CN112427033A - Method for preparing low-temperature denitration catalyst by utilizing manganese ore - Google Patents
Method for preparing low-temperature denitration catalyst by utilizing manganese ore Download PDFInfo
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Abstract
The invention belongs to the field of industrial flue gas denitration, and particularly relates to a method for preparing a low-temperature denitration catalyst from manganese ore. The method adopts manganese ore as a main raw material to prepare the low-temperature denitration catalyst, and comprises the steps of crushing, grinding, component blending, mulling, molding, drying and roasting; the manganese ore is one or more of manganite, pyrolusite and rhodochrosite, wherein the mass fraction of the manganite is more than or equal to 20 wt.%. By mass, 10-60 parts of manganese ore, 1-6 parts of tungsten/molybdenum (oxide), 30-80 parts of diatomite and 5-10 parts of forming aid. The method for preparing the low-temperature denitration catalyst by using the manganese ore realizes high-value utilization of the manganese ore and reduces the production cost of the low-temperature denitration catalyst.
Description
Technical Field
The invention belongs to the field of industrial flue gas denitration, and particularly relates to a method for preparing a low-temperature denitration catalyst from manganese ore.
Background
The low-temperature denitration of industrial flue gas is NOxDevelopment trend of ultra-low emission technology. The existing low-temperature denitration catalyst mainly comprises a high-content manganese catalyst or a high-content vanadium catalyst, and the preparation method of the low-temperature denitration catalyst adopts high-purity manganese salt or vanadium salt to be loaded on a titanium dioxide carrier, so that the cost of raw materials is extremely high, and the low-temperature denitration catalyst is expensive.
The utilization of manganese ore is generally to extract metal manganese elements through smelting, pure manganese-containing salt is adopted for preparing the low-temperature denitration catalyst, and the technology for preparing the low-temperature denitration catalyst by using the manganese ore in the prior art is rarely reported.
Patent CN108855124A discloses a method for preparing an SCR denitration catalyst by using steel-making sintering ash and manganese ore, which comprises mixing manganese ore and steel-making sintering ash, placing the mixture in a mixed acid and hydrogen peroxide solution, leaching manganese and iron, adding alkali liquor for precipitation, performing suction filtration, drying, roasting and ultraviolet irradiation to obtain the SCR denitration catalyst. The method utilizes manganese ore and steel-making sintering ash with high value, and takes manganese and iron in the manganese ore and the steel-making sintering ash as active components to prepare the denitration catalyst. However, this method uses a large amount of mixed acid solution with a solid-to-liquid ratio of 1: (4-10) g/mL, and is precipitated by alkali liquor, so that the process is complex, and a large amount of wastewater is generated. Patents CN110026059A, CN101574617A and CN106178947A disclose different methods for preparing a denitration agent using manganese ore as one of the raw materials, although these methods use manganese ore for treating NO in flue gasxHowever, a method for preparing a catalyst is not provided, but a method for preparing an adsorbent is provided, and the principle is completely different.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a low-temperature denitration catalyst by using manganese ores, which not only realizes high-value utilization of the manganese ores, but also reduces the production cost of the low-temperature denitration catalyst.
The invention is realized by the following technical scheme:
a method for preparing a low-temperature denitration catalyst by using manganese ore is characterized in that the low-temperature denitration catalyst is prepared by using the manganese ore as a main raw material and comprises the steps of crushing, grinding, component blending, mulling, molding, drying and roasting.
Further, the manganese ore is one or more of manganite, pyrolusite and rhodochrosite. The manganite is alkaline manganese hydroxide mineral, has a chemical formula of MnO (OH) and is easy to dissolve, so that the weight fraction of the manganite in the manganese ore raw material is controlled to be more than or equal to 20 wt%, and the manganese component is favorably controlledThe activity of the prepared catalyst is improved; the pyrolusite has MnO as component2The hardness is low, the manganese grade is high, and the grinding is easy; the main component of rhodochrosite is MnCO3The manganese-iron composite oxide denitration catalyst has low hardness and easy dissolution, is often accompanied by iron element, and can be formed. Manganese elements and associated iron elements in manganese ores are good catalyst active components, and elements such as Si, Al and the like in ores are good catalyst carriers, so that the denitration catalyst prepared from the manganese ores does not need to be purified.
The valence of the manganese element in different manganese ores is different, MnCO3、MnO(OH)、MnO2Respectively has +2, +3 and +4 valence, so that the active component in the prepared catalyst has various forms and valence states, including MnO and Mn2O3And MnO2And the like, to sufficiently exert the denitration performance thereof.
Further, the crushing is to crush the manganese ore to an average particle size of less than or equal to 2mm by adopting a physical method.
