CN106824168B - Catalyst for exhaust gas treatment and method for producing same - Google Patents
Catalyst for exhaust gas treatment and method for producing same Download PDFInfo
- Publication number
- CN106824168B CN106824168B CN201610862366.9A CN201610862366A CN106824168B CN 106824168 B CN106824168 B CN 106824168B CN 201610862366 A CN201610862366 A CN 201610862366A CN 106824168 B CN106824168 B CN 106824168B
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- Prior art keywords
- exhaust gas
- catalyst
- raw material
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- composite oxide
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000009826 distribution Methods 0.000 claims abstract description 14
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- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
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- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 2
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- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
Disclosed is a catalyst for exhaust gas treatment which exhibits high denitration performance even when used for treating low-temperature exhaust gas and which is less likely to be deactivated when used for exhaust gas containing a large amount of poisoning components including alkali metals or alkaline earth metals and ammonium sulfates. The catalyst satisfies the following conditions: specific surface area A (SA) of catalyst pores of 5nm to 5400nm based on mercury porosimetryHg) Is 25 to 50m2A/g range; in the pore size distribution, the maximum peak X is within the range of 20-50 nm; x10 when the pore diameter of the maximum peak is X‑0.25～X×10+0.25Specific surface area SA occupied by pore diameters in the nm rangeXRelative to the total specific surface area SA of the catalysttotalRatio of (SA)X/SAtotalThe catalyst is in the range of 0.65-0.90, and comprises a carrier, a structure directing agent and an active metal component, wherein the carrier is formed by at least more than 1 inorganic single oxide and/or inorganic composite oxide in titanium oxide and/or titanium composite oxide.
Description
Technical Field
The present invention relates to an exhaust gas treatment catalyst and a method for producing the same.
Background
For example, when heat recovery is performed using exhaust gas, the exhaust gas temperature may be about 80 ℃. Therefore, there is a demand for development of a catalyst that exhibits high denitration performance even when treating such exhaust gas at a low temperature (about 70 to 250 ℃).
Further, as a method for removing nitrogen oxides in combustion exhaust gas, a method of performing catalytic cracking in the presence of ammonia as a reducing agent is known, and generally, since sulfur dioxide is contained in combustion exhaust gas, when the decomposition temperature is 300 ℃ or lower, there is a problem that ammonium sulfate is precipitated on the catalyst surface by a reaction with ammonia, and the catalytic performance is lowered.
Further, when the exhaust gas contains a poisoning substance for the exhaust gas treatment catalyst, the exhaust gas treatment catalyst is easily deactivated. Here, the main poisoning substances include alkali metals and alkaline earth metals. For example, it is known that calcium is a main component of dust contained in exhaust gas from cement production (see patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-49580
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide an exhaust gas treatment catalyst which exhibits high denitration performance even when treating exhaust gas at low temperatures (about 70 to 250 ℃), and which is less likely to deactivate even when used in exhaust gas containing large amounts of poisoning components including alkali metals or alkaline earth metals (particularly calcium) and ammonium sulfates, and a method for producing the same.
In addition, there is a demand for the development of a catalyst having high denitration performance and heat resistance even when used for treating exhaust gas at 300 to 600 ℃, such as gas turbine exhaust gas using LNG as a fuel.
Means for solving the problems
The present inventors have conducted intensive studies in order to solve the above problems and completed the present invention.
The present invention is the following (1) to (7).
(1) An exhaust gas treatment catalyst satisfying the following conditions (i) to (iii):
(i) specific surface area A (SA) of catalyst pores of 5nm to 5400nm based on mercury porosimetryHg) Is 25 to 50m2A range of/g;
(ii) in the pore size distribution, the maximum peak X is within the range of 20-50 nm;
(iii) will be provided withX10 when the pore diameter of the maximum peak is X-0.25～X×10+0.25Specific surface area SA occupied by pore diameters in the nm rangeXRelative to the total specific surface area SA of the catalysttotalRatio of (SA)X/SAtotalIs in the range of 0.65-0.90,
the exhaust gas treatment catalyst comprises a carrier formed of at least 1 or more inorganic single oxides and/or inorganic composite oxides of titanium oxide and/or titanium composite oxides, a structure-directing agent, and an active metal component.
(2) The exhaust gas treatment catalyst according to the above (1), wherein the carrier is made of TiO2An inorganic single oxide formed, and/or an inorganic composite oxide of at least 1 selected from the group consisting of W, Mo, Si and V, and Ti.
(3) The exhaust gas treatment catalyst according to the above (1) or (2), wherein the active metal component is at least 1 selected from the group consisting of vanadium, molybdenum, manganese, lanthanum, yttrium and cerium.
(4) The exhaust gas treatment catalyst according to any one of the above (1) to (3), wherein the structure-directing agent is a compound containing silicon and/or calcium.
