CN115739071A - Denitration catalyst and preparation method thereof - Google Patents
Denitration catalyst and preparation method thereof Download PDFInfo
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- CN115739071A CN115739071A CN202211494642.2A CN202211494642A CN115739071A CN 115739071 A CN115739071 A CN 115739071A CN 202211494642 A CN202211494642 A CN 202211494642A CN 115739071 A CN115739071 A CN 115739071A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 40
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010937 tungsten Substances 0.000 claims abstract description 32
- -1 titanium-tungsten-zirconium-silicon oxide Chemical group 0.000 claims abstract description 31
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
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- 229910052796 boron Inorganic materials 0.000 claims description 37
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- 239000010936 titanium Substances 0.000 claims description 23
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- 239000011259 mixed solution Substances 0.000 claims description 19
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
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- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical group [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 7
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- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical group Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
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- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims 2
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- 238000012986 modification Methods 0.000 abstract description 4
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- Catalysts (AREA)
Abstract
The invention relates to the technical field of flue gas denitration catalysts, in particular to a denitration catalyst and a preparation method thereof, wherein the denitration catalyst comprises a carrier, an active component, a cocatalyst, a surfactant, a binder and a pore-forming agent, and the mass ratio of the carrier to the active component to the cocatalyst to the surfactant to the binder to the pore-forming agent is 100: (0.5-2): (1-15): (0.1-4): (0.5-5): (0.1-3), wherein the carrier is titanium-tungsten-zirconium-silicon oxide, the active component is vanadium-cerium-erbium-boron oxide, and the promoter is one or more oxides of tungsten, lanthanum, neodymium, tin, iron, indium and yttrium. Denitration catalyst of the inventionThe catalyst takes titanium-tungsten-zirconium-silicon oxide as a carrier, vanadium-cerium-erbium-boron oxide as an active component, one or more oxides of tungsten, lanthanum, neodymium, tin, iron, indium and yttrium as a cocatalyst, and is emulsified, dispersed, molded and subjected to micropore modification by using a surfactant, a binder and a pore-forming agent, SO that the obtained catalyst has good denitration activity and low SO at the temperature of 330-650 DEG C 2 Oxidation performance and high selectivity.
Description
Technical Field
The invention relates to the technical field of flue gas denitration catalysts, in particular to a denitration catalyst and a preparation method thereof.
Background
With the rapid development of economy, the emission of nitrogen oxides (NOx) is rapidly increased, and researches show that the NOx is an important reason for forming haze weather and becomes one of factors for restricting the development of socioeconomic.
Under the large background that the nation vigorously develops clean coal-burning technology and advocates ultra-low emission, the nation strengthens the emission control of pollutants of coal-burning units. The simple low-nitrogen combustion technology can not meet the requirements of the current emission standard, and the Selective Catalytic Reduction (SCR) technology has been widely popularized and applied to domestic coal-fired power plants due to the efficient and reliable denitration performance of the SCR technology. The main principle of SCR is NH 3 Is a reducing agent, and selectively reduces NOx into N under the action of a denitration catalyst 2 。
At present, SCR denitration catalysts are put into use on a large scale, and the most applied commercial catalyst is vanadium tungsten titanium based SCR catalyst V 2 O 5 -WO 3 (MoO 3 )/TiO 2 The activity window is 320-420 ℃, when the flue gas temperature exceeds the catalyst activity range, the catalyst has sintering inactivation phenomenon, sintering is easy to occur, the denitration activity is reduced, the selectivity is low, and SO is generated 2 /SO 3 The oxidation rate is high. This is due to anatase type TiO 2 Easily transform to rutile crystal form at high temperature (> 450 ℃). In addition, due to V 2 O 5 Strong oxidation of, SO in, flue gas 2 Often converted to SO 3 Then combined with ammonia water in the flue gas to generate NH 4 HSO 4 Corrosion of flue and equipment, and V 2 O 5 The product has toxicity and causes secondary pollution to the environment. Therefore, the denitration catalyst cannot meet the high-temperature flue gas denitration of distributed energy, fluidized bed furnaces, industrial kilns and the like.
Therefore, the catalyst is poor in high-temperature stability and SO (sulfur oxide) aiming at the traditional denitration catalyst 2 /SO 3 The development of a high-temperature denitration catalyst with low sulfur oxidation is a technical problem which needs to be solved urgently by a person skilled in the art.
Disclosure of Invention
The invention aims to provide a denitration catalyst and a preparation method thereof, wherein the denitration catalyst has good denitration activity and low SO at the temperature of 330-650 DEG C 2 Oxidation performance and high selectivity.
