerium oxide, and cerium nitrate; and/or

The addition amount of the active agent source is as follows: so that the content of the active agent in the prepared denitration catalyst is 1.2 to 4.0 weight percent; and/or

When the coagent comprises a tungsten source, the tungsten source is added in an amount of: so that in the prepared denitration catalyst, WO ₃ The content of (2) is 0.6-2.0wt%; and/or

When the coagent includes a molybdenum source, the molybdenum source is added in an amount of: so that MoO in the prepared denitration catalyst ₃ The content of (2) is more than 0 and less than or equal to 3.0wt%; and/or

When the coagent includes a zirconium source, the zirconium source is added in an amount of: so that in the prepared denitration catalyst, zrO ₂ The content of (2) is more than 0 and less than or equal to 1.0wt%; and/or

When the coagent includes a cerium source, the cerium source is added in an amount of: so that CeO in the prepared denitration catalyst ₂ The content of (C) is more than 0 and less than or equal to 2.8wt%.

The particle size of the first solid powder is 40-80 meshes; and/or

The particle size of the second solid powder is 40-80 meshes; and/or

The calcination temperature is 300-600 ℃, and the calcination time is 3-6 h.

Optionally, in some embodiments, a lubricant is also added to the catalyst precursor mixture, wherein,

the lubricant comprises glycerol; and/or

The mass ratio of the molding agent to the lubricant is 1 (1-4).

Correspondingly, the embodiment of the application also provides a denitration catalyst, wherein the denitration catalyst comprises a catalyst carrier prepared by the preparation method of the catalyst carrier and an active component loaded on the catalyst carrier; alternatively, the denitration catalyst includes the catalyst carrier and an active component supported on the catalyst carrier; or the denitration catalyst is prepared by a preparation method of the denitration catalyst.

Optionally, in some embodiments, the mass ratio of the active component to the catalyst support in the denitration catalyst is in the range of 1 (75 to 98); and/or

The active component comprises an active agent and a active auxiliary agent, wherein the active agent comprises V ₂ O ₅ The active auxiliary agent comprises WO ₃ 、MoO ₃ 、ZrO ₂ 、CeO ₂ One or more of the following.

Optionally, in some embodiments, the denitration catalyst includes V ₂ O ₅ V at the time of ₂ O ₅ The content of (2) is 1.2-4.0wt%; and/or

The denitration catalyst comprises WO ₃ When WO ₃ The content of (2) is 0.6-2.0wt%; and/or

The denitration catalyst comprises MoO ₃ When the MoO is ₃ The content of (2) is more than 0 and less than or equal to 3.0wt%; and/or

The denitration catalyst comprises ZrO ₂ When the ZrO is ₂ The content of (2) is more than 0 and less than or equal to 1.5wt%; and/or

The denitration catalyst comprises CeO ₂ When the CeO is ₂ The content of (C) is more than 0 and less than or equal to 2.8wt%.

The preparation method of the catalyst carrier combines a specific titanium source, an aluminum source and a silicon source in a specific proportionThe powder particle size, the calcination temperature and the calcination time of the catalyst carrier are prepared to obtain the high-strength low-ratio modified catalyst carrier, so that most of Ti-O-Ti bonds in the catalyst carrier in the denitration catalyst can be combined with active components, and the denitration catalyst has higher catalytic activity. In addition, in the preparation process of the catalyst carrier, by adding an aluminum source and a titanium source in a specific proportion, the electronegativity of Al and Si is better than that of Ti and the characteristic that the Al and the Si are preferentially combined with O is utilized, the number of Ti-O bonds with longer bond length is reduced, and the bonding of Al-O bonds with shorter bond length and Si-O bonds is increased, so that the catalyst carrier has stable structure and higher mechanical strength. Furthermore, the method obtains better Al through the titanium source, the aluminum source and the silicon source with specific proportions ₂ O ₃ And SiO ₂ In this way, the catalyst carrier with higher mechanical strength is ensured to be left with enough Ti sites which are favorable for SCR reaction, so that the denitration catalyst comprising the catalyst carrier has higher wear resistance and mechanical strength and higher catalytic activity.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a flow chart of a method for preparing a catalyst carrier according to an embodiment of the present application;

FIG. 2 is a flow chart of a method for preparing a denitration catalyst according to an embodiment of the present application;

FIG. 3 is XRD patterns of the catalyst supports of support example 1 and support comparative examples 1 to 3 of the present application;

fig. 4 is an XRD pattern of the catalysts of catalyst example 1 and catalyst comparative examples 12 to 13 of the present application.

Detailed Description

The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are obtained by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to the upper and lower positions of the device in actual use or operation, and specifically the orientation of the drawing figures; while "inner" and "outer" are for the outline of the device. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or on the order of construction.

In the present application, "and/or" describing the association relationship of the association object means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural.

In this application, "at least one" means one or more, and "a plurality" means two or more. "one or more," "at least one of the following," or the like, refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.

Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.

The prior art has been to upgrade TiO by mixing reinforcements, such as clay and glass fibers, in a carrier ₂ The mechanical strength of the support, however, the reinforcement tends to decrease the activity of the catalyst, affecting the catalytic effect. The prior art also adopts SiO ₂ Modified TiO ₂ A carrier for lifting TiO ₂ The strength of the carrier is improved, but the catalytic activity of the catalyst is reduced at the same time as the strength is improved.