(5) The method for producing an exhaust gas treatment catalyst according to any one of the above (1) to (4), comprising the steps of:
a step (a): dehydrating the slurry containing Ti or at least 1 selected from the group consisting of W, Mo, Si and V and Ti, and calcining to obtain a slurry containing TiO2And (3) forming an inorganic single oxide raw material or an inorganic composite oxide raw material of at least 1 selected from the group consisting of W, Mo, Si and V and Ti.
A step (b): and (b) forming a mixture of the inorganic single oxide raw material and/or inorganic composite oxide raw material obtained in the step (a), a compound containing silicon and/or calcium, and an active metal component, drying, and baking.
(6) The method for producing an exhaust gas treatment catalyst according to the item (5), further comprising a drying step of drying the mixture in the step (b) after the molding process, wherein the drying step is performed in an environment in which the humidity is reduced from 90% or more to 30% at a rate in the range of 0.20 to 0.97%/hour from the environment in which the humidity is 90% or more.
(7) A method for treating an exhaust gas, which comprises treating the exhaust gas with the exhaust gas treatment catalyst according to any one of (1) to (4) above.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a catalyst for treating exhaust gas, which exhibits high denitration performance even when treating exhaust gas at low temperatures (about 70 to 250 ℃), and which is less likely to be deactivated even when used for treating exhaust gas containing a large amount of poisoning components including alkali metals or alkaline earth metals (particularly calcium) and ammonium sulfate, and a method for producing the same.
Drawings
Fig. 1 is a schematic perspective view of a preferred example of the honeycomb structure.
FIG. 2 is a graph of the pore size distribution of the catalyst of example 1.
FIG. 3 is a graph of the pore size distribution of the catalyst of example 2.
Figure 4 is a plot of the pore size distribution for the catalyst of example 3.
Fig. 5 is a pore size distribution diagram for the catalyst of example 4.
Fig. 6 is a pore size distribution diagram of the catalyst of comparative example 1.
Detailed Description
< catalyst for treating exhaust gas of the present invention >
The exhaust gas treating catalyst of the present invention will be explained. Hereinafter, the exhaust gas treatment catalyst of the present invention is also referred to as "the catalyst of the present invention" or "the catalyst".
< vector >
The carrier in the catalyst of the present invention will be explained.
In the catalyst of the invention, the carrier is TiO2An inorganic composite oxide, or a mixture thereof.
The inorganic composite oxide is any one of composite oxides of at least 1 selected from the group consisting of W, Mo, Si and V and Ti.
The oxide-equivalent concentration of W, Mo, Si, and V in the composite oxide is preferably 0.05 to 40 mass%, and more preferably 0.1 to 20 mass%, based on the total amount of the above.
The catalyst preferably contains 50 to 95 mass%, more preferably 70 to 95 mass%, of the above-mentioned inorganic single oxide, inorganic composite oxide or a mixture thereof.
< Structure directing agent >
The catalyst also comprises a structure directing agent. By using the structure-directing agent, a catalyst having excellent pore distribution controllability and a narrow pore distribution (sharp) can be prepared. Further, the shape, orientation, and the like of the fine pores can be easily controlled.
Further, as the structure-directing agent, an inorganic structure-directing agent is preferable, and examples thereof include: carbon fibers, ceramic fibers, glass fibers, synthetic fibers, chopped fibers thereof, whiskers thereof, and the like. The structure-directing agent preferably contains 3 to 20 mass%, more preferably 5 to 10 mass%, of a compound containing silicon and/or calcium in addition to the above-described mixture of the inorganic single oxide and the inorganic composite oxide. Either crystalline or amorphous may be used.
The compound containing silicon and/or calcium, which may be contained as a structure-directing agent, may be a compound having a structure such as MCM-41, 48, SBA-15, SBA-16, etc., porous silica (micelle-templated silica) (see Langmuir 16(2),356(2000)), amorphous glass fibers, or a clay-based crystalline mineral such as a montmorillonite-based mineral.
Further, the structure directing agent may be in the form of fibers, columns, spindles, or plates.
< active Metal component >
The active metal component in the catalyst of the present invention will be explained.
The catalyst of the present invention has an active metal component supported on the carrier as described above.
In the catalyst of the present invention, the active metal component is preferably at least 1 selected from the group consisting of tungsten, vanadium, molybdenum, manganese, lanthanum, yttrium and cerium.
The catalyst of the present invention may contain components other than the above-described carrier and active metal component at a ratio of 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less. The catalyst of the present invention is preferably substantially composed of the carrier, the structure-directing agent and the active metal component. Here, "substantially" means that impurities derived from raw materials and inevitably contained in the production process may be contained, but the other cases are not included.
Examples of the components other than the carrier, structure-directing agent and active metal component include: cr, Fe, Co, Ni, Cu, Ag, Au, Pd, Nd, In, Sn and Ir.