In a first aspect, the invention provides a denitration catalyst, which comprises a carrier, an active component, a cocatalyst, a surfactant, a binder and a pore-forming agent, wherein the mass ratio of the carrier, the active component, the cocatalyst, the surfactant, the binder and the pore-forming agent is 100: (0.5-2): (1-15): (0.1-4): (0.5-5): (0.1-3), wherein the carrier is titanium-tungsten-zirconium-silicon oxide, the active component is vanadium-cerium-erbium-boron oxide, and the cocatalyst is one or more oxides of tungsten, lanthanum, neodymium, tin, iron, indium and yttrium.
The denitration catalyst provided by the invention takes titanium-tungsten-zirconium-silicon oxide as a carrier, vanadium-cerium-erbium-boron oxide as an active component, one or more oxides of tungsten, lanthanum, neodymium, tin, iron, indium and yttrium as a cocatalyst, and uses a surfactant, a binder and a pore-forming agent to carry out emulsification dispersion, molding and micropore modification, SO that the synergistic effect between the carrier and the active component and the cocatalyst is further optimized, the high-temperature denitration activity of the catalyst is improved, the modified pore structure further inhibits the SO of the catalyst 2 Oxidation of (2).
In the present embodiment, the molar ratio of Ti, W, zr, and Si in the carrier is preferably 100: (0.5-15): (0.1-10): (0.1-5); in the active components, the molar ratio of V, ce, er and B is 10: (0.1-8): (0.1-3): (0.1-3).
Research shows that when the molar ratio of each element in the carrier and the active component is the specific molar ratio, the prepared denitration catalyst has the strongest mutual synergistic effect among the carrier, the active component and the cocatalyst, and is favorable for regulating the acid positions B and L of the catalyst, SO that the high-temperature activity of the denitration catalyst is improved, and SO at high temperature is inhibited 2 Adsorption on the surface of the catalyst and migration in the pore channel, thereby reducing SO 2 Oxidation of (2).
The specific compositions of the surfactant, the binder and the pore-forming agent are not strictly limited, and the surfactant, the binder and the pore-forming agent commonly used in the traditional commercial denitration catalyst can be selected, wherein the surfactant mainly plays a role in emulsification and dispersion and comprises any one or more of glyceryl monostearate, lauric acid, polyether, glyceryl monostearate and fluorine-containing siloxane; the binder mainly plays a role in forming and comprises any one or more of carboxymethyl cellulose, ammonium polyacrylate, hydroxypropyl methyl cellulose, amino cellulose, aluminum sol and silica sol; the pore-forming agent mainly plays a role in modifying micropores and mainly comprises any one or more of starch, activated carbon powder, chitosan, polymethacrylate and methyl methacrylate.
In a second aspect, the invention also discloses a preparation method of the denitration catalyst, which is also supposed to belong to the protection scope of the invention, and specifically comprises the following steps:
pouring the mixed solution of vanadium, cerium, erbium and boron active components into a titanium-tungsten-zirconium-silicon oxide carrier, uniformly stirring, adding a saturated solution of a cocatalyst, continuously stirring, and sequentially adding a surfactant, a binder, a pore-forming agent and deionized water to prepare a catalyst paste; and sealing, ageing, drying, calcining and grinding the catalyst paste in sequence to obtain the denitration catalyst.
Preferably, in the technical solution, the preparation of the titanium-tungsten-zirconium-silicon oxide carrier comprises the following steps:
s1, respectively weighing a zirconium source and a tungsten source, dissolving the zirconium source and the tungsten source in deionized water, and adding a mixture of methanesulfonic acid and acetic acid to prepare a solution containing zirconium and tungsten;
s2, adding tetrabutyl titanate and ethyl silicate into the absolute ethyl alcohol solution, and uniformly stirring to obtain a titanium-containing solution and a silicon-containing solution;
s3, adding the solution containing zirconium and tungsten into the solution containing titanium and silicon, stirring, standing for at least 2h, and adding nano TiO 2 Stirring to obtain paste with water content of 30-45%;
s4, sequentially carrying out heat preservation, calcination and grinding on the paste to obtain a titanium-tungsten-zirconium-silicon oxide carrier;
the type of the zirconium source is not strictly limited, zirconium oxychloride or zirconium hydroxide or other soluble salt can be selected, and similarly, the type of the tungsten source is not strictly limited, ammonium metatungstate or other soluble salt can be selected, and the volume ratio of the deionized water to the acid mixture is 1: (0.01-0.3);
the specific conditions of heat preservation and calcination are not strictly limited, and in the preferred embodiment of the invention, during heat preservation, the paste is placed in a reaction kettle for heat preservation, the temperature of the reaction kettle is controlled to be 180-210 ℃, and the time is 12-36h; during the calcination, the temperature is controlled to be 600-750 ℃ and the time is 2-10h.
