CN111229291B - Composite non-noble metal denitration catalyst and preparation method thereof - Google Patents

Composite non-noble metal denitration catalyst and preparation method thereof Download PDF

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CN111229291B
CN111229291B CN202010215465.4A CN202010215465A CN111229291B CN 111229291 B CN111229291 B CN 111229291B CN 202010215465 A CN202010215465 A CN 202010215465A CN 111229291 B CN111229291 B CN 111229291B
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noble metal
substrate
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CN111229291A (en
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钱若棨
钱敬吉
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Suzhou Daoyizhicheng Nano Material Technology Co ltd
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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    • B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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    • B01D2258/0283—Flue gases

Abstract

The invention discloses a composite non-noble metal denitration catalyst and a preparation method thereof, which are realized through a coating and evaporation process, do not generate toxic or polluted substances in the whole process, and are environment-friendly and clean in the whole process; meanwhile, the used raw materials are high-purity target materials, impurities such as nitrate radical, chloride ion and the like do not need to be filtered and taken out in the preparation process, so that the toxic pollution of the impurities to the catalyst is reduced, the preparation steps are reduced, the activity of the catalyst and the utilization rate of the raw materials are improved, and the use amount of the raw materials is reduced due to the improvement of the utilization rate.

Description

Composite non-noble metal denitration catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a composite non-noble metal denitration catalyst and a preparation method thereof.
Background
With the continuous development of industrial technology, the environmental protection requirements for industrial technology are higher and higher, and especially the requirements for the treatment of waste gases such as industrial flue gas, industrial waste gas and automobile exhaust gas and the standard requirements for treatment are more strict. In the field of flue gas denitration, in order to make the final emission of flue gas meet the standard, the flue gas is generally treated by using denitration catalyst and/or adding reducing agent, such as NH3In SCR technology, V2O5-WOX/TiO2The catalyst is the most commercial denitration catalyst at present, the temperature of an active window is 300-400 ℃, but the catalyst is poor in thermal stability, sulfur dioxide is easily oxidized into sulfur trioxide due to the high temperature of the active window, and vanadium serving as an active component is toxic and easily causes harm to the environment and human health. In order to solve the above problem, chinese patent document CN108816274A discloses an NH3-a method for preparing an SCR flue gas denitration catalyst, comprising the steps of: dispersing a ZSM-5 zeolite carrier in a composite solution of ferric nitrate and copper nitrate, wherein the mass ratio of iron atoms to copper atoms in the composite solution is 1:4, the mass of the iron element is 10 percent of that of the ZSM-5 zeolite carrier, and the dispersion method comprises stirring for 4-6 hours at 50-60 ℃ by a magnetic stirrer and ultrasonic oscillation for 40 min; and standing the dispersion system for layering, pouring out the upper layer solution, drying the precipitate in an electric heating constant-temperature air-blast drying oven, grinding the dried precipitate into powder, roasting the powder in a muffle furnace, and grinding the roasted precipitate into powder again to obtain the flue gas denitration catalyst. The denitration rate of the catalyst can reach more than 90% within a wider temperature range of 250-450 ℃, and in the catalyst, the iron-copper active component is dispersed on the surface of a zeolite carrier in the form of amorphous oxide or exists in the form of nanoparticles, so that the catalyst has small-size effect, surface effect, quantum size effect and the like, and the catalytic activity efficiency is high. Although the denitration efficiency and catalytic activity efficiency of the above catalyst can be high under certain conditions, the denitration efficiency and catalytic activity for low-temperature flue gas such as flue gas less than 200 degrees are not significant, for this reason, chinese patent document CN105749962A discloses a low-temperature flue gas denitration catalyst, which comprises a catalyst coating layer and honeycomb ceramics, wherein the catalyst layer is coated on the surface of the honeycomb ceramics, and the catalyst layer is supported by slurry components including deionized water and the following mass percentages: 40-60% of zeolite, 10-30% of gamma-alumina, 10-20% of catalytic active component, 10% of catalytic auxiliary agent and 5% of binder, wherein deionized water is added according to the liquid-solid ratio of 1-3:1, the catalyst layer accounts for 5-12% of the total mass of the catalyst, and the zeolite is one of ZSM-5 type zeolite molecular sieve, A type zeolite molecular sieve, X type zeolite molecular sieve and Y type zeolite molecular sieveOr a combination of a plurality; the catalyst comprises a catalyst active component, a catalytic assistant and a binder, wherein the catalyst active component is one or a combination of more of manganese nitrate, chloroplatinic acid and palladium nitrate, the catalytic assistant is one or a combination of more of ammonium molybdate, cerium nitrate and ammonium tungstate, and the binder is polyvinyl alcohol, ammonium nitrate or calcium nitrate. Also, for example, chinese patent document CN105289648A discloses a spherical low-temperature flue gas denitration catalyst, and a preparation method and an application thereof, wherein the catalyst comprises 5-35% of a main active component, 1-10% of a first auxiliary active component, 1-5% of a second active component, and the balance being a carrier, the main active component comprises manganese dioxide, the first active component comprises cerium dioxide, the second active component comprises one or a combination of several of copper oxide, ferric oxide, nickel oxide, bismuth trioxide, chromium oxide, and cobalt oxide, and the carrier is a foamed ceramic material. The two catalysts can treat the smoke under the condition of less than 200 ℃, but the two preparation methods can generate toxic or polluted substances, so that the environmental protection property is poor, and meanwhile, the catalytic efficiency is not ideal in the actual use process of the catalysts.