< catalyst >
The honeycomb structure in the catalyst of the present invention will be described as an example. In addition, the shape of the catalyst of the present invention may be selected from a cylindrical shape, a tubular shape, and the like, in addition to the honeycomb structure.
Specific surface area A (SA) of catalyst pore diameter of 5nm to 5400nm based on mercury porosimetry of the catalyst of the inventionHg) Is 25 to 50m2A range of 30 to 50m, preferably2/g。
The mercury porosimetry is a mercury intrusion method using a porosimeter, and can be measured, for example, using a conventionally known measuring apparatus.
The catalyst of the present invention has a pore size distribution having a maximum peak in a range of 20 to 50nm, and the pore size is X0.562 (═ 10) relative to the apex Xnm of the maximum peak in the range of 20 to 50nm-0.25)～X×1.78(＝10+0.25) Specific surface area SA occupied by pore diameters in the nm rangeXRelative to the total specific surface area SA of the catalysttotalRatio of (SA)X/SAtotal0.65 to 0.90. The SAXThe value is preferably 25 to 30m2/g。
SAX/SAtotalWhen the ratio is in the range of 0.65 to 0.90, the reason is not clear, but it is considered that: for example, in a low temperature region of 70 to 250 DEG CIn the region, the diffusion of the reaction gas forming ammonia containing the reducing agent and the adsorption of ammonia to the active sites are in a balanced state, and low-temperature denitration properties are exhibited.
SAX/SAtotalIn the above range, the exhaust gas exhibits high denitration performance when treated at a low temperature of 70 ℃, and is less likely to be deactivated when used for a catalyst containing a poisoning component containing a large amount of an alkali metal or an alkaline earth metal (particularly calcium) and ammonium sulfate.
In addition, the catalyst of the invention has high denitration performance in the range of about 70-600 ℃, and also has high heat resistance.
< Honeycomb Structure >
The catalyst of the present invention is preferably a honeycomb structure in which an active metal component is supported on the carrier as described above.
The honeycomb structure is a structure having a plurality of small pores (cells) penetrating in parallel. The catalyst of such a structure is generally used while being closely packed in the reaction tube. The shape (cross-sectional shape) of the cell may be hexagonal, quadrangular, triangular, circular, or the like. In general, the size (diameter) of a cell is referred to as an opening, the cell-to-cell is referred to as a partition wall, and the distance between the centers of the opposing left and right or upper and lower walls when 1 cell is considered is referred to as a pitch.
Fig. 1 is a schematic perspective view illustrating a honeycomb structure corresponding to the catalyst of the present invention.
In fig. 1, the catalyst (1) of the present invention has cells (3) of 8 × 8 pores, and the cross-sectional shape of the cells (3) is a quadrilateral form. The size (diameter) of the cells (3) is also referred to as the width (5) of the opening, the spacing between the cells (3) and the cells (3) is also referred to as the partition wall (7), and the thickness (9) of the partition wall (7) is also referred to as the wall thickness. The surface of the unit (3) exposed from the opening is an end surface (11), and the other surfaces are side surfaces (13). The length of the honeycomb structure in the longitudinal direction is X.
< method for producing catalyst of the present invention >
Next, a method for producing the catalyst of the present invention will be described.
In the catalyst of the present invention, the carrier can be produced by the methods described in, for example, Japanese patent application laid-open Nos. 2004-41893 and 2005-021780.
The catalyst of the present invention can be produced by the following method: a method of obtaining a mixture of the carrier or the raw material thereof and the active metal component or the raw material thereof, and then molding the mixture into a honeycomb structure by an extrusion molding method or the like; a method of impregnating/supporting a carrier component and an active component on a substrate of a honeycomb structure; and a method of impregnating/supporting an active ingredient on a support component of a honeycomb structure.
The catalyst of the present invention is preferably produced by a production method including the following steps (a) to (b).
A step (a): dehydrating the slurry containing Ti or at least 1 selected from the group consisting of W, Mo, Si and V and Ti, and calcining to obtain a slurry containing TiO2And (3) forming an inorganic single oxide raw material or an inorganic composite oxide raw material of at least 1 selected from the group consisting of W, Mo, Si and V and Ti.
A step (b): extruding the mixture of the inorganic single oxide raw material or inorganic composite oxide raw material, silicon and/or calcium-containing compound, and active metal-containing component obtained in step (a) into a honeycomb shape, molding the honeycomb shape, and drying and baking the honeycomb shape.
The respective steps of such a preferred production method will be described below.
< Process (a) >
In the step (a), first, a slurry containing Ti or a slurry containing Ti and at least 1 selected from the group consisting of W, Mo, Si, and V is obtained.