The invention adopts a sol method and a mechanical blending method to prepare the titanium-tungsten-zirconium-silicon oxide carrier, effectively inhibits the diffusion between anatase microcrystals, and improves anatase TiO 2 The high-temperature stability of the catalyst solves the problems that the traditional vanadium-tungsten-titanium-based SCR catalyst is easy to sinter at high temperature, the denitration activity is reduced, the selectivity is low, and SO is generated 2 /SO 3 High oxidation rate and the like. In addition, in the carrier, the synergistic effect of the four substances of titanium, tungsten, zirconium and silicon provides more active component loading sites for the catalyst, forms more vacancy defects, is beneficial to the dispersion and loading of active substances, further promotes the catalytic reaction and improves the denitration activity.
Preferably, the technical solution is that the nano TiO 2 The mass ratio of the titanium oxide to the calcined tetrabutyl titanate is 1: (0.01-0.1).
Preferably, in the technical scheme, the preparation method of the vanadium-cerium-erbium-boron active component comprises the following steps:
sa, dissolving a vanadium source in oxalic acid to prepare a vanadium-containing solution;
sb, dissolving boric acid in deionized water to prepare a boron-containing solution;
sc, simultaneously dissolving a cerium source and an erbium source in deionized water to prepare a cerium-containing solution and an erbium-containing solution;
slowly pouring the boron-containing solution into the vanadium-containing solution, stirring, heating for 1-2h at 60-80 ℃, slowly adding the cerium-containing solution and the erbium-containing solution, and heating for 5-10h at 60-80 ℃ to prepare a mixed solution of vanadium, cerium, erbium and boron active components;
the invention does not strictly limit the types of vanadium sources, can select vanadyl oxalate or other soluble vanadium salts, and controls the temperature to be 60-80 ℃ during dissolution;
similarly, the invention is not limited to the types of cerium source and erbium source, wherein the cerium source can be cerium nitrate or other soluble cerium salt, and the erbium source can be erbium nitrate or other soluble erbium salt.
Preferably, in the present embodiment, the saturated solution of the cocatalyst is a saturated aqueous solution or a saturated acid solution of the cocatalyst. Furthermore, the promoter used in the preparation is preferably a promoter whose soluble salt is soluble in water or an acidic solution, where the acid-promoter soluble salt is selected from citric acid, oxalic acid or other acids.
Preferably, in the technical scheme, the temperature is controlled to be 15-30 ℃ and the time is 36-72h when the sealing and the ageing are carried out; during drying, the temperature is controlled to be 50-60 ℃ and the time is 240-480h; and during calcination, the temperature is controlled to be 450-650 ℃, and the time is 1-5h.
The catalyst prepared by ageing, drying and calcining under specific conditions shows good high-temperature activity and low SO 2 Oxidation efficiency and excellent N 2 And (4) selectivity.
The denitration catalyst disclosed by the invention at least has the following technical effects:
1. the denitration catalyst takes titanium-tungsten-zirconium-silicon oxide as a carrier, vanadium-cerium-erbium-boron oxide as an active component, and one or more oxides of tungsten, lanthanum, neodymium, tin, iron, indium and yttriumThe catalyst promoter is emulsified, dispersed, formed and micropore modified by using a surfactant, a binder and a pore-forming agent, and the obtained catalyst has good denitration activity and low SO content at the temperature of 330-650 DEG C 2 The catalyst has oxidation performance and high selectivity, is a denitration catalyst with high industrial application value, and can meet the high-temperature flue gas denitration of distributed energy, fluidized bed furnaces, industrial kilns and the like;
2. the titanium-tungsten-zirconium-silicon oxide carrier in the denitration catalyst effectively inhibits the diffusion between anatase microcrystals and improves anatase TiO 2 The high-temperature stability of the catalyst is realized, and meanwhile, the synergistic effect of the titanium, tungsten, zirconium and silicon provides more active component loading sites for the catalyst, so that more vacancy defects are formed, the dispersion and loading of active substances are facilitated, the catalytic reaction is further promoted, and the denitration activity is improved;
3. the good dispersant loading of the vanadium, cerium, erbium and boron active component in the denitration catalyst on the carrier improves the catalyst O α The content of the active component in the denitration catalyst reduces the oxygen bridge density of the catalyst, and simultaneously, the B acid and the L acid sites of the catalyst are modulated under the synergistic effect of the active component, the cocatalyst and the carrier, SO that the high-temperature activity of the denitration catalyst is improved, and SO at high temperature is inhibited 2 The adsorption on the surface of the catalyst and the migration in the pore channels reduce the SO of the catalyst 2 Oxidation of (2);