The technical scheme of the application is as follows:

in a first aspect, referring to fig. 1, an embodiment of the present application provides a method for preparing a catalyst carrier, including the following steps:

step S11, providing a first mixed solution and a titanium source solution, wherein the first mixed solution comprises an aluminum source, a silicon source and water, and mixing the first mixed solution and the titanium source solution to obtain a second mixed solution;

step S12, heating the second mixed solution to obtain a first solid;

step S13, grinding the first solid to obtain first solid powder;

and step S14, mixing the first solid powder with a forming agent and water to obtain a carrier precursor mixture, and forming and calcining the carrier precursor mixture to obtain the catalyst carrier.

The catalyst carrier comprises TiO modified by metal oxide ₂ The metal oxide includes Al ₂ O ₃ And SiO ₂ . In other words, the catalyst carrier is mainly composed of Al ₂ O ₃ And SiO ₂ Modified TiO ₂ A carrier. In the catalyst carrier, the Al ₂ O ₃ And SiO ₂ Is connected and/or bonded and/or adsorbed on the TiO ₂ Is a surface of the substrate.

In the step S11:

the molar ratio of the aluminum source to the silicon source is 1 (0.1-10), preferably the molar ratio of the aluminum source to the silicon source is 1 (1-3), for example, 1:0.1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc. In the range of the molar ratio, the formation of Si-O bonds and Al-O bonds in the catalyst carrier is facilitated, so that the formation of Ti-O-Ti bonds is reduced, the structural stability of the catalyst carrier is further improved, and the catalyst carrier has higher mechanical strength.

The molar ratio of the aluminum source to the titanium source is in the range of 1 (20-32), e.g., 1:20, 1:22, 1:24, 1:25, 1:26, 1:28, 1:30, 1:32, etc. In the range of the molar ratio, the prepared catalyst carrier not only has more Ti sites, but also can exert the characteristic of high strength of Al. When the molar ratio of the aluminum source to the titanium source is more than 1:20, the strength of the catalyst carrier is obviously improved, but Ti sites are fewer, so that the activity of the catalyst prepared by the catalyst carrier is inhibited; when the molar ratio of the aluminum source to the titanium source is less than 1:32, the catalyst carrier has more Ti sites, but the overall strength improvement is also very limited.

The aluminum source includes, but is not limited to, one or more of aluminum oxide, aluminum nitrate, aluminum chloride, aluminum sulfate.

The silicon source includes, but is not limited to, one or more of silicon dioxide, silicon chloride, ethyl orthosilicate.

The titanium source includes, but is not limited to, one or more of tetrabutyl titanate, titanium dioxide, titanium sulfate, titanium chloride, titanyl sulfate.

The amount of the water to be added in the first mixed solution is not limited as long as the aluminum source and the silicon source can be sufficiently dissolved or dispersed.

The concentration of the titanium source solution is not limited as long as the titanium source can be sufficiently dissolved or dispersed.

In some embodiments, the solvent in the titanium source solution is water.

In the step S12:

the heating temperature ranges from 55 to 100 ℃, for example, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, etc., and the time ranges from 6 to 8 hours, for example, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, etc. In the temperature and time range, the catalyst carrier with higher mechanical strength is prepared.

In the step S13:

the particle size of the first solid powder is 40 to 80 mesh, for example, 40 mesh, 45 mesh, 50 mesh, 55 mesh, 60 mesh, 65 mesh, 70 mesh, 75 mesh, 80 mesh, or the like. In the particle size range, the exposed active components of the denitration catalyst comprising the catalyst carrier prepared by the method can be uniformly dispersed, so that the catalytic activity of the denitration catalyst is improved, and the uniformity of the strength of the formed catalyst carrier and the intensity of the denitration catalyst can be ensured.

In the step S14:

the forming agent includes, but is not limited to, one or more of sodium carboxymethyl cellulose, hydroxypropyl cellulose, sesbania powder, and polyethylene oxide.

The mass ratio of the molding agent to the first solid powder is 1 (78-94), for example, 1:78, 1:80, 1:82, 1:83, 1:85, 1:87, 1:88, 1:89, 1:90, 1:92, 1:94, etc. In the ratio range, the subsequent forming is facilitated, and the improvement of the strength of the catalyst carrier is facilitated.

In the step S14, the first solid powder is taken as a substrate, and the adding amount of water is 18-33 wt%. In the range, the subsequent forming is facilitated, and the improvement of the strength of the catalyst carrier is facilitated.

In some embodiments, a lubricant is also added to the carrier precursor mixture. The lubricant can adjust the viscosity of the system, can properly reduce the dosage of the forming agent, and can also improve the glossiness of the catalyst carrier and the outer surface of the catalyst comprising the catalyst carrier.

In some embodiments, the lubricant includes, but is not limited to, one or more of glycerin.

In some embodiments, the mass ratio of the forming agent to the lubricant is 1 (1-4), e.g., 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, etc. In the range of the mass ratio, the first solid powder is favorable to be in a state of non-sticking to the wall during molding, thereby being favorable to molding.

The molding method may be a known method for molding a catalyst or a catalyst support, such as kneading molding or the like.