Further, the grinding is to grind the manganese ore to an average particle size of less than or equal to 50 μm, add an acidic substance during the grinding process and control the temperature to be 80-140 ℃. During the grinding process, acidic substances are added to dissolve and leach manganese components in the grinding process, and the temperature is controlled to be 80-140 ℃ to improve the leaching rate. The grinding process naturally raises the temperature, so that the energy consumption of temperature control can be reduced.
Further, the acidic substance is a mixture of oxalic acid and inorganic strong acid, and the amount of the oxalic acid in the acidic substance is 10% -40% by mass; the inorganic strong acid is one or two of nitric acid and sulfuric acid; the oxalic acid can be used for complexing manganese ions to improve the leaching rate of manganese and can be used as a reducing agent for assisting in dissolving and leaching MnO in pyrolusite2。
The amount of the acidic substance is 40-100% of the total amount of manganese in the ore by mass. The amount of acid used does not need to be excessive to completely leach the manganese element in the mineral, and in order to control the addition amount of the solution, the concentration of the added acidic substance should be increased to reduce the excessive addition amount of the solution, which causes the mud to be too thin.
Further, the components are prepared by adding one of a tungsten oxide precursor and a molybdenum oxide precursor into the ground material, and adding diatomite and a forming aid;
the diatomite mainly comprises SiO2The manganese-doped iron-based catalyst has large specific surface area and low cost, can adsorb manganese elements separated out in the grinding and acid leaching process when being added into a raw material for preparing the denitration catalyst by using manganese ores to form a supported catalyst, and improves the specific surface area of the catalyst.
10-60 parts of manganese ore, 1-6 parts of tungsten oxide precursor/molybdenum oxide precursor, 30-80 parts of diatomite and 5-10 parts of forming aid by mass; in order to design target components of the low-temperature denitration catalyst, the target components can be designed by adjusting the proportion of manganese ores with different components, for example, when the adopted pyrolusite grade is lower and the pyrolusite grade is higher, the proportion of the pyrolusite and the proportion of the pyrolusite can be reduced, namely, the manganese content in the catalyst can be adjusted, and meanwhile, the proportion of manganese components with different valence states can be designed, so that better denitration performance can be obtained.
The tungsten oxide precursor is one or two of ammonium metatungstate and tungsten trioxide;
the molybdenum oxide precursor is one or two of ammonium heptamolybdate and molybdenum trioxide;
the water content of the diatomite is less than or equal to 8 percent so as to improve the water absorption of the diatomite and control the water content of the catalyst mud material, thereby being beneficial to catalyst molding.
Further, the forming aid comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide.
Further, the mixing is to uniformly stir and mix the materials after the components are mixed, the mixing time is 4-8h, the temperature is 80-120 ℃, and the mixture is placed for 6-24h after mixing.
Further, the molding is to prepare the pug after mixing into one of honeycomb type, plate type, corrugated plate type and clover type blanks.
Further, the drying is to control the temperature to be 80-160 ℃, and the dry blank is obtained by slow dehydration in the air or steam atmosphere.
Further, the calcination is to calcine the catalyst dry blank at 300-700 ℃ for 4-24 h, and the heating rate is 1-15 ℃/min. And roasting to obtain the low-temperature denitration catalyst.
The technical principle of the invention is as follows:
(1) manganese ore naturally contains a manganese component with good denitration activity, has high average grade, has the manganese content of over 20 percent generally, and is a good manganese-based low-temperature denitration catalyst raw material. Iron is often associated with manganese ore, and the iron also has good low-temperature denitration activity, while components such as silicon, aluminum and the like contained in the manganese ore are good catalyst carriers. Therefore, the manganese ore has active components and a catalyst carrier of the low-temperature denitration catalyst, is a good raw material for preparing the low-temperature denitration catalyst at low cost, does not need a complex impurity removal process in the preparation process, and can fully utilize all the components in the manganese ore. According to the method, natural manganese elements and associated iron elements in manganese ores are used as active components, Si and Al components in the ores are used as carriers, diatom ooze is added to improve the specific surface area of the catalyst, the dispersion degree of the active components is further improved, and the low-temperature denitration catalyst is prepared;
(2) according to the method, in the grinding process, the manganese component in the mineral is leached by acid leaching to form ionic manganese, the mineral structure is reconstructed, the manganese element is fully exposed on the surface of the carrier, and the use amount of acid is controlled, so that no wastewater or waste residue is generated in the production process;
(3) the method adopts the combination of various manganese ores of manganite, pyrolusite and rhodochrosite to form the composite oxide with multiple valence states, and meets the working principle of the denitration catalyst, namely the electronic transfer among the manganese elements with multiple valence states promotes NOxAnd (3) carrying out redox reaction in the reduction process to obtain the high-activity low-temperature denitration catalyst.