4. the denitration catalyst provided by the invention adopts the surfactant, the binder and the pore-forming agent to carry out emulsification dispersion, molding and micropore modification, SO that the synergistic effect of the carrier-active component-cocatalyst is further optimized, the high-temperature denitration activity of the catalyst is improved, the modified pore structure is adopted, and the SO of the catalyst is further inhibited 2 Oxidation of (a);
5. the denitration catalyst prepared by ageing, drying and calcining has the denitration activity as high as 90.5-98.6% at the flue gas temperature of 330-650 ℃, and is used for treating SO 2 /SO 3 The conversion rate of (b) is between 0.02% and 0.15, N 2 The selectivity is as high as 90.1-98.3%, and the product has good high-temperature activity and low SO content 2 Oxidation efficiency and excellent selectivity。
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an", and "the" include plural forms as well, unless the context clearly indicates otherwise, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The denitration catalyst comprises the following components in percentage by weight:
the volume ratio of the deionized water to the acid is 1:0.01;
the molar ratio of the carrier elements Ti, W, zr and Si is 100:0.5:10:0.1;
the mol ratio of active component elements V, ce, er and B is 10:0.1:0.1:3;
the molar ratio of the promoter elements of tungsten, lanthanum and neodymium is 1:0.1:0.5;
the mass ratio of the carrier, the active component, the cocatalyst, the surfactant, the binder and the pore-forming agent is 100:0.5:15:0.1:5:2.
(1) Preparation of titanium tungsten zirconium oxide carrier
S1, respectively weighing zirconium oxychloride and ammonium metatungstate, dissolving in deionized water to prepare a solution, and adding a mixed solution of methanesulfonic acid and acetic acid to prepare a solution containing zirconium and tungsten;
s2, adding tetrabutyl titanate and ethyl silicate into the absolute ethyl alcohol solution, and uniformly stirring to obtain a titanium-containing solution and a silicon-containing solution;
s3, adding the solution containing zirconium and tungsten into the solution containing titanium and silicon, stirring uniformly, standing for 2h, and adding nano TiO 2 Uniformly stirring the powder to prepare a paste with the water content of 30%, and putting the paste into a reaction kettle, wherein the temperature of the reaction kettle is 180 ℃, and keeping the temperature for 36 hours;
s4, calcining the paste at 600 ℃ for 2h, and grinding the paste to obtain modified TiO 2 -WO 3 -ZrO 2 -SiO 2 A carrier powder;
(2) Preparation of vanadium cerium erbium boron active component
Sa, dissolving vanadyl oxalate in oxalic acid solution at the temperature of 80 ℃ to prepare vanadium-containing solution;
sb, dissolving boric acid in deionized water to prepare a boron-containing solution;
sc, dissolving cerium nitrate and erbium nitrate in deionized water simultaneously to prepare a cerium-and-erbium-containing solution;
sd, slowly pouring the boron-containing solution into the vanadium-containing solution, uniformly stirring, heating for 2 hours at the temperature of 60 ℃, slowly adding the cerium-containing solution and the erbium-containing solution, and heating for 5 hours at the temperature of 80 ℃ to prepare a mixed solution of vanadium, cerium, erbium and boron active components;
(3) Preparation of the cocatalyst
Dissolving soluble salts of promoters of tungsten, lanthanum and neodymium in a deionized aqueous solution, and stirring to prepare a uniform and stable promoter saturated solution;
(4) Preparation of denitration catalyst
Pouring a mixed solution of vanadium, cerium, erbium and boron active components into a titanium-tungsten-zirconium-silicon oxide carrier, uniformly stirring, adding a saturated solution of a cocatalyst, continuously stirring for 2 hours, and sequentially adding a surfactant, a binder, a pore-forming agent and deionized water step by step to prepare a catalyst paste;
and sealing and aging the catalyst paste at 30 ℃ for 36h, drying at 50 ℃ for 240h, calcining at 450 ℃ for 5h, and grinding to obtain the denitration catalyst.
Example 2
The catalyst comprises the following components in percentage by weight:
the volume ratio of the deionized water to the acid is 1:0.3;
the molar ratio of the carrier elements Ti, W, zr and Si is 100:2:2:2;
the mol ratio of active component elements V, ce, er and B is 10:1:0.5:0.6;
the molar ratio of the promoter elements tungsten to indium is 1:0.3;
the mass ratio of the carrier, the active component, the cocatalyst, the surfactant, the binder and the pore-forming agent is 100:2:5:1:2:1.2.