The calcination temperature is 300 to 600 ℃, such as 300 ℃, 320 ℃, 350 ℃, 380 ℃, 400 ℃, 430 ℃, 450 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃, 575 ℃, 600 ℃, and the like, and the calcination time is 3 to 6 hours, such as 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, and the like. In the temperature and time range of the calcination, the catalyst carrier is not only beneficial to the decarbonization and the dehydroxylation of the catalyst carrier, but also can improve the mechanical strength of the catalyst carrier and enable the TiO to be ₂ Has a crystal form transformation which is beneficial to the activity of the catalyst.

The calcination is favorable for the formation of aluminum oxide and silicon oxide, silicon ions and aluminum ions are easy to combine with O preferentially in the calcination process, the number of Ti-O bonds with longer bond length is reduced, and the bonding of Al-O bonds with shorter bond length and Si-O bonds is increased, so that the catalyst carrier has stable structure and higher mechanical strength.

In addition, during calcination, the molding machine and lubricant are combusted and converted into gas, which is beneficial to forming holes on the catalyst carrier when the gas overflows from the system, and is beneficial to the adsorption and desorption process of the catalyst comprising the catalyst carrier.

According to the preparation method of the catalyst carrier, the high-strength low-ratio modified catalyst carrier is prepared by combining the titanium source, the aluminum source and the silicon source in a specific proportion and the specific powder particle size, and the calcining temperature and time, so that most of Ti-O-Ti bonds in the catalyst carrier in the denitration catalyst can be combined with active components, and the denitration catalyst has higher catalytic activity. In addition, in the preparation process of the catalyst carrier, by adding an aluminum source and a titanium source in a specific proportion, the electronegativity of Al and Si is better than that of Ti and the characteristic that the Al and the Si are preferentially combined with O is utilized, the number of Ti-O bonds with longer bond length is reduced, and the bonding of Al-O bonds with shorter bond length and Si-O bonds is increased, so that the catalyst carrier has stable structure and higher mechanical strength. Furthermore, the method obtains better Al through the titanium source, the aluminum source and the silicon source with specific proportions ₂ O ₃ And SiO ₂ In this way, the catalyst carrier with higher mechanical strength is ensured to be left with enough Ti sites which are favorable for SCR reaction, so that the denitration catalyst comprising the catalyst carrier has higher wear resistance and mechanical strength and higher catalytic activity.

The high-strength carrier is obtained by a simple impregnation method, and the denitration catalyst comprising the catalyst carrier has higher catalytic activity and can be applied on a large scale.

In a second aspect, embodiments of the present application also provide a catalyst carrier, mainly used in a denitration catalyst. The catalyst support comprises metal oxide modified TiO ₂ The metal oxide includes Al ₂ O ₃ And SiO ₂ . In other words, the catalyst carrier is mainly composed of Al ₂ O ₃ And SiO ₂ Modified TiO ₂ A carrier.

In the catalyst carrier, the TiO ₂ 、Al ₂ O ₃ And SiO ₂ The mass ratio of (1) is (60-90): (0.4-10): (0.6-12), preferably the TiO ₂ 、Al ₂ O ₃ And SiO ₂ The mass ratio of (80-90): (1-4): (2-8), e.g., 60:0.4:0.6, 65:1:1, 68:2:3, 70:5:6, 72:6:8, 75:8:10, 80:9:11, 90:10:12, etc.

The catalyst carrier uses Al with specific proportion and low cost ₂ O ₃ And SiO ₂ For TiO ₂ The modified components and the content are synergistic, so that on one hand, the cost can be reduced; on the other hand, al ₂ O ₃ And SiO ₂ As an acidic oxide, more acidic sites can be introduced into the catalyst support, so that the NH of the catalyst surface comprising the catalyst support can be raised ₃ Attachment of species, thereby increasing the catalytic activity of the catalyst; on the other hand, the catalyst carrier has higher mechanical strength and can ensure most of TiO ₂ The Ti-O-Ti can provide enough attachment sites for the active components of the catalyst, so that the catalyst comprising the catalyst carrier has higher mechanical strength and higher catalytic activity.

In a third aspect, embodiments herein also provide a denitration catalyst including the above-described catalyst carrier and an active component supported on the catalyst carrier.

In the denitration catalyst, the mass ratio of the active component to the catalyst carrier is in the range of 1 (75 to 98), for example, 1:75, 1:78, 1:80, 1:82, 1:84, 1:85, 1:86, 1:88, 1:90, 1:92, 1:94, 1:96, 1:98, and the like.

In some embodiments, the active component includes an active agent and a co-agent.

The active agent includes but is not limited to V ₂ O ₅ 。

The coagent includes but is not limited to WO ₃ 、MoO ₃ 、ZrO ₂ 、CeO ₂ One or more of the following.

The denitration catalyst comprises V ₂ O ₅ V at the time of ₂ O ₅ The content of (2) is 1.2-4.0wt%; the denitration catalyst comprises WO ₃ When WO ₃ The content of (2) is 0.6-2.0wt%; the denitration catalyst comprises MoO ₃ When the MoO is ₃ The content of (2) is 0-3.0wt%; the denitration catalyst comprises ZrO ₂ When the ZrO is ₂ The content of (2) is 0-1.5 wt%; the denitration catalyst comprises CeO ₂ When the CeO is ₂ The content of (C) is 0-2.8 wt%.