The invention has the beneficial technical effects that:
(1) the method for preparing the low-temperature denitration catalyst by using the manganese ore realizes high-value utilization of the manganese ore, reduces the production cost of the denitration catalyst, and has important environmental benefit and economic value;
(2) the method for preparing the low-temperature denitration catalyst by using the manganese ore has the advantages of simple preparation process, no waste water or waste residue, and comprehensive utilization of elements such as manganese, iron, silicon, aluminum and the like in the manganese ore;
(3) according to the method for preparing the low-temperature denitration catalyst by using the manganese ore, the prepared denitration catalyst contains manganese oxides with various valence states, has good low-temperature activity, and can greatly promote the popularization and application of a low-temperature SCR technology.
Drawings
Fig. 1 is a flowchart of a method for preparing a low-temperature denitration catalyst by using manganese ore according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.
Example 1
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite as a main raw material. Firstly, crushing manganese ore to an average particle size of 2mm, grinding at 80 ℃ to an average particle size of 5 mu m, and adding oxalic acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 10 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 40 percent of the total amount of manganese in the ore; the material comprises 14 parts of manganese ore, 1 part of tungsten trioxide, 80 parts of diatomite and 5 parts of a forming aid by mass; the precursor of the tungsten is ammonium metatungstate; the water content of the diatomite is 8%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 80 ℃ for 4h, standing for 6h after mixing, preparing a honeycomb type blank, drying in an air atmosphere at 80 ℃ to obtain a dry blank, and finally heating to 300 ℃ at 15 ℃/min and roasting for 24 h.
Example 2
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite and pyrolusite as main raw materials, wherein the mass fraction of the manganite is 20 wt.%. Firstly, crushing manganese ore to an average particle size of 1.9mm, grinding at 85 ℃ to an average particle size of 10 mu m, and adding oxalic acid and nitric acid during grinding, wherein the oxalic acid accounts for 15 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 45 percent of the total amount of manganese in the ore; the material comprises, by mass, 10 parts of manganese ore, 2 parts of molybdenum trioxide, 73 parts of diatomite and 5 parts of a forming aid; the precursor of the molybdenum is molybdenum trioxide; the water content of the diatomite is 8%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 85 deg.C for 4.5h, standing for 7h, preparing into plate blank, drying at 85 deg.C in steam atmosphere to obtain dry blank, and heating to 350 deg.C at 13 deg.C/min for roasting for 20 h.
Embodiment 3
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 25 wt.%. Firstly, crushing manganese ore to an average particle size of 1.8mm, grinding at 90 ℃ to an average particle size of 15 mu m, and adding oxalic acid, nitric acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 20% (by mass), and the amount of acidic substances accounts for 50% of the total mass of manganese in the ore; the material comprises 15 parts of manganese ore, 3 parts of molybdenum trioxide, 73 parts of diatomite and 9 parts of a forming aid by mass; the precursor of the molybdenum is ammonium heptamolybdate; the water content of the diatomite is 8%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 95 ℃ for 5h, standing for 8h after mixing, preparing a corrugated plate type blank, drying in an air atmosphere at 90 ℃ to obtain a dry blank, and finally heating to 400 ℃ at the speed of 11 ℃/min and roasting for 16 h.
Example 4
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite, pyrolusite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 50 wt.%. Firstly, crushing manganese ore to an average particle size of 1.7mm, grinding at 95 ℃ to an average particle size of 20 mu m, and adding oxalic acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 25 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 55 percent of the total amount of manganese in the ore; the material comprises, by mass, 20 parts of manganese ore, 4 parts of tungsten trioxide, 68 parts of diatomite and 8 parts of a forming aid; the precursor of the tungsten is tungsten trioxide; the water content of the diatomite is 8%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 95 deg.C for 5.5h, standing for 9h, preparing into clover-shaped blank, drying at 95 deg.C in steam atmosphere to obtain dry blank, and roasting at 9 deg.C/min to 450 deg.C for 12 h.
Example 5
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite as a main raw material. Firstly, crushing manganese ore to an average particle size of 1.6mm, grinding at 100 ℃ to an average particle size of 6 mu m, and adding oxalic acid and nitric acid during grinding, wherein the oxalic acid accounts for 30 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 60 percent of the total amount of manganese in the ore; the material comprises 25 parts of manganese ore, 5 parts of tungsten trioxide, 63 parts of diatomite and 7 parts of a forming aid by mass; the precursor of the tungsten is ammonium metatungstate; the water content of the diatomite is 8%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 100 ℃ for 6h, standing for 10h after mixing, preparing a honeycomb type blank, drying in an air atmosphere at 100 ℃ to obtain a dry blank, and finally heating to 500 ℃ at the speed of 7 ℃/min and roasting for 8 h.