(1) Preparation of titanium tungsten zirconium oxide carrier
S1, respectively weighing zirconium oxychloride and ammonium metatungstate, dissolving in deionized water to prepare a solution, and adding a mixed solution of methanesulfonic acid and acetic acid to prepare a solution containing zirconium and tungsten;
s2, adding tetrabutyl titanate and ethyl silicate into the absolute ethyl alcohol solution, and uniformly stirring to obtain a titanium-containing solution and a silicon-containing solution;
s3, adding the solution containing zirconium and tungsten into the solution containing titanium and silicon, stirring uniformly, standing for 2 hours, and adding nano TiO 2 Uniformly stirring the powder to prepare a paste with the water content of 38%, and putting the paste into a reaction kettle, wherein the temperature of the reaction kettle is 195 ℃, and the heat preservation is carried out for 30 hours;
s4, calcining the paste at 650 ℃ for 5h, and grinding to obtain modified TiO 2 -WO 3 -ZrO 2 -SiO 2 A carrier powder;
(2) Preparation of vanadium cerium erbium boron active component
a. Dissolving vanadyl oxalate in oxalic acid at 70 ℃ to prepare a vanadium-containing solution;
b. dissolving boric acid in deionized water to prepare a boron-containing solution;
c. dissolving cerium nitrate and erbium nitrate in deionized water simultaneously to prepare a cerium-and-erbium-containing solution;
d. slowly pouring the boron-containing solution into the vanadium-containing solution, stirring uniformly, heating for 2h at 60 ℃, slowly adding the cerium-containing solution and the erbium-containing solution, and heating for 5h at 80 ℃ to obtain a mixed solution of vanadium, cerium, erbium and boron active components;
(3) Preparation of the cocatalyst
Dissolving soluble salts of promoters of tungsten and indium in a citric acid solution, and stirring to prepare a uniform and stable promoter saturated solution;
(4) Preparation of the catalyst
Pouring a mixed solution of vanadium, cerium, erbium and boron active components into a titanium-tungsten-zirconium-silicon oxide carrier, uniformly stirring, adding a saturated solution of a cocatalyst, continuously stirring for 1h, sequentially adding a surfactant, a binder and a pore-forming agent step by step, and adding deionized water to prepare a catalyst paste;
and sealing and aging the catalyst paste at 25 ℃ for 48h, drying at 55 ℃ for 300h, calcining at 600 ℃ for 3h, and grinding to obtain the denitration catalyst.
Example 3
The catalyst comprises the following components in percentage by weight:
the volume ratio of the deionized water to the acid is 1:0.2;
the molar ratio of the carrier elements Ti, W, zr and Si is 100:15:10:5;
the mol ratio of active component elements V, ce, er and B is 10:8:3:0.1,
the molar ratio of the promoter elements of iron to tin is 1:1.5;
the mass ratio of the carrier, the active component, the cocatalyst, the surfactant, the binder and the pore-forming agent is 100:2:1:4:0.5:0.1.
(1) Preparation of titanium tungsten zirconium oxide carrier
S1, respectively weighing zirconium oxychloride and ammonium metatungstate, dissolving in deionized water to prepare a solution, and adding a mixed solution of methanesulfonic acid and acetic acid to prepare a solution containing zirconium and tungsten;
s2, adding tetrabutyl titanate and ethyl silicate into the anhydrous ethanol solution, and uniformly stirring to obtain a titanium-containing and silicon-containing solution;
s3, adding the solution containing zirconium and tungsten into the solution containing titanium and silicon, stirring uniformly, standing for 2h, and adding nano TiO 2 Pulverizing, stirring to obtain paste with water content of 45%, placing into reaction kettle, and maintaining the temperature of the reaction kettleKeeping the temperature at 210 ℃ for 12h;
s4, calcining the paste at 750 ℃ for 3h, and grinding the paste to obtain modified TiO 2 -WO 3 -ZrO 2 -SiO 2 A carrier powder;
(2) Preparation of vanadium cerium erbium boron active component
Sa, dissolving vanadyl oxalate in oxalic acid solution at 70 ℃ to prepare vanadium-containing solution;
sb, dissolving boric acid in deionized water to prepare a boron-containing solution;
sc, dissolving cerium nitrate and erbium nitrate in deionized water simultaneously to prepare a cerium-and-erbium-containing solution;
sd, slowly pouring the boron-containing solution into the vanadium-containing solution, uniformly stirring, heating for 2 hours at the temperature of 60 ℃, slowly adding the cerium-containing solution and the erbium-containing solution, and heating for 5 hours at the temperature of 80 ℃ to prepare a mixed solution of vanadium, cerium, erbium and boron active components;
(3) Preparation of the cocatalyst
Dissolving soluble salts of promoter iron and tin in oxalic acid solution, and stirring to prepare uniform and stable promoter saturated solution;
(4) Preparation of the catalyst
Pouring the mixed solution of the vanadium, cerium, erbium and boron active components into a titanium-tungsten-zirconium-silicon oxide carrier, uniformly stirring, adding a saturated solution of a cocatalyst, continuously stirring for 1h, and sequentially adding a surfactant, a binder, a pore-forming agent and deionized water step by step to prepare a catalyst paste;
and sealing and aging the catalyst paste at 30 ℃ for 72h, drying at 60 ℃ for 240h, calcining at 450 ℃ for 5h, and grinding to obtain the denitration catalyst.