V ₂ O ₅ The content of the active sites determines most of the activity, wherein the excessive V is easy to increase the cost of the catalyst, the activity is not obviously improved, the stability of the catalyst against sulfur and water is reduced, the overall activity is easy to be lower than 1.2% due to the excessively low V, and the overall average activity of the catalyst is lower than 75%; said WO ₃ The content of (2) is 0.6-2.0wt%; the activity at medium and high temperature (250-400 ℃) below this proportion of catalyst is affected, the cost is increased above this proportion of catalyst, moO ₃ The content of Mo is 0-3.0 wt%, mo is used as an auxiliary agent for modification, the Mo mainly plays a role in the sulfur resistance and water resistance stability of the catalyst, and the low-temperature activity (150-250 ℃) of the catalyst is easily reduced when the content of the Mo is higher than 3.0wt%; zrO (ZrO) ₂ The catalyst mainly plays a role in stabilizing the particle size, is beneficial to the dispersion of the surface catalyst, and when the proportion is higher than the above proportion, agglomeration is easy to cause to influence the activity; ceO (CeO) ₂ The content of the catalyst is 0 to 2.8 weight percent, has the function of oxygen storage and is beneficial to CeO ₂ With Ce ³⁺ And Ce (Ce) ⁴⁺ Is capable of retaining lattice oxygen. The catalyst is beneficial to improving the low-temperature activity of the catalyst and the electron transfer process with V with high oxidability, and the sulfur resistance and water resistance stability of the catalyst can be influenced by the too high cerium content.

The denitration catalyst disclosed in the application comprises the catalyst carrier disclosed in the application, and has high mechanical strength and high catalytic activity.

In a fourth aspect, referring to fig. 2, the embodiment of the present application further provides a method for preparing the denitration catalyst, including the following steps:

step S21: providing a first mixed solution and a titanium source solution, wherein the first mixed solution comprises an aluminum source, a silicon source and water, and the first mixed solution and the titanium source solution are mixed to obtain a second mixed solution;

s22, adding an active component source into the second mixed solution, and heating to obtain a second solid;

step S23, grinding the second solid to obtain second solid powder;

and step S24, mixing the second solid powder with a forming agent and water to obtain a catalyst precursor mixture, and forming and calcining the catalyst precursor mixture to obtain the denitration catalyst.

The components and proportions of the first mixed solution, the titanium source solution, and the forming agent are as described above, and are not described herein. The parameters of the heating and calcining are described above and will not be described in detail herein.

In some embodiments, the active ingredient source added to the second mixed solution is an active ingredient source solution. The solvent in the active component source solution is water.

In the step S21, the amount of water added in the preparation process of the denitration catalyst may be such that the pH of the system after the active component source is added to the second mixed solution is 0.8 to 5.5. In the pH value range, the denitration catalyst with higher catalytic activity is prepared.

In at least some embodiments, the water is added in an amount of: 45-70 mL of water is needed in the whole process of preparing 10g of denitration catalyst (comprising a catalyst carrier and an active component), wherein the volume ratio of water in the first mixed solution to water in the titanium source solution is 1 (1-2), and the water in the active component source solution is 10-25 mL.

The particle size of the second solid powder is 40 to 80 mesh, for example, 40 mesh, 45 mesh, 50 mesh, 55 mesh, 60 mesh, 65 mesh, 70 mesh, 75 mesh, 80 mesh, or the like. In the particle size range, the exposed active components of the denitration catalyst prepared by the method can be uniformly dispersed, so that the catalytic activity of the denitration catalyst is improved, and the uniformity of the strength of the denitration catalyst after molding can be ensured.

The active ingredient sources include an active agent source and a co-agent source. Wherein the active agent source includes, but is not limited to, a vanadium source and the coagent source includes, but is not limited to, one or more of a tungsten source, a molybdenum source, a zirconium source, and a cerium source.

The vanadium source includes, but is not limited to, ammonium metavanadate.

The tungsten source includes, but is not limited to, one or more of ammonium tungstate, ammonium metatungstate.

The molybdenum source includes, but is not limited to, one or more of molybdenum oxide, ammonium heptamolybdate, and molybdenum sulfate.

The zirconium source includes, but is not limited to, one or more of zirconium dioxide, zirconium nitrate, zirconium chloride.

The cerium source includes, but is not limited to, one or more of cerium sulfate, cerium oxide, and cerium nitrate.

In some embodiments, the molar ratio of the active component source to the titanium source ranges from 1 (9.3 to 16.4), preferably the molar ratio of the active component source to the titanium source ranges from 1 (9.5 to 11.3), e.g., 1:9.3, 1:9.5, 1:10, 1:10.5, 1:10.8, 1:11, 1:11.2, 1:11.5, 1:11.6, 1:12, 1:12.2, 1:12.4, 1:12.5, 1:12.7, 1:13, 1:13.5, 1:14, 1:14.5, 1:15, 1:15.5, 1:16, 1:16.4, etc. In the range of the molar ratio, the denitration catalyst is favorable to have higher catalytic activity.

In some embodiments, the active agent source is added in an amount of: so that the content of the active agent in the prepared denitration catalyst is 1.2 to 4.0 weight percent.

When the coagent comprises a tungsten source, the tungsten source is added in an amount of: so that in the prepared denitration catalyst, WO ₃ The content of (C) is 0.6-2.0 wt%.