Disclosure of Invention
In order to solve the technical problems, the invention provides a composite non-noble metal denitration catalyst, which comprises a substrate, wherein a catalyst layer is arranged on the surface of the substrate, and the catalyst layer is a compound of one metal of Ti, V, Cr, Mn, Fe, Co, Ni and Cu or a compound of a plurality of compounds of one metal or a compound of a plurality of compounds of a plurality of metals; wherein the compound is an oxide, a nitride or a complex.
Further, a protective layer is provided on the surface of the catalyst layer, the protective layer being a sulfide, carbide or nitride of one of W, Mo, Ni, and Zr, wherein the sulfide, carbide or nitride is a single valence compound or a mixed valence compound.
Further, a base material coating is arranged between the surface of the base material and the catalyst layer, and the base material coating is one or a combination of a plurality of oxides of La, Ce, Zr, Ti, Nb, Si and Al.
Further, the substrate comprises a carrier, and the carrier is one or a combination of several of zeolite, electrospun nanofiber, glass fiber, ceramic fiber, foamed ceramic and alloy wire mesh.
Further, the base material also comprises a micro-nano porous material layer arranged on the surface of the carrier, and the micro-nano porous material layer is one or a combination of multiple micro-nano porous materials of gamma-Al 2O3, graphene and activated carbon.
Further, the specific surface area of the micro-nano porous material is greater than or equal to 100m 2/g.
Further, the thickness of the catalyst layer is 3-10 nm.
Further, the thickness of the protective layer is 2-10 nm.
Further, the thickness of the substrate coating is 5-20 nm.
Further, the thickness of the micro-nano porous material layer is 30-100 nm.
The invention also discloses a preparation method of the composite non-noble metal denitration catalyst, which comprises the following steps: a layer of catalyst layer is deposited on the base material through a vacuum film plating machine, and the catalyst layer is a compound of one metal or a compound of a plurality of compounds of a plurality of metals in Ti, V, Cr, Mn, Fe, Co, Ni and Cu; wherein the compound is an oxide, a nitride or a complex.
Further, a layer of the protective layer is evaporated on the catalyst layer through a vacuum coating machine, the protective layer is sulfide, carbide or nitride of one of W, Mo, Ni and Zr, and the sulfide, carbide or nitride is a single valence compound or a mixed compound of multiple valence compounds.
Further, before the catalyst layer is evaporated, a layer of the substrate coating is evaporated on the substrate through a vacuum coating machine, wherein the substrate coating is one or a combination of a plurality of oxides of La, Ce, Zr, Ti, Nb, Si and Al.
Further, the substrate comprises a carrier, and the carrier is one or a combination of several of zeolite, electrospun nanofiber, glass fiber, ceramic fiber, foamed ceramic and alloy wire mesh.
Further, a micro-nano porous material layer is evaporated on the carrier through a vacuum coating machine, and the micro-nano porous material layer is gamma-Al2O3One micro-nano porous material or a combination of multiple micro-nano porous materials in graphene and active carbon.
Further, the specific surface area of the micro-nano porous material is greater than or equal to 100m 2/g.
Further, the thickness of the catalyst layer is 3-10 nm.
Further, the thickness of the protective layer is 2-10 nm.
Further, the thickness of the substrate coating is 5-20 nm.
Further, the thickness of the micro-nano porous material layer is 30-100 nm.
Further, the evaporation condition parameters are as follows: the vacuum degree of the vacuum chamber is less than 5 x 10-3Pa, the temperature of the vacuum chamber is-10-300 ℃, the used gas is argon and/or nitrogen and/or oxygen, and the target parameters are as follows: 1-3mm particles with density not less than 60%, electron gun current set at 100-500mA, deposition rate controlled at
Figure BDA0002423330530000041
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the composite non-noble metal denitration catalyst and the preparation method are realized through the process of coating and evaporation, no toxic or polluted substance is generated in the whole process, and the catalyst is totally environment-friendly and clean; meanwhile, the used raw materials are high-purity target materials, impurities such as nitrate radical, chloride ion and the like do not need to be filtered and taken out in the preparation process, so that the toxic pollution of the impurities to the catalyst is reduced, the preparation steps are reduced, the activity of the catalyst and the utilization rate of the raw materials are improved, and the use amount of the raw materials is reduced due to the improvement of the utilization rate.