Example 4
The catalyst comprises the following components in percentage by weight: the volume ratio of the deionized water to the acid is 1:0.15;
the molar ratio of the carrier elements Ti, W, zr and Si is 100:3:6:2;
the mol ratio of active component elements V, ce, er and B is 10:5:2.3:0.8;
the molar ratio of neodymium, yttrium and tin as promoter elements is 1: 0.8;
the mass ratio of the carrier, the active component, the cocatalyst, the surfactant, the binder and the pore-forming agent is 100:1.2:8:2.5:3.5:2.1.
(1) Preparation of titanium tungsten zirconium oxide carrier
a. Respectively weighing zirconium hydroxide and ammonium metatungstate, dissolving in deionized water to prepare a solution, and adding a mixed solution of methanesulfonic acid and acetic acid to prepare a solution containing zirconium and tungsten;
b. adding tetrabutyl titanate and ethyl silicate into an absolute ethyl alcohol solution, and uniformly stirring to obtain a titanium-containing solution and a silicon-containing solution;
c. adding the solution containing zirconium and tungsten into the solution containing titanium and silicon, stirring uniformly, standing for 2h, adding nano TiO 2 Uniformly stirring the powder to prepare a paste with the water content of 31%, and putting the paste into a reaction kettle, wherein the temperature of the reaction kettle is 190 ℃, and the heat preservation time is 20 hours;
d. calcining the paste at 550 ℃ for 7h, and grinding to obtain modified TiO 2 -WO 3 -ZrO 2 -SiO 2 A carrier powder;
(2) Preparation of vanadium cerium erbium boron active component
a. Dissolving vanadyl oxalate in oxalic acid at 70 ℃ to prepare a vanadium-containing solution;
b. dissolving boric acid in deionized water to prepare a boron-containing solution;
c. dissolving cerium nitrate and erbium nitrate in deionized water simultaneously to prepare a cerium-and-erbium-containing solution;
d. slowly pouring the boron-containing solution into the vanadium-containing solution, stirring uniformly, heating for 2h at 60 ℃, slowly adding the cerium-containing solution and the erbium-containing solution, and heating for 7h at 72 ℃ to prepare a mixed solution of vanadium, cerium, erbium and boron active components;
(3) Preparation of the cocatalyst
Dissolving soluble salts of promoter iron and tin in oxalic acid solution, and stirring to prepare uniform and stable promoter saturated solution;
(4) Preparation of the catalyst
Pouring the mixed solution of the vanadium, cerium, erbium and boron active components into a titanium-tungsten-zirconium-silicon oxide carrier, uniformly stirring, adding a saturated solution of a cocatalyst, continuously stirring for 1h, sequentially adding a surfactant, a binder and a pore-forming agent step by step, and adding deionized water to prepare a catalyst paste;
and sealing and aging the catalyst paste at 18 ℃ for 62h, drying at 58 ℃ for 380h, calcining at 520 ℃ for 4h, and grinding to obtain the denitration catalyst.
Example 5
The catalyst comprises the following components in percentage by weight: the volume ratio of the deionized water to the acid is 1:0.05;
the molar ratio of the carrier elements Ti, W, zr and Si is 100:7:1:0.1;
the mol ratio of active component elements V, ce, er and B is 10:0.2:1.8:1.8;
the molar ratio of the promoter elements indium to yttrium is 1:0.7;
the mass ratio of the carrier, the active component, the cocatalyst, the surfactant, the binder and the pore-forming agent is 100:1.0:10:0.1:1.0:1.0.