This slurry can be obtained, for example, as follows: the compound containing Ti and the compound containing W, Mo, Si, and V are dissolved in a solvent such as water, and then the pH is adjusted with an acid or a base, whereby an oxide of Ti and an oxide of W, Mo, Si, and V can be precipitated. After the precipitation, the mixture is preferably cured at 20 to 98 ℃ for 0.5 to 24 hours.
Here, as the Ti-containing compound, a titanium sulfate solution obtained through a titanium dioxide production process by a sulfuric acid method or metatitanic acid is preferable.
Examples of the compound containing W include: tungsten-containing nitrogen compounds such as ammonium paratungstate, ammonium metatungstate, ammonium phosphotungstate and ammonium tetrathiotungstate, tungsten-containing sulfur compounds such as tungsten disulfide and tungsten trisulfide, tungsten hexachloride, tungsten dichloride, tungsten trichloride, tungsten tetrachloride, tungsten pentachloride, tungsten dioxide dichloride and tungsten oxide tetrachloride.
As the Mo-containing compound, there may be mentioned: molybdenum-containing nitrogen compounds such as ammonium paramolybdate, ammonium phosphomolybdate and ammonium tetrathiomolybdate, molybdenum-containing sulfur compounds such as molybdenum disulfide and molybdenum trisulfide, molybdenum hexachloride, molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum dichloride dioxide and molybdenum tetrachloride oxide.
Here, examples of the compound containing Si include: silica sol, silicic acid solution, fumed silica, silicon alkoxide, and the like.
Here, examples of the compound containing V include: vanadyl sulfate, vanadyl oxalate, ammonium metavanadate, and the like.
When a compound containing W, Mo, Si and V is used in addition to the compound containing Ti, the ratio of the amount of the compound containing Ti to the amount of the compound containing W, Mo, Si and V is not particularly limited, but is preferably based on TiO2(assuming all Ti is TiO)2The equivalent of (d) 100 mass% to 3 to 20 mass%.
After the slurry is obtained as described above, it is dehydrated and calcined.
The dehydration method is not particularly limited, and for example, dehydration can be performed by applying a conventionally known method, specifically, a centrifugal separation method or the like.
The firing method is not particularly limited, and for example, firing can be performed by a conventionally known method, specifically, a firing furnace or the like. The firing temperature is, for example, 110 ℃ or higher (preferably 300 ℃ or higher) and 700 ℃ or lower.
Drying may also be carried out after dewatering and before calcining the obtained filter cake (cake). For drying, a conventionally known method, specifically, an electric dryer or the like can be used. The drying temperature is set to 30 to 200 ℃, for example.
By the step (a), a slurry containing Ti or an inorganic composite oxide raw material containing Ti and at least 1 selected from the group consisting of W, Mo, Si, and V can be obtained.
< Process (b) >
In the step (b), the inorganic single oxide raw material or inorganic composite oxide raw material obtained in the step (a), the compound containing silicon and/or calcium, and the active metal component are preferably mixed together after adding water.
The mixing ratio is not particularly limited, but the ratio of the inorganic single oxide raw material or inorganic composite oxide raw material to the total amount of the inorganic single oxide raw material or inorganic composite oxide raw material, the compound containing silicon and/or calcium, the active metal component, and the moisture ((inorganic single oxide raw material or inorganic composite oxide raw material)/(inorganic single oxide raw material or inorganic composite oxide raw material + compound containing silicon and/or calcium + active metal component + moisture) × 100) is preferably 10 to 70 mass%.
The ratio of the compound containing silicon and/or calcium ((compound containing silicon and/or calcium)/(inorganic single oxide raw material or inorganic composite oxide raw material + compound containing silicon and/or calcium + active metal component + moisture) × 100) is preferably 15% by mass or less.
The ratio of the active metal component (active metal component/(inorganic single oxide raw material or inorganic composite oxide raw material + compound containing silicon and/or calcium + active metal component + moisture) × 100) is preferably 5 mass% or less.
When the inorganic single oxide raw material or inorganic composite oxide raw material, the compound containing silicon and/or calcium, and the active metal component are mixed together after adding water as described above, a forming aid may be further added and mixed as necessary.
As the molding aid, for example, conventionally known ones can be used, and specific examples thereof include: organic substances such as polyethylene oxide, crystalline cellulose, glycerin, and polyvinyl alcohol.
Then, the obtained mixture is formed into, for example, a honeycomb shape by using a conventionally known forming machine, and then fired. Here, it is preferable to dry after molding.
The drying method is preferably performed after the molding process in an environment in which the humidity is reduced from 90% or more to 30% at a rate in the range of 0.20 to 0.97%/hour. Specifically, the drying may be performed by using a humidity-controlling and temperature-adjusting dryer or the like. The drying temperature is set to 30 to 200 ℃, for example.
When the humidity decrease rate is faster than 0.97%/hour, cracks may occur, and the strength of the molded article may not be practically acceptable.