When the coagent includes a molybdenum source, the molybdenum source is added in an amount of: so that MoO in the prepared denitration catalyst ₃ The content of (C) is more than 0 and less than or equal to 3.0wt%.

When the coagent includes a zirconium source, the zirconium source is added in an amount of: so that in the prepared denitration catalyst, zrO ₂ The content of (C) is more than 0 and less than or equal to 1.0wt%.

In some embodiments, a lubricant is also added to the catalyst precursor mixture. The lubricant can adjust the viscosity of the system, properly reduce the dosage of the forming agent and improve the glossiness of the catalyst carrier and the outer surface of the catalyst.

According to the preparation method of the denitration catalyst, by combining the specific titanium source, the aluminum source, the silicon source and the active component source in a specific proportion and combining the specific second solid powder particle size and the calcining temperature and time, most of Ti-O-Ti bonds in the catalyst carrier in the denitration catalyst can be combined with the active components, so that the denitration catalyst has higher catalytic activity. Further, in the preparation process of the denitration catalyst carrier, by adding an aluminum source and a titanium source in a specific proportion, the electronegativity of Al and Si is better than that of Ti and the characteristic that the Al and the Si are preferentially combined with O is utilized, the number of Ti-O bonds with longer bond length is reduced, and the bonding of Al-O bonds with shorter bond length and Si-O bonds is increased, so that the structure of the catalyst carrier is stable and has higher mechanical strength, and the structure of the denitration catalyst is stable and has higher mechanical strength. Furthermore, the method obtains better Al through the titanium source, the aluminum source and the silicon source with specific proportions ₂ O ₃ And SiO ₂ In such a way that a higher mechanical strength is advantageously obtainedThe catalyst carrier ensures that enough Ti sites favorable for SCR reaction are reserved on the catalyst carrier, so that the denitration catalyst comprising the catalyst carrier has higher wear resistance and mechanical strength and higher catalytic activity.

The present application is specifically illustrated by the following examples, which are only some of the examples of the present application and are not limiting of the present application. The raw materials used in the following examples are all commercially available products unless otherwise specified.

Carrier example 1

Mixing aluminum nitrate and silicon dioxide into water to obtain a first mixed solution, dissolving titanium dioxide into the water to obtain a titanium source solution, and adding the first mixed solution into the titanium source solution, wherein the molar ratio of the aluminum nitrate to the silicon dioxide to the titanium dioxide is 1:2:26 to obtain a second mixed solution;

heating and stirring to dryness at 75 ℃ to obtain a solid;

grinding and sieving the solid to obtain solid powder with the particle size of 60 meshes, and adding a forming agent carboxymethyl cellulose and a lubricant glycerol into the solid powder, wherein the weight ratio of the forming agent to the lubricant to the solid powder is 1:2.5:88, molding and calcining at 500 ℃ for 4 hours to obtain the catalyst carrier.

Carrier example 2

Mixing aluminum chloride and silicon dioxide into water to obtain a first mixed solution, dissolving titanium sulfate into the water to obtain a titanium source solution, and adding the first mixed solution into the titanium source solution, wherein the molar ratio of the aluminum chloride to the silicon dioxide to the titanium sulfate is 1:1:20, obtaining a second mixed solution;

heating and stirring to dryness at 75 ℃ to obtain a solid;

grinding and sieving the solid to obtain solid powder with the particle size of 80 meshes, and adding sodium hydroxypropyl cellulose serving as a forming agent and glycerin serving as a lubricant into the solid powder, wherein the weight ratio of the forming agent to the solid powder is 1:1:78, molding and calcining at 600 ℃ for 6 hours to obtain the catalyst carrier.

Carrier example 3

Mixing aluminum oxide and silicon chloride into water to obtain a first mixed solution, dissolving tetrabutyl titanate into the water to obtain a titanium source solution, and adding the first mixed solution into the titanium source solution, wherein the molar ratio of the aluminum oxide to the silicon chloride to the tetrabutyl titanate is 0.5:3:32 to obtain a second mixed solution;

heating and stirring to dryness at 75 ℃ to obtain a solid;

grinding and sieving the solid to obtain solid powder with the particle size of 80 meshes, and adding a forming agent polyethylene oxide and a lubricant glycerol into the solid powder, wherein the weight ratio of the forming agent to the lubricant to the solid powder is 1:3:85, molding and calcining at 400 ℃ for 3.5h to obtain the catalyst carrier.

Carrier example 4

Mixing aluminum sulfate and silicon chloride into water to obtain a first mixed solution, dissolving tetrabutyl titanate into the water to obtain a titanium source solution, and adding the first mixed solution into the titanium source solution, wherein the molar ratio of aluminum oxide to silicon chloride to tetrabutyl titanate is 1:3:26, obtaining a second mixed solution;

heating and stirring to dryness at 75 ℃ to obtain a solid;

grinding and sieving the solid to obtain solid powder with the particle size of 70 meshes, and adding forming agent sesbania powder and lubricant glycerol into the solid powder, wherein the weight ratio of the forming agent to the lubricant to the solid powder is 1:4:90, molding and calcining at 550 ℃ for 5 hours to obtain the catalyst carrier.