(2) According to the composite non-noble metal denitration catalyst and the preparation method, the material source is gasified into gaseous atoms, molecules or partial ions in the evaporation process, and the active ingredients of the catalyst are dispersed and embedded in a sub-nanometer manner in a plasma (or low-pressure gas) process, so that the dispersion is uniform, the dispersion degree is high, and the activity efficiency of the catalyst is high; the particle size of the catalyst active ingredient molecular cluster and/or atomic cluster can reach 0.5-10nm (can be detected or characterized by TEM or HRTEM); the binding force between the coating film layers is large, the hardness of the film layers is higher, the wear resistance and the corrosion resistance are better, the performance of the film layers is more stable, and the service life of the catalyst is longer.
(3) The invention relates to a composite non-noble metal denitration catalyst and a preparation method thereof, wherein the catalyst comprises a bimetallic alloy and a multilayer composite combined action, when the alloy is formed, the atomic distance is stretched or shrunk due to different metal atom unit cell parameters, if a metal with small atomic radius is placed on the technical surface with large atomic radius to form the alloy, if Ni, Co and the like are placed on Pt to form a covering layer, the overlap of d bands among atoms is reduced, the d bands are narrowed, the center of the d bands moves towards high energy and is close to a Fermi level, or if the metal with large atomic radius is placed on the metal with small atomic radius to form the alloy, if Pt and the like are placed on Ni and Co to form the covering layer, the center of the d bands moves towards low energy and is far away from the Fermi level, the distance between the center of the d bands of the catalyst and the Fermi level can, the catalyst of the invention can replace the noble metal compound with cheap metal compound and realize the high catalytic efficiency by replacing the noble metal with cheap metal by the way.
(4) According to the composite non-noble metal denitration catalyst and the preparation method, the protective layer is arranged, the distance between the center of the atomic d-band and the Fermi surface is adjusted, S, N, Cl poisoning of the catalyst is prevented on the basis of improving the activity of the catalyst, the grain growth is limited, and the overall structure of the catalyst is stabilized.
(5) According to the composite non-noble metal denitration catalyst and the preparation method, the base material coating is arranged, so that the loading rate and the dispersion rate of catalytic active substances can be improved, namely, the atomic number of the catalytic active substances in unit area (per square nanometer) is increased, the coverage rate of surface active substances is increased, and the TOF is improved; of course, the catalytic activity can also be enhanced by the intrinsic properties of the substrate coating, such as ceria, which can store oxygen and can act as an oxygen buffer, while the oxygen vacancies of ceria can act as active sites to promote the formation of hydroxyl radicals.
(6) According to the composite non-noble metal denitration catalyst and the preparation method thereof, the micro-nano porous material layer is further arranged, and the structure is formed on the base material, so that a base specific surface junction is provided for the whole catalyst as far as possible, and the catalytic activity of the catalyst is further improved.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying examples, in which some, but not all embodiments of the invention are shown. The embodiments in the present invention, other embodiments obtained by persons skilled in the art without any inventive work, belong to the protection scope of the present invention.
Example 1
A catalyst layer is evaporated and plated on the zeolite by a vacuum film plating machine, and the catalyst layer is Ti02It may be in single crystal form of Ti02Or mixed oxide with various crystal forms, such as rutile type Ti02And anatase type Ti02In this example, the catalyst layer is rutile type Ti02And anatase type Ti02The mixed oxide of (2), which has a thickness of 10 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 4.9 x 10-3Pa, the temperature of the vacuum chamber is 200 ℃, the used gas is argon, and the target material parameters are as follows: ti02Target material, 1mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 100mA, deposition rate of 100mA
Figure BDA0002423330530000061
By XRD standard card contrast, gold after evaporationRed stone type TiO2Anatase type TiO2＝6.1:1.0(Wt％)。
In this example, the zeolite is a Y-type zeolite molecular sieve, and the chemical formula is Na2O·Al2O3·4.9SiO2·9.4H2O, pore diameter of about 0.9-1.0nm, specific surface area of 300mg/m3(ii) a Of course, the present invention is not limited to the above-mentioned zeolite, and any kind of zeolite may be used.