Example 6
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite and pyrolusite as main raw materials, wherein the mass fraction of the manganite is 30 wt.%. Firstly, crushing manganese ore to an average particle size of 1.5mm, grinding at 105 ℃ to an average particle size of 30 mu m, and adding oxalic acid, nitric acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 35 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 65 percent of the total amount of manganese in the ore; the material comprises 30 parts of manganese ore, 6 parts of molybdenum trioxide, 58 parts of diatomite and 6 parts of a forming aid by mass; the precursor of the molybdenum is molybdenum trioxide; the water content of the diatomite is 8%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 105 deg.C for 6.5h, standing for 11h, preparing into plate-type blank, drying at 105 deg.C in steam atmosphere to obtain dry blank, and heating to 550 deg.C at 5 deg.C/min for roasting for 4 h.
Example 7
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 35 wt.%. Firstly, crushing manganese ore to an average particle size of 1.4mm, grinding at 110 ℃ to an average particle size of 35 mu m, and adding oxalic acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 40% (by mass), and the amount of acidic substances accounts for 70% of the total mass of manganese in the ore; the material comprises, by mass, 35 parts of manganese ore, 1 part of molybdenum trioxide, 59 parts of diatomite and 5 parts of a forming aid; the precursor of the molybdenum is ammonium heptamolybdate; the water content of the diatomite is 7%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 110 ℃ for 7h, standing for 12h after mixing, preparing a corrugated plate type blank, drying in an air atmosphere at 110 ℃ to obtain a dry blank, and finally heating to 600 ℃ at 3 ℃/min and roasting for 4 h.
Example 8
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite, pyrolusite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 40 wt.%. Firstly, crushing manganese ore to an average particle size of 1.3mm, grinding at 115 ℃ to an average particle size of 40 mu m, and adding oxalic acid and nitric acid during grinding, wherein the oxalic acid accounts for 12 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 75 percent of the total amount of manganese in the ore; the material comprises 40 parts of manganese ore, 2 parts of tungsten trioxide, 48.5 parts of diatomite and 9.5 parts of a forming aid by mass; the precursor of the tungsten is tungsten trioxide; the water content of the diatomite is 7%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 115 deg.C for 7.5h, standing for 13h, preparing into clover-shaped blank, drying at 115 deg.C in steam atmosphere to obtain dry blank, and heating to 650 deg.C at 1 deg.C/min for roasting for 4 h.
Example 9
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite as a main raw material. Firstly, crushing manganese ore to an average particle size of 1.2mm, grinding at 120 ℃ to an average particle size of 7 mu m, and adding oxalic acid, nitric acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 17% (by mass), and the amount of acidic substances accounts for 62% of the total mass of manganese in the ore; the material comprises, by mass, 45 parts of manganese ore, 3 parts of tungsten trioxide, 43.5 parts of diatomite and 8.5 parts of a forming aid; the precursor of the tungsten is ammonium metatungstate; the water content of the diatomite is 7%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 82 ℃ for 8h, standing for 15h after mixing, preparing a honeycomb type blank, drying in an air atmosphere at 120 ℃ to obtain a dry blank, and finally heating to 700 ℃ at 14 ℃/min to roast for 4 h.
Embodiment 10
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite and pyrolusite as main raw materials, wherein the mass fraction of the manganite is 45 wt.%. Firstly, crushing manganese ore to an average particle size of 1.1mm, grinding at 125 ℃ to an average particle size of 50 mu m, and adding oxalic acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 22 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 85 percent of the total amount of manganese in the ore; the material comprises, by mass, 50 parts of manganese ore, 4 parts of molybdenum trioxide, 38.5 parts of diatomite and 7.5 parts of a forming aid; the precursor of the molybdenum is molybdenum trioxide; the water content of the diatomite is 7%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 82 deg.C for 8h, standing for 15h, preparing into plate blank, drying at 125 deg.C in steam atmosphere to obtain dry blank, and baking at 12 deg.C/min to 320 deg.C for 22 h.
Example 11
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 50 wt.%. Firstly, crushing manganese ore to an average particle size of 1mm, grinding at 130 ℃ to an average particle size of 10 mu m, and adding oxalic acid and nitric acid during grinding, wherein the oxalic acid accounts for 27% (by mass), and the amount of acidic substances accounts for 90% of the total mass of manganese in the ore; the material comprises 55 parts of manganese ore, 5 parts of molybdenum trioxide, 33.5 parts of diatomite and 6.5 parts of a forming aid by mass; the precursor of the molybdenum is ammonium heptamolybdate; the water content of the diatomite is 6%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 87 deg.C for 4.7h, standing for 16h, preparing into corrugated board type blank, drying at 130 deg.C in air atmosphere to obtain dry blank, and heating to 370 deg.C at 10 deg.C/min for baking for 18 h.