Carrier example 5

This example is essentially the same as the carrier example 1, except that: the molar ratio of aluminum nitrate to silica in this example was 1:0.5.

Carrier example 6

This example is essentially the same as the carrier example 1, except that: the molar ratio of aluminum nitrate to silica in this example was 1:5.

Carrier example 7

This example is essentially the same as the carrier example 1, except that: in this example, the molar ratio of aluminum nitrate, silica, and titanium dioxide is 1:1:20.

Carrier example 8

This example is essentially the same as the carrier example 1, except that: in this example, the molar ratio of aluminum nitrate, silica, and titanium dioxide is 1:3:32.

carrier example 9

This example is essentially the same as the carrier example 1, except that: the weight ratio of the molding agent to the lubricant in this example was 1:1.

Carrier example 10

This example is essentially the same as the carrier example 1, except that: the weight ratio of the molding agent to the lubricant in this example was 1:2.

Carrier example 11

This example is essentially the same as the carrier example 1, except that: the weight ratio of the molding agent to the lubricant in this example was 1:4.

Carrier example 12

This example is essentially the same as the carrier example 1, except that: the calcination temperature in this example was 300 ℃.

Carrier example 13

This example is essentially the same as the carrier example 1, except that: the calcination temperature in this example was 450 ℃.

Carrier example 14

This example is essentially the same as the carrier example 1, except that: the calcination temperature in this example was 600 ℃.

Comparative example 1 with Carrier

Heating and stirring the titanium dioxide solution in water at 75 ℃ to obtain a solid;

grinding and sieving the solid to obtain solid powder with the particle size of 60 meshes;

Adding a forming agent of carboxymethyl cellulose and a lubricant of glycerin into solid powder, wherein the weight ratio of the forming agent to the lubricant to the solid powder is 1:2.5:88, molding, calcining at 500 ℃ for 4 hours to obtain TiO ₂ A carrier.

Comparative example 2 with Carrier

Aluminum nitrate and titanium dioxide solution are dissolved in water, wherein the molar ratio of the aluminum nitrate to the titanium dioxide is 1:26, heating and stirring to dryness at 75 ℃ to obtain a solid;

adding a forming agent sodium carboxymethyl cellulose and lubrication glycerol into solid powder, wherein the weight ratio of the forming agent to the lubrication agent to the solid powder is 1:2.5:88, molding, calcining at 500 ℃ for 4 hours to obtain Al ₂ O ₃ Modified TiO ₂ A carrier.

Comparative example 3 with Carrier

The silica and titania solution in water, wherein the mole ratio of silica to titania is 1:26, heating and stirring to dryness at 75 ℃ to obtain a solid;

adding a forming agent of carboxymethyl cellulose and a lubricant of glycerin into the solid powder, wherein the weight ratio of the forming agent to the lubricant to the solid powder is 1:2.5:88, molding, calcining at 500 ℃ for 4 hours to obtain Al ₂ O ₃ Modified TiO ₂ A carrier.

Comparative example 4 with carrier

This comparative example is essentially identical to the vector example 1, except that: the molar ratio of aluminum nitrate to silica in this comparative example was 1:0.5.

Comparative example 5 with Carrier

This comparative example is essentially identical to the vector example 1, except that: the molar ratio of aluminum nitrate to silica in this comparative example was 1:4.

Comparative example 6 with Carrier

This comparative example is essentially identical to the vector example 1, except that: the molar ratio of aluminum nitrate, silicon dioxide and titanium dioxide in this comparative example was 1:5:10.

Comparative example 7 with carrier

This comparative example is essentially identical to the vector example 1, except that: the molar ratio of aluminum nitrate, silica and titanium dioxide in this comparative example was 1:0.5:40.

Comparative example 8 with Carrier

This comparative example is essentially identical to the vector example 1, except that: the weight ratio of the molding agent to the lubricant in this comparative example was 1:0.5.

Comparative example 9 with Carrier

This comparative example is essentially identical to the vector example 1, except that: the weight ratio of the molding agent to the lubricant in this comparative example was 1:5.

Comparative example 10 with Carrier

This comparative example is essentially identical to the vector example 1, except that: the calcination temperature in this comparative example was 250 ℃.

Comparative example 11 with Carrier

This comparative example is essentially identical to the vector example 1, except that: the calcination temperature in this comparative example was 700 ℃.

The strength test was carried out on the catalyst supports of support examples 1 to 14 and support comparative examples 1 to 11, respectively, and the test results are shown in Table I.

The method for testing the strength comprises the steps of dividing the extruded and calcined carrier into long strips with the length of about 0.5 cm to 1cm, measuring by using a strength tester, adjusting the testing mode to be 1 (a strip catalyst), testing according to a program set in the tester, and removing the highest and lowest values after testing for 10 times, wherein the strength value of each sample is the average value after removing the highest and lowest values.