Example 2
A catalyst layer is evaporated and plated on the electrospun nanofiber through a vacuum coating machine, wherein the catalyst layer is V2O5The thickness of the film is 7 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 4 x 10-3Pa, the temperature of the vacuum chamber is 250 ℃, the used gas is nitrogen, and the target material parameters are as follows: v2O5Target material, 2mm particles, density of 62 percent, purity of 99.96 percent, electron gun current set to 200mA, deposition rate controlled at
Figure BDA0002423330530000071
In this example, the electrospun nanofiber was a nylon 6 electrospun nanofiber having a BET specific surface area of 133mg/m3。
Example 3
A catalyst layer is evaporated and plated on the glass fiber by a vacuum film plating machine, and the catalyst layer is Cr2O3The thickness of the film is 5 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 3 x 10-3Pa, the temperature of the vacuum chamber is 300 ℃, the used gas is argon, and the target material parameters are as follows: cr (chromium) component2O3Target material, 3mm particles, 82% density, 99.95% purity, electron gun current set at 300mA, deposition rate controlled at
Figure BDA0002423330530000072
Example 4
A catalyst layer is evaporated and plated on the ceramic fiber by a vacuum film plating machine, and the catalyst layer is Mn4N, the thickness of which is 3 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 2 x 10-3Pa, the temperature of the vacuum chamber is 150 ℃, the used gases are nitrogen and argon, and the target material parameters are as follows: mn target material, 1mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 400mA, deposition rate controlled at
Figure BDA0002423330530000073
Example 5
A catalyst layer is evaporated on the foamed ceramic with the mesh number of 100ppi through a vacuum film coating machine, wherein the catalyst layer is FeCoN and the thickness of the catalyst layer is 3 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 1 x 10-3Pa, the temperature of the vacuum chamber is 100 ℃, the used gas is argon and nitrogen, and the target material parameters are as follows: FeCo composite target material with particle size of 2mm, density of 84 percent and purity of 99.95 percent, the current of an electron gun is set to be 500mA, and the deposition rate is controlled to be
Figure BDA0002423330530000074
Example 6
Evaporating a catalyst layer on an alloy wire mesh with the mesh number of 100ppi by a vacuum film plating machine, wherein the catalyst layer is Co2O3The thickness of the film is 5 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 9 x 10-4Pa, the temperature of the vacuum chamber is 50 ℃, the used gas is nitrogen, and the target material parameters are as follows: co2O3Target material, 3mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 100mA, deposition rate controlled
Figure BDA0002423330530000081
Example 7
Evaporating a catalyst layer on the zeolite and alloy wire mesh by a vacuum coating machine, wherein the catalyst layer is NiO, and the thickness of the catalyst layer is 7 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 6 x 10-4Pa, the temperature of the vacuum chamber is 20 ℃,the gas used was argon, the target parameters: NiO target material, 1mm of particles, 82 percent of density, 99.96 percent of purity, 200mA of electron gun current and controlled deposition rate
Figure BDA0002423330530000082
Wherein the mesh number of the alloy wire mesh is 80ppi, and the specific surface area of the zeolite is 150mg/m2。
Example 8
A catalyst layer is vapor-plated on the zeolite through a vacuum film plating machine, wherein the catalyst layer is Cu0, and the thickness of the catalyst layer is 10 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 5 x 10-4Pa, the temperature of the vacuum chamber is 200 ℃, the used gas is nitrogen, and the target material parameters are as follows: cu0 target material, 2mm particles, 80% density, 99.95% purity, 300mA electron gun current, deposition rate controlled at
Figure BDA0002423330530000083
Wherein the zeolite is 5A type zeolite molecular sieve with chemical formula of 0.7 CaO.0.3 Na2O·Al2O3·2SiO2·4.5H2O, pore diameter of about 0.5nm, specific surface area of more than 150mg/m2。
Example 9
A catalyst layer is evaporated on the zeolite by a vacuum coating machine, and the catalyst layer is a Cu-Ti bimetal mixed oxide with the thickness of 5 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 3 x 10-4Pa, the temperature of the vacuum chamber is 200 ℃, the used gases are nitrogen and oxygen, and the target material parameters are as follows: TiO 22Target material, 2mm particles, density 84%, purity 99.95%; CuO target material, 2mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 300mA, deposition rate controlled at
Figure BDA0002423330530000084
After evaporation, the mass ratio of Cu to Ti was 7: 3.
Wherein the zeolite is YZeolite molecular sieve of formula Na2O·Al2O3·4.9SiO2·9.4H2O, pore diameter of about 0.9-1.0nm, specific surface area of 260mg/m3。
Example 10
Evaporating a catalyst layer on the foamed ceramic with the mesh number of 30ppi by a vacuum coating machine, wherein the catalyst layer is CuN-TiO2A mixture having a thickness of 7 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 1 x 10- 4Pa, the temperature of the vacuum chamber is 250 ℃, the used gas is argon and oxygen, and the target material parameters are as follows: TiO 22Target material, 2mm particles, density 84%, purity 99.95%; cu target material, 3mm particles, density of 80 percent, purity of 99.99 percent, electron gun current of 300mA, deposition rate controlled at
Figure BDA0002423330530000091
Controlling the introduction amount of nitrogen when a Cu layer is evaporated, so that oxygen reacts with Cu; after evaporation, the mass ratio of Cu to Ti was 6: 4.
Example 11
In this embodiment, after the evaporation of the catalyst layer, a protective layer is further evaporated on the catalyst layer, wherein the protective layer is MoS2The thickness of the film is 10 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 4 x 10-3Pa, the temperature of the vacuum chamber is 100 ℃, the used gas is nitrogen, and the target material parameters are as follows: MoS2Target material, 1mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 100mA, deposition rate of 100mA
Figure BDA0002423330530000092
Example 12
In this embodiment, after the evaporation of the catalyst layer, a protective layer is further evaporated on the catalyst layer in the embodiment 2, wherein the protective layer is W3N4And W2Mixed nitride of N, with a thickness of 7 nm; the parameters of the evaporation conditions in the above process are as follows: the vacuum degree of the vacuum chamber is 3 x 10-3Pa, the temperature of the vacuum chamber is 150 ℃, the used gases are nitrogen and argon, and the target material parameters are as follows: pure tungsten target material, 2mm particles, 82% density, 99.99% purity, electron gun current set at 200mA, deposition rate controlled at
Figure BDA0002423330530000093
Wherein, the nitrogen gas is reacted with the tungsten by controlling the introduction amount of the nitrogen gas.