If the humidity is decreased at a rate lower than 0.20%/hour, the efficiency of production may be poor and the application may be impossible.
The firing method is not particularly limited, and for example, firing can be performed by a conventionally known method, specifically, a firing furnace or the like. The baking temperature is set to 400 to 700 ℃, for example.
The catalyst of the present invention can be obtained by the production method of the present invention.
< exhaust gas treatment method >
The catalyst of the present invention can be preferably used as a catalyst for treating exhaust gas from a thermal power plant, cement production exhaust gas, waste incineration exhaust gas, glass-melting furnace exhaust gas, or steel coke oven exhaust gas.
The catalyst of the present invention can be used in a device for decomposing and removing organic chlorinated compounds (dioxins and the like) when the exhaust gas contains such compounds.
The catalyst of the present invention can be used in a device for halogenating mercury in the case where mercury is contained in the exhaust gas.
[ examples ]
The present invention will be described below based on examples. The present invention is not limited to these examples.
[ raw Material preparation 1(Ti oxide raw Material: TiO)2Raw material-1)]
Metatitanic acid slurry (available from stone industries, Ltd.) was charged into a mixer with a reflux unit so as to be opposed to TiO290 parts by mass of H2O235% by mass of H was added to 9 parts by mass2O2Water, slowly adding 25 mass% ammonia water to make pH 9.0, then at 40 ℃ over 3 hours to fully stir, at constant temperature curing. Thereafter, 25 mass% sulfuric acid water was slowly added thereto so that the pH became 2.0, followed by sufficient stirring at 40 ℃ over 1 hour, and further 25 mass% ammonia water was slowly added thereto so that the pH became 7.5, followed by sufficient stirring at 40 ℃ over 3 hours while carrying out constant-temperature aging. Then, the obtained slurry was dewatered and washed, and the dewatered cake was dried at 110 ℃ and then calcined at 150 ℃ to obtain a Ti oxide raw material-1.
[ raw Material preparation 2(Ti oxide raw Material: TiO)2Raw materials-2)]
Metatitanic acid slurry (made by stone industries, Ltd.) was charged into a stirrer with a reflux unit, 25 mass% ammonia water was added to adjust the pH to 7.5 or more, and the mixture was heated and aged while sufficiently stirring at 60 ℃ for 3 hours. Then, the obtained slurry was dewatered and washed, and the dewatered cake was dried at 110 ℃ and then calcined at 600 ℃ to obtain Ti oxide raw material-2.
[ raw Material preparation 3(Ti-W-V raw Material: TiO)25% by mass of WO3-4.35％V2O5Composite oxide raw material)]
A metatitanic acid slurry (available from Stone Ltd.) was charged into a stirrer with a reflux unit and stirred with TiO288.5 parts by mass of H2O235% by mass of H was added so as to be 8.9 parts by mass2O2Water, in turn, in relation to TiO288.85 parts by mass, WO3Ammonium paratungstate (manufactured by Nippon Metal Co., Ltd.) was added so as to be 5 parts by mass, and the amount of the ammonium paratungstate was adjusted to TiO288.85 parts by mass of V2O5Vanadyl sulfate (manufactured by Nippon chemical industries, Ltd.) was added so that the amount of the solution became 6.15 parts by mass, and 25% by mass of ammonia water was added so that the pH became 7.5 or more, and then the mixture was heated and aged while sufficiently stirring at 60 ℃ for 3 hours. Then, the obtained slurry is dewatered and washed, and the dewatered pulp is filteredThe cake is dried at 110 ℃ and then roasted at 400 ℃ to obtain a Ti-W-V composite oxide raw material A. Next, metatitanic acid slurry (available from Stone Ltd.) was charged into a stirrer with a reflux unit, and TiO derived from metatitanic acid slurry was added thereto2The Ti-W-V composite oxide raw material a was added in such a manner that 30 parts by mass of the Ti-W-V composite oxide raw material a became 70 parts by mass, and further 25 mass% ammonia water was slowly added thereto so that the pH became 7.2, followed by sufficient stirring at 40 ℃ for 3 hours while carrying out constant temperature aging. And then, dehydrating and cleaning the obtained slurry, drying the dehydrated filter cake at 110 ℃, and then roasting at 600 ℃ to obtain the Ti-W-V composite oxide raw material.
[ raw Material preparation 4(Ti-Mo-Si raw Material: TiO)2-5 mass% MoO3-10 mass% SiO2Composite oxide raw Material)]
A metatitanic acid slurry (available from Stone Ltd.) was charged into a stirrer with a reflux unit and stirred with TiO290 parts by mass of H2O2To 10 parts by mass, 35% by mass of H was added2O2Water, in turn, in relation to TiO285 parts by mass of MoO3Ammonium paramolybdate was added so as to be 5 parts by mass based on TiO285 parts by mass of SiO2Silica sol (S-20L, manufactured by Nikkiso Kagaku Co., Ltd.) was added to 10 parts by mass, and 25% by mass of ammonia water was slowly added thereto so that the pH became 7.2, followed by sufficiently stirring at 40 ℃ for 24 hours and aging at a constant temperature. And then, dehydrating and cleaning the obtained slurry, drying the dehydrated filter cake at 110 ℃, and then roasting at 500 ℃ to obtain the Ti-Mo-Si composite oxide raw material.