(1) Preparation of titanium tungsten zirconium oxide carrier
S1, respectively weighing zirconium hydroxide and ammonium metatungstate, dissolving the zirconium hydroxide and the ammonium metatungstate in deionized water to prepare a solution, and adding a mixed solution of methanesulfonic acid and acetic acid to prepare a solution containing zirconium and tungsten;
s2, adding tetrabutyl titanate and ethyl silicate into the anhydrous ethanol solution, and uniformly stirring to obtain a titanium-containing and silicon-containing solution;
s3, adding the solution containing zirconium and tungsten into the solution containing titanium and silicon, stirring uniformly, standing for 2h, and adding nano TiO 2 Uniformly stirring the powder to prepare a paste with the water content of 38%, and putting the paste into a reaction kettle, wherein the temperature of the reaction kettle is 200 ℃, and keeping the temperature for 12 hours;
s4, calcining the paste at 580 ℃ for 2h, and grinding the paste to obtain modified TiO 2 -WO 3 -ZrO 2 -SiO 2 A carrier powder;
(2) Preparation of vanadium cerium erbium boron active component
Sa, dissolving vanadyl oxalate in oxalic acid solution at 70 ℃ to prepare vanadium-containing solution;
sb, dissolving boric acid in deionized water to prepare a boron-containing solution;
sc, dissolving cerium nitrate and erbium nitrate in deionized water simultaneously to prepare a cerium-and-erbium-containing solution;
slowly pouring the boron-containing solution into the vanadium-containing solution, uniformly stirring, heating for 2 hours at the temperature of 60 ℃, slowly adding the cerium-containing solution and the erbium-containing solution, and heating for 8 hours at the temperature of 62 ℃ to prepare a mixed solution of vanadium, cerium, erbium and boron active components;
(3) Preparation of the cocatalyst
Dissolving soluble salts of promoter iron and tin in oxalic acid solution, and stirring to prepare uniform and stable promoter saturated solution;
(4) Preparation of the catalyst
Pouring a mixed solution of vanadium, cerium, erbium and boron active components into a titanium-tungsten-zirconium-silicon oxide carrier, uniformly stirring, adding a saturated solution of a cocatalyst, continuously stirring for 1h, sequentially adding a surfactant, a binder and a pore-forming agent step by step, and adding deionized water to prepare a catalyst paste;
sealing and ageing the catalyst paste at 25 ℃ for 50h, drying at 50 ℃ for 450h, calcining at 560 ℃ for 3h, and grinding to obtain the denitration catalyst.
Comparative example 1
Selecting anatase type TiO 2 As a carrier;
the composition of the active component and the cocatalyst are the same as in example 1;
the mass ratio of the carrier, the active component, the cocatalyst, the surfactant, the binder and the pore-forming agent is 100:0.5:15:0.1:5:2.
comparative example 2
Selecting W, ce, er and B as active components, wherein the molar ratio of W to Ce to Er to B is 10:0.1:0.1:3;
the composition of the support and cocatalyst was the same as in example 1;
the mass ratio of the carrier, the active component, the cocatalyst, the surfactant, the binder and the pore-forming agent is 100:0.5:15:0.1:5:2.
comparative example 3
V, ce and Er are selected as active components, and the molar ratio of V to Ce to Er is 10:0.1:0.1;
the composition of the support and cocatalyst was the same as in example 1;
the mass ratio of the carrier, the active component, the cocatalyst, the surfactant, the binder and the pore-forming agent is 100:0.5:15:0.1:5:2.
in order to investigate the activity of the denitration catalysts prepared in the above examples and comparative examples, activity test was performed at a flue gas temperature of 330-650 ℃, and the test results are shown in table 1.
TABLE 1 respective catalyst Activity
| Denitration activity% | SO 2 /SO 3 Percent conversion% | N 2 Selectivity% | |
| Example 1 | 92.9 | ＜0.15 | ＞90.1 |
| Example 2 | 98.6 | ＜0.02 | ＞95.6 |
| Example 3 | 93.8 | ＜0.13 | ＞96.3 |
| Example 4 | 95.1 | ＜0.08 | ＞90.3 |
| Example 5 | 90.5 | ＜0.12 | ＞98.3 |
| Comparative example 1 | 69.5 | ＜0.17 | ＞75.5 |
| Comparative example 2 | 77.4 | ＜0.16 | ＞80.7 |
| Comparative example 3 | 82.9 | ＜0.29 | ＞81.8 |
In conclusion, the denitration activity of the denitration catalyst prepared by the invention reaches 90.5-98.6% when the flue gas temperature is 330-650 ℃, and the denitration activity is high for SO 2 /SO 3 The conversion rate of (b) is between 0.02% and 0.15, N 2 The selectivity is as high as 90.1-98.3%, and the product has good high-temperature activity and low SO content 2 Oxidation efficiency and excellent selectivity.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A denitration catalyst is characterized by comprising a carrier, an active component, a cocatalyst, a surfactant, a binder and a pore-forming agent,
the mass ratio of the carrier, the active component, the cocatalyst, the surfactant, the binder and the pore-forming agent is 100: (0.5-2): (1-15): (0.1-4): (0.5-5): (0.1-3),
the carrier is titanium-tungsten-zirconium-silicon oxide, the active component is vanadium-cerium-erbium-boron oxide, and the catalyst promoter is one or more oxides of tungsten, lanthanum, neodymium, tin, iron, indium and yttrium.