Example 13
In this embodiment, after the evaporation of the catalyst layer, a protective layer of Ni is further evaporated on the catalyst layer in example 33N, the thickness of which is 5 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 5 x 10-4Pa, the temperature of the vacuum chamber is 200 ℃, the used gases are nitrogen and argon, and the target material parameters are as follows: ni target material, 3mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 300mA, deposition rate controlled
Figure BDA0002423330530000101
Example 14
In this embodiment, after the evaporation of the catalyst layer is completed, a protective layer is further evaporated on the catalyst layer, wherein the protective layer is SiN and has a thickness of 2 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 1 x 10-3Pa, the temperature of the vacuum chamber is 250 ℃, the used gases are nitrogen and argon, and the target material parameters are as follows: si target material, 1mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 400mA, deposition rate controlled
Figure BDA0002423330530000102
Example 15
In this embodiment, after the evaporation of the catalyst layer is completed, a protective layer is further evaporated on the catalyst layer, where the protective layer is ZrN and has a thickness of 5 nm; vapor deposition condition parameters in the above processThe following were used: the vacuum degree of the vacuum chamber is 1 x 10-4Pa, the temperature of the vacuum chamber is 200 ℃, the used gases are nitrogen and argon, and the target material parameters are as follows: zr target material, 2mm particles, 82 percent of density, 99.95 percent of purity, 500mA of current of an electron gun, and controlled deposition rate
Figure BDA0002423330530000103
Example 16
In this example, after the evaporation of the catalyst layer was completed, a protective layer was further evaporated on the catalyst layer, wherein the protective layer was W2C, the thickness of the material is 7 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 2 x 10-3Pa, the temperature of the vacuum chamber is 250 ℃, the used gas is argon, and the target material parameters are as follows: w target material, 3mm particles, density of 82%, purity of 99.95%, graphite target material, 3mm particles, density of 80%, purity of 99.95%, electron gun current set to 100mA, deposition rate controlled at
Figure BDA0002423330530000104
Example 17
In this example, after the evaporation of the catalyst layer was completed, a protective layer of Mo was further evaporated on the catalyst layer2N, the thickness of which is 10 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 5 x 10-4Pa, the temperature of the vacuum chamber is 150 ℃, the used gases are nitrogen and argon, and the target material parameters are as follows: mo target material, 1mm particles, density of 80%, purity of 99.95%, electron gun current set to 200mA, deposition rate controlled at
Figure BDA0002423330530000111
Example 18
In this embodiment, after the evaporation of the catalyst layer, a protective layer of MoS was further deposited on the catalyst layer in this embodiment2The thickness of the film is 5 nm; the above processThe evaporation condition parameters in the process are as follows: the vacuum degree of the vacuum chamber is 9 x 10-4Pa, the temperature of the vacuum chamber is 200 ℃, the used gas is argon, and the target material parameters are as follows: MoS2Target material, 2mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 300mA, deposition rate of 300mA
Figure BDA0002423330530000112
Example 19
In this embodiment, in example 9, after the evaporation of the catalyst layer, a protective layer of Mo was further evaporated on the catalyst layer2N and MoN with a thickness of 7 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 2 x 10-3Pa, the temperature of the vacuum chamber is 300 ℃, the used gases are nitrogen and argon, and the target material parameters are as follows: mo target material, 3mm particles, density of 80%, purity of 99.95%, electron gun current of 400mA, deposition rate controlled at
Figure BDA0002423330530000113
Example 20
In this embodiment, after the evaporation of the catalyst layer, a protective layer was further evaporated on the catalyst layer in accordance with embodiment 10, where the protective layer was WN or W2N, the thickness of which is 10 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 3 x 10-3Pa, the temperature of the vacuum chamber is 200 ℃, the used gases are nitrogen and argon, and the target material parameters are as follows: w target material, 2mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 500mA, deposition rate controlled at
Figure BDA0002423330530000114
Example 21
This example is a further improvement on example 11 in that a substrate coating, which is La, is deposited by evaporation before the catalyst layer is deposited by evaporation2O3The thickness of the film is 20 nm; vapor deposition conditions in the above processThe parameters are as follows: the vacuum degree of the vacuum chamber is 3 x 10-4Pa, the temperature of the vacuum chamber is 100 ℃, the used gas is nitrogen, and the target material parameters are as follows: la2O3Target material, 3mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 500mA, deposition rate controlled