[ raw Material preparation 5(Ti-Si raw Material: TiO raw Material)2-20 mass% SiO2Composite oxide raw material)]
A sulfuric acid solution of titanyl sulfate (a solution obtained by dissolving TM crystals made by TEIKA CORPORATION in water) was put into a stirrer with a reflux unit, and the solution was stirred into TiO280 parts by mass of H2O235% by mass was added to make 8 parts by massH2O2Water, further to it to TiO280 parts by mass of SiO2Silica sol (S-20L, manufactured by Nikkiso Kagaku Co., Ltd.) was added in an amount of 20 parts by mass, and the amount of the silica sol was adjusted to TiO280 parts by mass of urea and 27 parts by mass of urea were added with 32.5% by mass of urea water, heated to 95 ℃, and then aged while being sufficiently stirred for 12 hours. And then, dehydrating and cleaning the obtained slurry, drying the dehydrated filter cake at 110 ℃, and then roasting at 500 ℃ to obtain the Ti-Si composite oxide raw material.
< preparation of catalyst >
[ example 1]
To 22.7kg of the Ti oxide raw material-1 obtained as described above, 1.285kg of ammonium metavanadate (manufactured by New chemical Co., Ltd.), 920g of ammonium paramolybdate (TAIYO KOKOKO Co., manufactured by LTD., Ltd.), 1.25kg of glass fiber, 2.10kg of 25 mass% aqueous ammonia, water, 125g of polyethylene glycol (PEG-20000 manufactured by first Industrial pharmaceutical Co., Ltd.), and 125g of crystalline cellulose (Ceolus TG-101) were added, kneaded by a mixer so that the water concentration became 30 mass%, and then extruded into a honeycomb shape. The obtained molded article was dried in an environment in which the humidity was gradually decreased from 90% to 30% (corresponding to a decrease rate of 0.83%/hour) over 3 days and the temperature was gradually increased from 40 ℃ to 60 ℃ over 3 days. Thereafter, the reaction mixture was calcined at 500 ℃ for 3 hours to obtain a catalyst. The obtained honeycomb catalyst had a wall thickness of partition walls: 0.50mm, opening: 3.20mm and 75mm in external shape.
Comparative example 1
Similarly, to 24.7kg of the Ti oxide raw material-2 obtained as described above, 1.285kg of ammonium metavanadate (manufactured by Nippon chemical Co., Ltd.), 2.30kg of 25 mass% aqueous ammonia, water, 125g of polyethylene glycol (PEG-20000 manufactured by first Industrial pharmaceutical Co., Ltd.), and 125g of crystalline cellulose (Ceolus TG-101) were added, kneaded so that the water concentration became 30 mass%, and then formed into a honeycomb shape, dried under the same drying conditions as in example 1, and then calcined at 500 ℃ for 3 hours, thereby obtaining a honeycomb catalyst having a partition wall thickness of 0.50mm, an opening of 3.20mm, and an outer diameter of 75 mm.
[ example 2]
To 23.7kg of the Ti-W-V composite oxide raw material obtained as described above, 1.02kg of lanthanum nitrate hexahydrate, 1.28kg of yttrium nitrate hexahydrate, 1.25kg of glass fiber, 2.10kg of 25 mass% aqueous ammonia, 125g of water, polyethylene glycol (PEG-20000 manufactured by first Industrial pharmaceutical Co., Ltd.), and 125g of crystalline cellulose (Ceolus TG-101) were added, kneaded by a mixer so that the water concentration became 30 mass%, molded into a honeycomb shape, dried under the same drying conditions as in example 1, and then calcined at 500 ℃ for 3 hours to obtain a honeycomb catalyst having a partition wall thickness of 0.50mm, an opening of 3.20mm, and an outer diameter of 75 mm.
[ example 3]
To 22.7kg of the Ti-Mo-Si composite oxide raw material obtained as described above, 4.52kg of a 50 mass% manganese nitrate aqueous solution, 1.89kg of cerium nitrate hexahydrate, 1.25kg of activated clay, 2.10kg of 25 mass% aqueous ammonia, 125g of water, polyethylene glycol (PEG-20000 manufactured by first Industrial pharmaceutical Co., Ltd.), and 125g of crystalline cellulose (Ceolus TG-101) were added, kneaded by a mixer so that the water concentration became 30 mass%, molded into a honeycomb shape, dried under the same drying conditions as in example 1, and fired at 500 ℃ for 3 hours to obtain a honeycomb catalyst having a partition wall thickness of 0.50mm, an opening of 3.20mm, and an outer diameter of 75 mm.