Table one:

/>

from Table one can see:

the calcining temperature of the carrier directly influences the mechanical strength of the carrier, when the temperature is lower than 300 ℃, the strength of the carrier is greatly reduced, when the temperature is higher than 600 ℃, the strength of the carrier is improved very limited, and from the aspects of comprehensive strength and energy consumption cost, the calcining interval of the carrier is 300-600 ℃; in the process of optimizing the molding process, the quality of the molding agent, the lubricant and the carrier powder also has an influence on the molding strength of the carrier, and the proportion of the molding agent, the lubricant and the carrier powder can influence the viscous state of the carrier powder and the dry-wet state of the material during extrusion molding, can influence the pressure strength of an extruder, and further influence the carrier strength; the titanium source, the silicon source and the aluminum source of the carrier are the material properties of the carrier, and the strength of the carrier can be influenced to a certain extent, but as a preferred scheme of the experiment, the activity of the carrier after the active components are loaded is considered, so that the carrier synthesized by adopting aluminum silicon only has higher strength (higher than that of the embodiment 1), but the carrier cannot be applied to the titanium-vanadium-based catalyst of the system.

XRD tests were carried out on the catalyst supports of support example 1 and support comparative examples 1 to 3 to obtain XRD patterns shown in FIG. 3.

As can be seen from FIG. 3, the catalyst supports of comparative examples 1 and 3 and example 1 have no significant difference in crystal structure, and each peak can be matched to TiO ₂ It can be seen that SiO in carrier example 1 ₂ No change in lattice, dispersed in TiO ₂ The surface of the carrier. Al was labeled in comparative example 2 ₂ O ₃ The catalyst support of support example 1 also had Al as shown by the weaker peak at the corresponding position in support example 1 ₂ O ₃ And Al is ₂ O ₃ Uniformly dispersed in TiO ₂ The surface of the carrier.

Catalyst example 1

This example is substantially the same as the carrier example 1 except that this example includes, after the second mixed liquid is obtained:

providing an active component source solution, and adding the active component source solution into the second mixed solution, wherein the active component source solution comprises ammonium metavanadate and ammonium tungstate which are respectively expressed as V ₂ O ₅ And WO ₃ Calculating to obtain solid powder with particle diameter of 60 meshes, adding forming agent hydroxypropyl cellulose and lubricant glycerin into the solid powder, wherein the forming agent comprises 3wt% and 1.6wt% of ammonium metavanadate, heating and stirring to dry at 75 ℃, grinding and sieving to obtain solid powder with particle diameter of 60 meshes, and the forming agent comprises the following components of The weight ratio of the lubricant to the solid powder is 1:2.5:88, molding and calcining at 500 ℃ for 4 hours to obtain the denitration catalyst.

Catalyst examples 2 to 11

Catalyst examples 2 to 11 are substantially the same as catalyst example 1 except that catalyst examples 2 to 11 are added with the active component source solutions to the second mixed solutions of support examples 2 to 11, respectively.

Catalyst example 13

This example is essentially the same as catalyst example 1, except that in this example ammonium metavanadate and ammonium tungstate are each prepared as a catalyst in the form of V ₂ O ₅ And WO ₃ Calculated to be added to the second mixed liquor in an amount of 1.2wt% and 0.6 wt%.

Catalyst example 14

Catalyst example 1 of this example is essentially the same except that in this example ammonium metavanadate and ammonium tungstate are each prepared as a catalyst in the form of V ₂ O ₅ And WO ₃ Calculated, the addition amounts of 4% and 2% were added to the second mixed solution.

Catalyst comparative examples 1 to 10

Catalyst comparative examples 1 to 10 are substantially the same as catalyst example 1 except that catalyst comparative examples 1 to 10 use the catalyst carriers of carrier comparative examples 1 to 10, respectively, instead of the catalyst carrier of example 1.

Catalyst comparative example 11

This comparative example is essentially identical to catalyst example 1, except that in this comparative example the ammonium metavanadate is present as V ₂ O ₅ Calculated to be added to the second mixed solution in an amount of 3 wt%.

Catalyst comparative example 12

This comparative example is substantially identical to catalyst example 1, except that in this comparative example ammonium tungstate is used as a catalyst in the form of WO ₃ Calculated to be added to the second mixed liquor in an amount of 0.5 wt%.

Catalyst comparative example 13

This comparative example is substantially the same as catalyst example 1, except that in this comparative example ammonium metavanadate and ammonium tungstate are each prepared as a catalyst in the form of V ₂ O ₅ And WO ₃ Calculated to be added to the second mixed solution in an amount of 1wt% and 0.5 wt%.

Catalyst comparative example 14

This comparative example is substantially the same as catalyst example 1, except that in this comparative example ammonium metavanadate and ammonium tungstate are each prepared as a catalyst in the form of V ₂ O ₅ And WO ₃ Calculated to be added to the second mixed solution in addition amounts of 5wt% and 3 wt%.

The denitration catalysts of catalyst examples 1 to 14 and catalyst comparative examples 1 to 14 were respectively examined for mechanical strength, reaction temperature window, and highest denitration efficiency, and the examination results are referred to in Table II.

The detection method of the reaction temperature window is to adopt self-control software to perform programmed temperature rise on the fixed bed reactor, detect the actual temperature inside the catalyst bed layer through thermocouple, and set the temperature window tested by the thermocouple to select the denitration activity of different temperature points;

The detection method of the highest denitration efficiency is that the denitration rate refers to the removal rate of NOx in the flue gas, and the calculation method is as follows: (NOx content in flue gas at reactor inlet (mg/Nm) ³ ) NOx content (mg/Nm) in the flue gas at the reactor outlet ³ ) NOx content (mg/Nm) in the flue gas at the reactor inlet ³ ) X 100%. And testing the denitration efficiency of different temperature sections, and taking the highest value as the highest denitration efficiency.