Figure BDA0002423330530000121
Example 22
This example is a further improvement on example 12 in that a substrate coating, which is CeO, is deposited prior to depositing the catalyst layer2The thickness of the film is 15 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 5 x 10-4Pa, the temperature of the vacuum chamber is-10 ℃, the used gas is argon, and the target material parameters are as follows: CeO (CeO)2Target material, 2mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 400mA, deposition rate controlled
Figure BDA0002423330530000122
Example 23
This example is a further improvement on example 13 in that prior to the deposition of the catalyst layer, a layer of a substrate coating of ZrO is deposited2The thickness of the film is 10 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 6 x 10-4Pa, the temperature of the vacuum chamber is 200 ℃, the used gas is argon, and the target material parameters are as follows: ZrO (ZrO)2Target material, 1mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 300mA, deposition rate of 300mA
Figure BDA0002423330530000123
Example 24
This example is a further example of example 14 wherein a substrate coating, which is TiO, is deposited prior to depositing the catalyst layer2The thickness of the film is 5 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 2 x 10- 3Pa, the temperature of the vacuum chamber is 250 ℃, the used gas is nitrogen, and the target material parameters are as follows: TiO 22Target material, 1mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 200mA, deposition rate controlled
Figure BDA0002423330530000124
Example 25
In this example, a base material coating is evaporated before the catalyst layer is evaporated in example 15, wherein the base material coating is NiO and has a thickness of 5 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 4 x 10- 3Pa, the temperature of the vacuum chamber is 300 ℃, the used gas is argon, and the target material parameters are as follows: NiO target material, 2mm particles, 80% density, 99.95% purity, electron gun current set to 100mA, deposition rate controlled at
Figure BDA0002423330530000131
Example 26
This example is a further improvement on example 16 in that a substrate coating, which is SiO, is deposited prior to the deposition of the catalyst layer2The thickness of the film is 10 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 4 x 10-4Pa, the temperature of the vacuum chamber is 250 ℃, the used gas is nitrogen, and the target material parameters are as follows: SiO 22Target material, 3mm particles, 82% density, 99.95% purity, electron gun current set to 100mA, deposition rate controlled at
Figure BDA0002423330530000132
Example 27
This example is a further improvement on example 17 in that prior to the deposition of the catalyst layer, a substrate coating layer is deposited by evaporation, said substrate coating layer being γ -Al2O3The thickness of the film is 15 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 3 x 10-3Pa, the temperature of the vacuum chamber is 200 ℃, the used gas is nitrogen, and the targetMaterial parameters: al (Al)2O3Target material, 1mm particles, 82% density, 99.95% purity, electron gun current set at 200mA, deposition rate controlled at
Figure BDA0002423330530000133
Example 28
This example is a method of example 18 wherein a substrate coating of CeO is deposited prior to depositing the catalyst layer2And ZrO2A thickness of 20 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 2 x 10-4Pa, the temperature of the vacuum chamber is-10 ℃, the used gas is nitrogen, and the target material parameters are as follows: CeO (CeO)2Target material, 2mm particles, density 60%, purity 99.95%; ZrO (ZrO)2Target material, 2mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 200mA, deposition rate controlled
Figure BDA0002423330530000134
After vapor deposition, the mass ratio of Ce to Zr was 9: 1.
example 29
This example is a method of example 19 wherein a substrate coating of CeO is deposited prior to depositing the catalyst layer2The thickness of the film is 20 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 3 x 10-4Pa, the temperature of the vacuum chamber is-10 ℃, the used gas is argon, and the target material parameters are as follows: CeO (CeO)2Target material, 2mm particles, density 60%, purity 99.95%, electron gun current set to 200mA, deposition rate controlled at
Figure BDA0002423330530000141
After evaporation, cubic crystal form CeO2And amorphous CeO2The mass ratio of (A) to (B) is 3: 2.
example 30
This example is a further improvement on example 20 in that a substrate coating, which is TiO, is evaporated prior to the evaporation of the catalyst layer2、Ti3O5And CeO2The thickness of the film is 10 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 3 x 10-4Pa, the temperature of the vacuum chamber is 100 ℃, the used gas is argon, and the target material parameters are as follows: TiO 22Target material, 2mm particles, 80% density, 99.95% purity, Ti3O5Target material, 3mm particles, density 80%, purity 99.95%, CeO2Target material, 2mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 300mA, deposition rate of 300mA
Figure BDA0002423330530000142
After evaporation, the mass ratio of the three components is 7:1: 3.