[ example 4]
A catalyst was obtained in the same manner as in example 1, except that 22.7kg of the Ti — Si composite oxide raw material was used.
Comparative example 2
The molded article obtained after molding into a honeycomb form in the same manner as in example 2 was dried in an environment in which the humidity was rapidly decreased from 90% to 30% (corresponding to a decrease rate of 2.5%/hour) over 1 day and the temperature was rapidly increased from 40 ℃ to 60 ℃ over 1 day. As a result, a plurality of cracks were generated in the honeycomb, and the sample could not be collected.
Test example 1 estimation of specific surface area based on measurement of specific surface area by Mercury porosimeter
The catalysts obtained in examples and comparative examples were subjected to specific surface area distribution measurement in the range of 5nm to 5400nm based on mercury porosimetry.
Mercury porosimeter specific surface area measuring apparatus: quantachrome PoreMaster
Mercury porosimeter specific surface area measurement conditions: pretreatment is carried out for 1 hour at 300 ℃, the mercury intrusion angle is 130 degrees, and the surface tension is 473erg/cm2
Specific surface area distributions of 5nm to 500nm among specific surface area distributions of 5nm to 5400nm of each catalyst measured by mercury porosimetry are shown in fig. 1 to 5. No peak of specific surface area was recognized at 500nm or more.
[ test example 2]From CaCl2Accelerated degradation test of catalyst by solution spraying and ammonium sulfate
Each of the catalysts obtained in examples and comparative examples was cut into 4X 107mmL (wall thickness: 0.50mm, opening width: 3.20mm) and mounted on a quartz reaction tube, and the denitration performance of the catalyst in a Fresh (Fresh) state was measured. Here, the denitration rate of nitrogen oxides (NOx) in the gas before and after the contact of the catalyst can be obtained by the following formula. At this time, the concentration of NOx was measured by a chemiluminescence type NOx analyzer (ECL-88 AO, manufactured by ANATEC YANACO CORPORATION).
Denitration rate (%) { (NOx in non-contact gas (volume ppm) — NOx in post-contact gas (volume ppm))/NOx in non-contact gas (volume ppm) } × 100
Let η be the initial denitration rate obtained here0(%). Further, a reaction rate constant k was calculated0＝-AV×ln(1-η0/100)。
Then, a quartz reaction tube was provided for spraying CaCl2Nozzle of the solution, adding CaCl from the upstream side of the catalyst2And (3) solution. A nozzle was provided at a distance of 300mm from the upstream end face of the quartz reaction tube. With CaCl2The concentration of the solution was 0.1 mass% and the spraying time was 48 hours. CaCl2After the solution was sprayed, the denitration performance of the catalyst was measured again. K ═ AV × ln (1-. eta/100) was calculated from the post-deterioration denitration rate η (%) obtained in this way. Then, k/k is obtained0A comparison is made of the performance with the Fresh (Fresh) state. Performance measurement and CaCl2The solution is sprayed to be 1At 30 ℃. The measurement conditions are as follows.
Activity measurement conditions
Reaction temperature: 130 deg.C, SV 3000(1/h), air flow rate 0.075 (Nm)3/h)、AV＝3.30(Nm3/m2h) NO 180 (vol ppm), NH3180 (ppm by volume), SO240 (volume ppm), O27% by volume, H210% by volume of O and N2The balance being
Accelerated degradation test conditions
SV 3000(1/h), air flow rate 0.075 (Nm)3/h)、AV＝3.30(Nm3/m2h) NO ═ 0 (ppm by volume), NH30 (volume ppm), SO21000 (volume ppm), O27% by volume, H2O10 vol% (with CaCl)2Solution meter), N2The balance being
The results are shown in Table 1. As compared with the catalyst of comparative example 1, it was found that the catalysts of examples 1 to 4 were in CaCl2The activity after solution spraying is also high.
[ test example 3] Low-temperature denitration test
Each of the catalysts obtained in examples and comparative examples was cut into 4X 107mmL (wall thickness: 0.50mm, opening width: 3.20mm) and mounted on a quartz reaction tube, and then the low-temperature denitration performance was measured.
Here, Nitrogen Oxides (NO) in the gas before and after the catalyst contactX) The denitration rate of (2) is determined by the above formula. At this time NOXThe concentration of (B) was measured by a chemiluminescent NOx analyzer (ECL-88 AO, manufactured by ANATEC YANACO CORPORATION).
The measurement method of the low-temperature denitration performance is as follows.