2. The denitration catalyst according to claim 1, wherein the carrier has a molar ratio of Ti, W, zr, and Si of 100: (0.5-15): (0.1-10): (0.1-5).
3. The denitration catalyst according to claim 1, wherein the active component has a molar ratio of V, ce, er and B of 10: (0.1-8): (0.1-3): (0.1-3).
4. The denitration catalyst according to claim 1, wherein the surfactant comprises any one or more of glycerol monostearate, lauric acid, polyether, glycerol monostearate and fluorine-containing siloxane;
the binder comprises any one or more of carboxymethyl cellulose, ammonium polyacrylate, hydroxypropyl methyl cellulose, amino cellulose, aluminum sol and silica sol;
the pore-forming agent comprises any one or more of starch, activated carbon powder, chitosan, polymethacrylate and methyl methacrylate.
5. The method for producing the denitration catalyst of any one of claims 1 to 4, comprising the steps of:
pouring the mixed solution of the vanadium, cerium, erbium and boron active components into a titanium-tungsten-zirconium-silicon oxide carrier, uniformly stirring, adding the saturated solution of the cocatalyst, continuously stirring, and sequentially adding the surfactant, the binder, the pore-forming agent and deionized water to prepare a catalyst paste;
and sealing, ageing, drying, calcining and grinding the catalyst paste in sequence to obtain the denitration catalyst.
6. The preparation method according to claim 5, characterized in that the preparation of the TiW-Zr-Si oxide carrier comprises the following steps:
s1, respectively weighing a zirconium source and a tungsten source, dissolving the zirconium source and the tungsten source in deionized water, and adding a mixture of methanesulfonic acid and acetic acid to prepare a solution containing zirconium and tungsten;
s2, adding tetrabutyl titanate and ethyl silicate into the absolute ethyl alcohol solution, and uniformly stirring to obtain a titanium-containing solution and a silicon-containing solution;
s3, adding the solution containing zirconium and tungsten into the solution containing titanium and silicon, stirring, standing, and adding nano TiO 2 Stirring to obtain paste with water content of 30-45%;
s4, sequentially carrying out heat preservation, calcination and grinding on the paste to obtain a titanium-tungsten-zirconium-silicon oxide carrier;
preferably, in step S1, the zirconium source is zirconium oxychloride or zirconium hydroxide, the tungsten source is ammonium metatungstate, and the volume ratio of deionized water to acid is 1: (0.01-0.3);
preferably, in step S3, the standing time is at least 2h;
preferably, in the step S4, during the heat preservation, the temperature of the reaction kettle is controlled to be 180-210 ℃ and the time is 12-36h; and during calcination, the temperature is controlled to be 600-750 ℃, and the time is 2-10h.
7. The method of claim 6The preparation method is characterized in that the nano TiO 2 The mass ratio of the titanium oxide to the calcined tetrabutyl titanate is 1: (0.01-0.1).
8. The preparation method according to claim 5, characterized in that the preparation method of the vanadium cerium erbium boron active component comprises the following steps:
sa, dissolving a vanadium source in oxalic acid to prepare a vanadium-containing solution;
sb, dissolving boric acid in deionized water to prepare a boron-containing solution;
sc, simultaneously dissolving a cerium source and an erbium source in deionized water to prepare a cerium-and-erbium-containing solution;
sd, slowly pouring the boron-containing solution into the vanadium-containing solution, stirring, heating for 1-2h at 60-80 ℃, slowly adding the cerium-containing solution and the erbium-containing solution, and heating for 5-10h at 60-80 ℃ to prepare a mixed solution of vanadium, cerium, erbium and boron active components;
preferably, the vanadium source is vanadyl oxalate, and the temperature is controlled to be 60-80 ℃ when the vanadium source is dissolved;
preferably, the cerium source is cerium nitrate and the erbium source is erbium nitrate.
9. The method according to claim 5, wherein the saturated solution of the cocatalyst is a saturated aqueous solution or a saturated acid solution of the cocatalyst.
10. The preparation method according to claim 5, wherein the temperature is controlled to be 15-30 ℃ and the time is 36-72h during sealing and ageing;
during drying, the temperature is controlled to be 50-60 ℃ and the time is 240-480h;
and during calcination, the temperature is controlled to be 450-650 ℃, and the time is 1-5h.
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