Example 31
In this embodiment, in example 21, before the coating layer is deposited on the substrate, a micro-nano porous material layer is deposited on the substrate, wherein the micro-nano porous material layer is γ -Al2O3The thickness of the film is 30 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 3 x 10-4Pa, the temperature of the vacuum chamber is 200 ℃, the used gas is argon, and the target material parameters are as follows: gamma-Al2O3(correct) target material, 2mm particles, 80% density, 99.95% purity, electron gun current set at 200mA, deposition rate controlled at
Figure BDA0002423330530000143
Wherein, gamma-Al2O3BET specific surface area of 106mg/m3。
Example 32
In this embodiment, in example 22, before a coating layer of a substrate is evaporated, a micro-nano porous material layer is evaporated on the substrate, wherein the micro-nano porous material layer is graphene and has a thickness of 60 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 4 x 10-4Pa, the temperature of the vacuum chamber is 250 ℃, the used gas is nitrogen, and the target material parameters are as follows: graphite target material, 3mm particles, density of 80%, purity of 99.95%, and electron gun current setting300mA, and the deposition rate is controlled at
Figure BDA0002423330530000151
Example 33
In this embodiment, in example 22, before a coating layer of a substrate is evaporated, a micro-nano porous material layer is evaporated on the substrate, wherein the micro-nano porous material layer is activated carbon and has a thickness of 100 nm; the parameters of the evaporation condition in the process are as follows: the vacuum degree of the vacuum chamber is 5 x 10-3Pa, the temperature of the vacuum chamber is 200 ℃, the used gas is nitrogen, and the target material parameters are as follows: carbon target material, 1mm particles, density of 80 percent, purity of 99.95 percent, electron gun current of 400mA, deposition rate controlled
Figure BDA0002423330530000152
Wherein the BET specific surface area of the activated carbon is 800mg/m3。
Comparative example 1
Step one, material preparation:
1) taking an H-ZSM-5 zeolite molecular sieve (SiO 2/Al2O3 ═ 27, chemical reagent factory of Tianjin south Ken university), treating for 3 hours by adopting a muffle furnace at 500 ℃ to remove water and impurities, and cooling to room temperature to be used as a carrier;
2) weighing 40.4g of ferric nitrate Fe (NO 3) 2.9H 2O (analytical purity in Tianjin Maotai chemical reagent factory) by an electronic balance, and fully dissolving the ferric nitrate Fe (NO 3) 2.9H 2O in 500mL of distilled water to prepare 0.2mol/L ferric nitrate solution;
3) weighing 24.16g of copper nitrate Cu (NO 3) 2.3H 2O (analytical purity in Tianjin Damao chemical reagent factory) by an electronic balance, and fully dissolving the 24.16g of copper nitrate Cu (NO 3) 2.3H 2O in 500ml of distilled water to prepare 0.2mol/L copper nitrate solution;
step two, preparation of a catalyst:
1) taking 90mL of 0.2mol/L ferric nitrate solution and 22.5mL of 0.2mol/L cupric nitrate solution, and uniformly stirring by using a glass rod to obtain a composite solution of ferric nitrate and cupric nitrate;
2) dispersing 10g of H-ZSM-5 zeolite carrier in a composite solution of ferric nitrate and copper nitrate by a magnetic stirrer at 50-60 ℃ for 4-6H and ultrasonically oscillating for 40 min;
3) standing the dispersion system for layering, pouring out supernatant, and drying the precipitate in an electric heating constant temperature air blast drying oven at the drying temperature of 110 ℃ for 10-12 h;
4) drying, grinding into powder, roasting in a muffle furnace at 450 ℃ in air atmosphere for 3-4 h;
5) and grinding the mixture into powder again after roasting, and filling the powder into a sample bag marked as Fe-Cu/ZSM-51:4 to obtain the flue gas denitration catalyst.
Comparative example 2
(1) Preparing coating slurry: weighing 45g of ZSM-5 type zeolite molecular sieve, 30% of gamma-alumina, 10% of catalytic active ingredient, 10% of catalytic auxiliary agent and 5% of polyvinyl alcohol according to the mass percentage, adding deionized water according to a liquid-solid ratio of 2:1 into a ball mill, moving the mixture into a slurry tank, wherein the ball milling time is 24 hours, and placing the ball-milled coating slurry into the slurry tank;
(2) coating: stacking the honeycomb ceramics in a cavity of a vacuum suction device, sealing the cavity, pumping the cavity of the vacuum suction device to a vacuum degree of 1KPa by using a vacuum pump, opening a valve between the cavity of the vacuum suction device and a slurry tank, and coating the coating slurry on the hole wall of the honeycomb ceramics by using the negative pressure in the cavity of the vacuum suction device to form a uniform coating with certain bonding strength;
(3) roasting: and drying the coated honeycomb ceramic at 120 ℃ for 12 hours, and then roasting at 500 ℃ for 5 hours to obtain the denitration catalyst.
Test example
The catalysts obtained in the examples and comparative examples were tested as follows: the catalytic efficiency of the catalyst was evaluated by a conventional catalytic oxidation reaction apparatus. Wherein, the manufacturer of the catalytic oxidation reaction device is the XianWaudes instruments and equipments Co., Ltd,the model is VDRT-200 SCR; catalytic efficiency (inlet gas concentration-outlet gas concentration)/inlet gas concentration 100%; the composition of the simulated flue gas was as follows: NO2,NO,N2O,CO,C3H6(ii) a The wind speed was 1.8 m/s.
The test results are shown in Table 1.
TABLE 1
Figure BDA0002423330530000171
Figure BDA0002423330530000181
As can be seen from the data in table 1, the catalyst prepared according to the present invention has a higher catalytic efficiency at 60 to 180 degrees than the catalyst of the prior art, especially compared to comparative example 1; meanwhile, in the test process, the catalyst of the present invention can achieve good catalytic efficiency without adding ammonia.