Example 12
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite, pyrolusite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 55 wt.%. Firstly, crushing manganese ore to an average particle size of 0.9mm, grinding at 135 ℃ to an average particle size of 13 mu m, and adding oxalic acid, nitric acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 32% (by mass), and the amount of acidic substances accounts for 95% of the total mass of manganese in the ore; the material comprises, by mass, 60 parts of manganese ore, 4.5 parts of tungsten trioxide, 30 parts of diatomite and 5.5 parts of a forming aid; the precursor of the tungsten is tungsten trioxide; the water content of the diatomite is 6%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 92 deg.C for 5.2h, standing for 17h, preparing into clover-shaped blank, drying at 135 deg.C in steam atmosphere to obtain dry blank, and heating to 420 deg.C at 8 deg.C/min for 14 h.
Example 13
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite as a main raw material. Firstly, crushing manganese ore to an average particle size of 0.8mm, grinding at 140 ℃ to an average particle size of 8 mu m, and adding oxalic acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 37% (by mass), and the amount of acidic substances accounts for 100% of the total mass of manganese in the ore; the material comprises 12 parts of manganese ore, 1 part of tungsten trioxide, 77.3 parts of diatomite and 9.7 parts of forming auxiliary agent by mass; the precursor of the tungsten is ammonium metatungstate; the water content of the diatomite is 6%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 97 ℃ for 5.7h, standing for 18h after mixing, preparing a honeycomb type blank, drying in the air atmosphere at 140 ℃ to obtain a dry blank, and finally heating to 470 ℃ at 6 ℃/min and roasting for 10 h.
Embodiment 14
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite and pyrolusite as main raw materials, wherein the mass fraction of the manganite is 60 wt.%. Firstly, crushing manganese ore to an average particle size of 0.7mm, grinding at 83 ℃ to an average particle size of 83 mu m, and adding oxalic acid and nitric acid during grinding, wherein the oxalic acid accounts for 14 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 100 percent of the total amount of manganese in the ore; the material comprises, by mass, 17 parts of manganese ore, 2 parts of molybdenum trioxide, 71.8 parts of diatomite and 9.2 parts of a forming aid; the precursor of the molybdenum is molybdenum trioxide; the water content of the diatomite is 6%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 102 deg.C for 6.2h, standing for 19h, preparing into plate blank, drying at 145 deg.C in steam atmosphere to obtain dry blank, and heating to 520 deg.C at 4 deg.C/min for roasting for 6 h.
Example 15
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 65 wt.%. Firstly, crushing manganese ore to an average particle size of 0.6mm, grinding at 88 ℃ to an average particle size of 22 mu m, and adding oxalic acid, nitric acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 19 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 100 percent of the total amount of manganese in the ore; the material comprises 22 parts by mass of manganese ore, 3 parts by mass of molybdenum trioxide, 66.3 parts by mass of diatomite and 8.7 parts by mass of a forming aid; the precursor of the molybdenum is ammonium heptamolybdate; the water content of the diatomite is 5%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 107 deg.C for 6.7h, standing for 20h, preparing into corrugated board type blank, drying at 150 deg.C in air atmosphere to obtain dry blank, and heating to 570 deg.C at 2 deg.C/min for roasting for 4 h.
Example 16
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite, pyrolusite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 70 wt.%. Firstly, crushing manganese ore to an average particle size of 0.5mm, grinding at 98 ℃ to an average particle size of 9 mu m, and adding oxalic acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 24% (by mass), and the amount of acidic substances accounts for 100% of the total mass of manganese in the ore; the material comprises, by mass, 27 parts of manganese ore, 4 parts of tungsten trioxide, 60.8 parts of diatomite and 8.2 parts of a forming aid; the precursor of the tungsten is tungsten trioxide; the water content of the diatomite is 5%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 112 deg.C for 7.2h, standing for 21h, preparing into clover-shaped blank, drying at 155 deg.C in steam atmosphere to obtain dry blank, and roasting at 11 deg.C/min to 620 deg.C for 4 h.