Reaction temperature: 110 deg.C, empty tower Speed (SV) 3000hr-1
Typical gas composition: NOX180 ppm by volume NH3180 ppm by volume of O27% by volume, H210% by volume of O and N2The balance being
[ test example 4] denitration test
Each of the catalysts obtained in examples and comparative examples was cut into 4X 272mmL (wall thickness: 0.50mm, opening width: 3.20mm), and mounted on a quartz reaction tube, and the denitration performance was measured.
Here, Nitrogen Oxides (NO) in the gas before and after the catalyst contactX) The denitration rate of (2) is determined by the above formula. At this time NOXThe concentration of (B) was measured by a chemiluminescent NOx analyzer (ECL-88 AO, manufactured by ANATEC YANACO CORPORATION).
The measurement method of the low-temperature denitration performance is as follows.
Reaction temperature: 350 deg.C, and Superficial Velocity (SV) 29300hr-1
Typical gas composition: NOX180 ppm by volume NH3180 ppm by volume of O27% by volume, H210% by volume of O and N2The balance being
The results are shown in Table 1.
[ Table 1]
TABLE 1
Claims (6)
1. An exhaust gas treatment catalyst satisfying the following conditions (i) to (iii):
(i) specific surface area A of catalyst pores of 5nm to 5400nm based on mercury porosimetry, namely SAHgIs 25 to 50m2A range of/g;
(ii) in the pore size distribution, the maximum peak X is within the range of 20-50 nm;
(iii) x10 when the pore diameter of the maximum peak is X-0.25～X×10+0.25Specific surface area SA occupied by pore diameters in the nm rangeXRelative to the total specific surface area SA of the catalysttotalRatio of (SA)X/SAtotalIs in the range of 0.65-0.90,
the exhaust gas treatment catalyst comprises a carrier formed of at least 1 inorganic single oxide and/or inorganic composite oxide of titanium oxide and/or titanium composite oxide, a structure-directing agent, and an active metal component,
the structure directing agent contains 3-20% by mass of a compound containing silicon and/or calcium.
2. The exhaust gas treatment catalyst according to claim 1, wherein the carrier is made of TiO2And/or an inorganic composite oxide of at least 1 selected from the group consisting of W, Mo, Si and V and Ti.
3. The exhaust gas treatment catalyst according to claim 1 or 2, wherein the active metal component is at least 1 selected from the group consisting of vanadium, molybdenum, manganese, lanthanum, yttrium, and cerium.
4. The method for producing the exhaust gas treatment catalyst according to any one of claims 1 to 3, comprising the steps of:
a step (a): dehydrating the slurry containing Ti or at least 1 selected from the group consisting of W, Mo, Si and V and Ti, and calcining to obtain a slurry containing TiO2A step of forming an inorganic single oxide raw material or an inorganic composite oxide raw material of at least 1 selected from the group consisting of W, Mo, Si and V and Ti;
a step (b): and (b) forming a mixture of the inorganic single oxide raw material and/or inorganic composite oxide raw material obtained in the step (a), a compound containing silicon and/or calcium, and an active metal component, drying, and baking.
5. The method for producing an exhaust gas treatment catalyst according to claim 4, further comprising a drying step after the molding of the mixture in the step (b), wherein the drying step is performed in an environment in which the humidity is reduced from 90% or more to 30% at a rate in the range of 0.20 to 0.97%/hour.
6. A method for treating exhaust gas, which comprises treating exhaust gas with the catalyst for treating exhaust gas according to any one of claims 1 to 3.
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| CN107552041A (en) * | 2017-09-30 | 2018-01-09 | 湖北神雾热能技术有限公司 | A kind of wear-resisting denitrating catalyst of the grey high calcium operating mode of suitable height and preparation method thereof |
| CN107694558A (en) * | 2017-09-30 | 2018-02-16 | 湖北神雾热能技术有限公司 | A kind of SCR catalyst for having denitration heat accumulation function concurrently and preparation method thereof |
| CN112584928B (en) | 2018-08-22 | 2021-11-23 | 三井金属矿业株式会社 | Porous structure for exhaust gas purification catalyst, exhaust gas purification catalyst using same, and exhaust gas purification method |
| KR102079475B1 (en) * | 2019-07-29 | 2020-02-20 | 노한길 | Fabrication method of SCR catalyst for removal of dioxin |
| CN110339847B (en) * | 2019-08-08 | 2021-05-25 | 清华大学 | Denitration catalyst and preparation method and application thereof |
| CN111974399A (en) * | 2020-08-18 | 2020-11-24 | 山东大学 | Red mud-based SCR denitration catalyst and preparation method and application thereof |
| CN112206768B (en) * | 2020-09-24 | 2022-06-03 | 四川大学 | Cerium-doped modified lanthanum-manganese composite oxide SCR denitration catalyst and preparation method thereof |
| CN113198455B (en) * | 2021-05-17 | 2022-12-09 | 南昌航空大学 | Molybdenum trioxide/molybdenum mesh photocatalyst and preparation method and application thereof |
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