It should be noted that the model of the vacuum coating machine is ZX-1350, and the manufacturer is Beijing Zhongwei industry Instrument Co., Ltd; the particle size of the base material is not particularly limited, and the particle size of the base material in the above embodiments is only for the specific embodiments; the mesh size of the ceramic foam and the alloy wire mesh is preferably between 30ppi and 200 ppi.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (21)

1. The composite non-noble metal denitration catalyst is characterized by comprising a substrate, wherein a catalyst layer is arranged on the surface of the substrate, and the catalyst layer is a compound of one metal of Ti, V, Cr, Mn, Fe, Co, Ni and Cu, or a compound of a plurality of compounds of one metal or a compound of a plurality of compounds of a plurality of metals; the compound is oxide and nitride, a protective layer is arranged on the surface of the catalyst layer, and the protective layer is sulfide, carbide or nitride of one of W, Mo, Ni and Zr, wherein the sulfide, carbide or nitride is a single valence compound or a mixed compound of multiple valence compounds.
2. The composite non-noble metal denitration catalyst of claim 1, wherein a substrate coating is further disposed between the surface of the substrate and the catalyst layer, and the substrate coating is one or a combination of oxides of La, Ce, Zr, Ti, Nb, Si and Al.
3. The composite non-noble metal denitration catalyst according to any one of claims 1 to 2, wherein the substrate comprises a carrier, and the carrier is one or a combination of zeolite, electrospun nanofiber, glass fiber, ceramic fiber, foamed ceramic and alloy wire mesh.
4. The composite non-noble metal denitration catalyst of claim 3, wherein the substrate further comprises a micro-nano porous material layer arranged on the surface of the carrier, and the micro-nano porous material layer is gamma-Al2O3One micro-nano porous material or a combination of multiple micro-nano porous materials in graphene and active carbon.
5. The composite non-noble metal denitration catalyst of claim 4, wherein the specific surface area of the micro-nano porous material is greater than or equal to 100m2/g。
6. The composite non-noble metal denitration catalyst of claim 1, wherein the thickness of the catalyst layer is 3-10 nm.
7. The composite non-noble metal denitration catalyst of claim 1, wherein the thickness of the protective layer is 2-10 nm.
8. The composite non-noble metal denitration catalyst of claim 2, wherein the thickness of the substrate coating is 5-20 nm.
9. The composite non-noble metal denitration catalyst of claim 4, wherein the thickness of the micro-nano porous material layer is 30-100 nm.
10. The method for preparing the composite non-noble metal denitration catalyst according to claim 1, wherein a layer of the catalyst layer is deposited on the substrate by a vacuum coater, and the catalyst layer is a nitride of one of Ti, V, Cr, Mn, Fe, Co, Ni and Cu or a composite of a plurality of compounds of one of the metals or a composite of a plurality of compounds of the metals; wherein the compound is oxide or nitride.
11. The production method according to claim 10, wherein a protective layer which is a sulfide, a carbide or a nitride of one of W, Mo, Ni and Zr is deposited on the catalyst layer by vacuum coater, wherein the sulfide, the carbide or the nitride is a single valence compound or a mixed valence compound.
12. The method according to claim 11, wherein a layer of the substrate coating is deposited on the substrate by a vacuum coater before the catalyst layer is deposited, wherein the substrate coating is one or more of La, Ce, Zr, Ti, Nb, Si and Al.
13. The method according to any one of claims 10 to 12, wherein the substrate comprises a carrier, and the carrier is one or a combination of zeolite, electrospun nanofiber, glass fiber, ceramic fiber, foamed ceramic and alloy wire mesh.
14. The preparation method of claim 13, wherein a micro-nano porous material layer is further evaporated on the carrier by a vacuum coating machine, and the micro-nano porous material layer is gamma-Al2O3One micro-nano porous material or a combination of multiple micro-nano porous materials in graphene and active carbon.
15. The preparation method according to claim 14, wherein the specific surface area of the micro-nano porous material is greater than or equal to 100m2/g。
16. The production method according to claim 10, wherein the thickness of the catalyst layer is 3 to 10 nm.
17. The method of claim 11, wherein the protective layer has a thickness of 2 to 10 nm.
18. The method of claim 12, wherein the substrate coating has a thickness of 5 to 20 nm.
19. The preparation method according to claim 14, wherein the thickness of the micro-nano porous material layer is 30-100 nm.
20. The production method according to any one of claims 10 to 12, wherein the evaporation is performed under the following conditions: the vacuum degree of the vacuum chamber is less than 5 x 10-3Pa, the temperature of the vacuum chamber is-10-300 ℃, the used gas is argon and/or nitrogen and/or oxygen, and the target parameters are as follows: 1-3mm particles with density not less than 60%, electron gun current set at 100-500mA, deposition rate controlled at
Figure FDA0002847313360000032
21. The method according to claim 14, wherein the evaporation conditions are as follows: the vacuum degree of the vacuum chamber is less than 5 x 10-3Pa, the temperature of the vacuum chamber is-10-300 ℃, the used gas is argon and/or nitrogen and/or oxygen, and the target parameters are as follows: 1-3mm particles with density not less than 60%, electron gun current set at 100-500mA, deposition rate controlled at
Figure FDA0002847313360000031
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