Example 17
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite as a main raw material. Firstly, crushing manganese ore to an average particle size of 0.4mm, grinding at 98 ℃ to an average particle size of 9 mu m, and adding oxalic acid and nitric acid during grinding, wherein the oxalic acid accounts for 29 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 100 percent of the total amount of manganese in the ore; the material comprises 32 parts of manganese ore, 5 parts of tungsten trioxide, 55.3 parts of diatomite and 7.7 parts of forming auxiliary agent in parts by mass; the precursor of the tungsten is ammonium metatungstate; the water content of the diatomite is 5%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 117 deg.C for 7.7h, standing for 22h, preparing into honeycomb type blank, drying at 160 deg.C in air atmosphere to obtain dry blank, and heating to 670 deg.C at 10 deg.C/min for roasting for 4 h.
Example 18
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite and pyrolusite as main raw materials, wherein the mass fraction of the manganite is 75 wt.%. Firstly, crushing manganese ore to an average particle size of 0.3mm, grinding at 103 ℃ to an average particle size of 31 mu m, and adding oxalic acid, nitric acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 34 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 100 percent of the total amount of manganese in the ore; the material comprises, by mass, 37 parts of manganese ore, 6 parts of molybdenum trioxide, 49.8 parts of diatomite and 7.2 parts of a forming aid; the precursor of the molybdenum is molybdenum trioxide; the water content of the diatomite is 5%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 84 deg.C for 4.4h, standing for 23h after mixing, preparing into plate blank, drying at 83 deg.C in steam atmosphere to obtain dry blank, and heating to 340 deg.C at 9 deg.C/min for roasting for 17 h.
Example 19
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 80 wt.%. Firstly, crushing manganese ore to an average particle size of 0.2mm, grinding at 108 ℃ to an average particle size of 34 mu m, and adding oxalic acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 39% (by mass), and the amount of acidic substances accounts for 60% of the total mass of manganese in the ore; the material comprises 42 parts of manganese ore, 1 part of molybdenum trioxide, 50.3 parts of diatomite and 6.7 parts of a forming aid in parts by mass; the precursor of the molybdenum is ammonium heptamolybdate; the water content of the diatomite is 4%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 89 ℃ for 4.9h, standing for 24h after mixing, preparing a corrugated plate type blank, drying in an air atmosphere at 88 ℃ to obtain a dry blank, and finally heating to 390 ℃ at 8 ℃/min and roasting for 15 h.
Embodiment 20
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite, pyrolusite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 85 wt.%. Firstly, crushing manganese ore to an average particle size of 0.1mm, grinding at 113 ℃ to an average particle size of 37 mu m, and adding oxalic acid and nitric acid during grinding, wherein the oxalic acid accounts for 16 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 60 percent of the total amount of manganese in the ore; the material comprises 47 parts by mass of manganese ore, 2 parts by mass of tungsten trioxide, 44.8 parts by mass of diatomite and 6.2 parts by mass of a forming aid; the precursor of the tungsten is tungsten trioxide; the water content of the diatomite is 4%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 94 deg.C for 8h, standing for 8.5h, preparing into clover-shaped blank, drying at 93 deg.C in steam atmosphere to obtain dry blank, and heating to 440 deg.C at 7 deg.C/min for roasting for 13 h.
Example 21
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite as a main raw material. Firstly, crushing manganese ore to an average particle size of 0.08mm, grinding at 118 ℃ to an average particle size of 10 mu m, and adding oxalic acid, nitric acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 21 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 60 percent of the total amount of manganese in the ore; the material comprises, by mass, 52 parts of manganese ore, 3 parts of tungsten trioxide, 39.3 parts of diatomite and 5.7 parts of a forming aid; the precursor of the tungsten is ammonium metatungstate; the water content of the diatomite is 4%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 99 ℃ for 5.9h, standing for 9.5h after mixing, preparing a honeycomb type blank, drying in an air atmosphere at 98 ℃ to obtain a dry blank, and finally heating to 490 ℃ at 6 ℃/min and roasting for 11 h.
Embodiment 22
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite and pyrolusite as main raw materials, wherein the mass fraction of the manganite is 90 wt.%. Firstly, crushing manganese ore to an average particle size of 0.5mm, grinding at 123 ℃ to an average particle size of 43 mu m, and adding oxalic acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 26 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 60 percent of the total amount of manganese in the ore; the material comprises, by mass, 57 parts of manganese ore, 4 parts of molybdenum trioxide, 33.8 parts of diatomite and 5.2 parts of a forming aid; the precursor of the molybdenum is molybdenum trioxide; the water content of the diatomite is 4%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 104 deg.C for 6.4h, standing for 10.5h, preparing into plate blank, drying at 103 deg.C in steam atmosphere to obtain dry blank, and baking at 5 deg.C/min to 540 deg.C for 9 h.