And (II) table:

/>

from Table II, it can be seen that:

the weight proportion of the shaping agent, the lubricating agent and the carrier dry powder only affects the strength of the catalyst, and the effect of promoting the activity of the catalyst is small (almost negligible); too low/too high a calcination temperature of the catalyst affects the activity of the catalyst when the temperature is too highAt high levels, the catalyst support TiO ₂ The crystal morphology of the catalyst is changed, the activity of the catalyst is inhibited, and when the temperature is too low, the mechanical strength of the catalyst is influenced, and meanwhile, the activity of the catalyst is inhibited; the reason is that the higher the temperature is, the stronger the lattice oxygen action on the catalyst surface is, and the electron transfer between metals can occur to change the redox performance of the catalyst, to NH ₃ -the SCR system plays a critical role; the main active site V has the main effect on the activity, the content of the V directly affects the activity of the catalyst, but too high vanadium also has an inhibiting effect on the activity, and W only has an auxiliary effect, when V does not exist, the reaction activity of the V is very low (less than 15%), and the ratio of the V and the V are matched with each other, so that the activity of the catalyst can be greatly improved.

XRD tests were conducted on the catalysts of catalyst example 1 and catalyst comparative examples 12 to 13 to obtain XRD patterns shown in FIG. 4.

As can be seen from FIG. 4, the catalyst supports of comparative examples 12 to 13 and example 1 have no significant difference in crystal structure, and each peak can be matched to TiO ₂ Is a diffraction peak of (2).

The foregoing has outlined the detailed description of the embodiments of the present application, and specific examples have been presented herein to illustrate the principles and embodiments of the present application, the above examples being provided solely to assist in the understanding of the methods and core ideas of the present application; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.

Claims

1. A method for preparing a catalyst support, comprising the steps of:

heating the second mixed solution to obtain a first solid;

Grinding the first solid to obtain first solid powder;

2. The method of claim 1, wherein,

the molar ratio of the aluminum source to the silicon source is 1 (0.1-10), preferably the molar ratio of the aluminum source to the silicon source is 1 (1-3); and/or

The mass ratio of the molding agent to the first solid powder is 1 (78-94).

3. The method of claim 1, wherein,

the aluminum source comprises one or more of aluminum oxide, aluminum nitrate, aluminum chloride and aluminum sulfate; and/or

4. The method of claim 1, wherein,

the heating temperature ranges from 55 ℃ to 100 ℃, and the heating time ranges from 6 hours to 8 hours; and/or

The particle size of the first solid powder is 40-80 meshes; and/or

The calcination temperature is 300-600 ℃, and the calcination time is 3-6 h.

5. The method of claim 1, wherein a lubricant is further added to the carrier precursor mixture, wherein,

the lubricant comprises glycerol; and/or

The mass ratio of the molding agent to the lubricant is 1 (1-4).

6. A catalyst carrier prepared by the preparation method according to any one of claims 1 to 5, characterized in that the catalyst carrier comprises a metal oxide modified TiO ₂ Wherein the metal oxide comprises Al ₂ O ₃ And SiO ₂ 。

7. The catalyst support according to claim 6, wherein,

the TiO ₂ 、Al ₂ O ₃ And SiO ₂ The mass ratio of (1) is (60-90): (0.4-10): (0.6-12), preferably, the TiO ₂ 、Al ₂ O ₃ And SiO ₂ The mass ratio of (80-90): (1-4): (2-8); and/or

8. The preparation method of the denitration catalyst is characterized by comprising the following steps of:

grinding the second solid to obtain second solid powder;

9. The method of claim 8, wherein,

10. The method of manufacturing as claimed in claim 8, wherein the active ingredient source comprises an active agent source and a co-agent source, wherein,

the active agent source comprises a vanadium source; and/or

11. The method of claim 10, wherein,

the vanadium source comprises ammonium metavanadate; and/or

12. The method of claim 8, wherein,

13. The method of claim 8, wherein,

The particle size of the first solid powder is 40-80 meshes; and/or

The particle size of the second solid powder is 40-80 meshes; and/or

The calcination temperature is 300-600 ℃, and the calcination time is 3-6 h.

14. The method of claim 8, wherein a lubricant is further added to the catalyst precursor mixture, wherein,

the lubricant comprises glycerol; and/or

The mass ratio of the molding agent to the lubricant is 1 (1-4).

15. A denitration catalyst, which is characterized by comprising a catalyst carrier prepared by the preparation method according to any one of claims 1 to 5 and an active component loaded on the catalyst carrier; alternatively, the denitration catalyst comprises the catalyst carrier as defined in any one of claims 6 to 7 and an active component supported on the catalyst carrier; or the denitration catalyst is prepared by the preparation method of any one of claims 8 to 14.

16. The denitration catalyst according to claim 15,

In the denitration catalyst, the mass ratio of the active component to the catalyst carrier is 1 (75-98); and/or

17. The denitration catalyst according to claim 16, wherein,

the denitration catalyst comprises V ₂ O ₅ V at the time of ₂ O ₅ The content of (2) is 1.2-4.0wt%; and/or

The denitration catalyst comprises WO ₃ When WO ₃ Contains (1)The amount is 0.6 to 2.0 weight percent; and/or