Example 23
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 95 wt.%. Crushing manganese ore to an average particle size of 1.4mm, grinding at 128 ℃ to an average particle size of 46 mu m, and adding oxalic acid and nitric acid during grinding, wherein the oxalic acid accounts for 31 percent (by mass), and the amount of acidic substances accounts for 50 percent of the total mass of manganese in the ore; the material comprises 14 parts by mass of manganese ore, 5 parts by mass of molybdenum trioxide, 71.4 parts by mass of diatomite and 9.6 parts by mass of a forming aid; the precursor of the molybdenum is ammonium heptamolybdate; the water content of the diatomite is 3%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 109 ℃ for 6.9h, standing for 11.5h after mixing, preparing a corrugated plate type blank, drying in an air atmosphere at 108 ℃ to obtain a dry blank, and finally heating to 590 ℃ at 4 ℃/min and roasting for 7 h.
Embodiment 24
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite, pyrolusite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 22 wt.%. Firstly, crushing manganese ore to an average particle size of 1.6mm, grinding at 133 ℃ to an average particle size of 49 mu m, and adding oxalic acid, nitric acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 36% (by mass), and the amount of acidic substances accounts for 50% of the total mass of manganese in the ore; the material comprises, by mass, 19 parts of manganese ore, 6 parts of tungsten trioxide, 65.9 parts of diatomite and 9.1 parts of a forming aid; the precursor of the tungsten is tungsten trioxide; the water content of the diatomite is 3%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 114 deg.C for 7.4h, standing for 12.5h, preparing into clover-shaped blank, drying at 113 deg.C in steam atmosphere to obtain dry blank, and baking at 3 deg.C/min to 640 deg.C for 5 h.
Example 25
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite as a main raw material. Firstly, crushing manganese ore to an average particle size of 1.8mm, grinding at 138 ℃ to an average particle size of 11 mu m, and adding oxalic acid, nitric acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 11 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 50 percent of the total amount of manganese in the ore; the material comprises, by mass, 24 parts of manganese ore, 5 parts of tungsten trioxide, 62.4 parts of diatomite and 8.6 parts of a forming aid; the precursor of the tungsten is ammonium metatungstate; the water content of the diatomite is 3%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 119 ℃ for 7.9h, standing for 13.5h after mixing, preparing a honeycomb type blank, drying at 118 ℃ in the air atmosphere to obtain a dry blank, and finally heating to 690 ℃ at 2 ℃/min and roasting for 4 h.
Example 26
A method for preparing a low-temperature denitration catalyst by utilizing manganese ores adopts manganite and pyrolusite as main raw materials, wherein the mass fraction of the manganite is 33 wt.%. Firstly, crushing manganese ore to an average particle size of 1.9mm, grinding at 86 ℃ to an average particle size of 15 mu m, and adding oxalic acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 16 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 50 percent of the total amount of manganese in the ore; the material comprises 29 parts by mass of manganese ore, 6 parts by mass of molybdenum trioxide, 56.9 parts by mass of diatomite and 8.1 parts by mass of a forming aid; the precursor of the molybdenum is molybdenum trioxide; the water content of the diatomite is 3%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 86 ℃ for 4.6h, standing for 14.5h after mixing, preparing a plate blank, drying in a steam atmosphere at 123 ℃ to obtain a dry blank, and finally heating to 360 ℃ at 1 ℃/min for roasting for 6 h.
Example 27
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 27 wt.%. Firstly, crushing manganese ore to an average particle size of 0.2mm, grinding at 91 ℃ to an average particle size of 21 mu m, and adding oxalic acid, nitric acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 18 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 40 percent of the total amount of manganese in the ore; the material comprises, by mass, 34 parts of manganese ore, 3 parts of molybdenum trioxide, 55.4 parts of diatomite and 7.6 parts of a forming aid; the precursor of the molybdenum is ammonium heptamolybdate; the water content of the diatomite is 8%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the materials at 91 ℃ for 5.1h, standing for 15.5h after mixing, preparing a corrugated plate type blank, drying in an air atmosphere at 128 ℃ to obtain a dry blank, and finally heating to 410 ℃ at 3 ℃/min and roasting for 8 h.
Example 28
A method for preparing a low-temperature denitration catalyst by utilizing manganese ore adopts manganite, pyrolusite and rhodochrosite as main raw materials, wherein the mass fraction of the manganite is 38 wt.%. Firstly, crushing manganese ore to an average particle size of 0.3mm, grinding at 96 ℃ to an average particle size of 26 mu m, and adding oxalic acid and sulfuric acid during grinding, wherein the oxalic acid accounts for 22 percent (calculated by the amount of substances), and the amount of acidic substances accounts for 90 percent of the total amount of manganese in the ore; the material comprises, by mass, 39 parts of manganese ore, 4 parts of tungsten trioxide, 49.9 parts of diatomite and 7.1 parts of a forming aid; the precursor of the tungsten is tungsten trioxide; the water content of the diatomite is 8%; the forming auxiliary agent comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide. Further mixing the above materials at 96 deg.C for 5.6h, standing for 16.5h, preparing into clover-shaped blank, drying in steam atmosphere at 133 deg.C to obtain dry blank, and heating to 460 deg.C at 5 deg.C/min for roasting for 9 h.
Claims (10)
1. A method for preparing a low-temperature denitration catalyst by using manganese ore is characterized in that the low-temperature denitration catalyst is prepared by using the manganese ore as a main raw material, natural manganese element and associated iron element in the manganese ore are used as active components, and Si and Al components in the ore are used as carriers; comprises the steps of crushing, grinding, component blending, mixing, molding, drying and roasting.
2. The method for preparing the low-temperature denitration catalyst by using manganese ore according to claim 1, wherein the manganese ore is one or more of manganite, pyrolusite and rhodochrosite, and the mass fraction of the manganite is not less than 20 wt.%.
3. The method for preparing the low-temperature denitration catalyst by using manganese ore according to claim 1, wherein the crushing is to physically crush the manganese ore to an average particle size of 2mm or less.
4. The method for preparing the low-temperature denitration catalyst by using manganese ore according to claim 1, wherein the grinding is carried out by grinding the manganese ore until the average particle size is less than or equal to 50 μm, and the acidic substance is added during the grinding process and the temperature is controlled to be 80-140 ℃.
5. The method for preparing the low-temperature denitration catalyst by using manganese ore according to claim 4, wherein the acidic substance is a mixture of oxalic acid and inorganic strong acid; in the acidic substance, the consumption of oxalic acid is 10% -40% by mass of the substance; the inorganic strong acid is one or two of nitric acid and sulfuric acid;
the amount of the acidic substance is 40-100% of the total amount of manganese in the ore by mass.
6. The method for preparing the low-temperature denitration catalyst by using manganese ore according to claim 1, wherein the components are prepared by adding one of a tungsten oxide precursor and a molybdenum oxide precursor to a ground material, and adding diatomite and a forming aid;
10-60 parts of manganese ore, 1-6 parts of tungsten oxide precursor/molybdenum oxide precursor, 30-80 parts of diatomite and 5-10 parts of forming aid by mass;
the tungsten oxide precursor is one or two of ammonium metatungstate and tungsten trioxide;
the molybdenum oxide precursor is one or two of ammonium heptamolybdate and molybdenum trioxide;
the water content of the diatomite is less than or equal to 8 percent;
the forming aid comprises clay, stearic acid, glass fiber, carboxymethyl cellulose and polyethylene oxide.
7. The method for preparing the low-temperature denitration catalyst by using manganese ore according to claim 1, wherein the mulling is to uniformly stir and mix the materials prepared by the components, the mulling time is 4-8 hours, the temperature is 80-120 ℃, and the mixture is placed for 6-24 hours after mulling.
8. The method for preparing the low-temperature denitration catalyst by using manganese ore according to claim 1, wherein the forming is to prepare the pug after the mulling into one of honeycomb-type, plate-type, corrugated plate-type and clover-type blanks.
9. The method for preparing the low-temperature denitration catalyst by using manganese ore according to claim 1, wherein the drying is carried out by controlling the temperature to be 80-160 ℃, and the formed blank is slowly dehydrated in air or steam atmosphere to obtain a dry blank.
10. The method for preparing the low-temperature denitration catalyst by using manganese ore as claimed in claim 1, wherein the roasting is carried out by roasting the catalyst dry blank at 300-700 ℃ for 4-24 h, and the heating rate is 1-15 ℃/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1256640A (en) * | 1997-05-17 | 2000-06-14 | 韩国电力技术株式会社 | Method for removing nitrogen oxides using natural manganese ores |
| CN101300068A (en) * | 2005-09-27 | 2008-11-05 | 韩国电力技术株式会社 | Vanadium/titania catalyst comprising natural manganese ore for removing nitrogen oxides and dioxin in wide operating temperature range and method of using the same |
| CN108855124A (en) * | 2018-07-11 | 2018-11-23 | 武汉理工大学 | A method of SCR denitration is prepared with manganese ore using steel-making sintering ash |
| CN111589442A (en) * | 2020-06-07 | 2020-08-28 | 四川大学 | Application of natural manganese ore in preparation of denitration catalyst, denitration catalyst and preparation method of denitration catalyst |
| CN111729666A (en) * | 2020-06-18 | 2020-10-02 | 北京科技大学 | Method for preparing denitration catalyst from vanadium titano-magnetite |
-
2020
- 2020-11-17 CN CN202011289497.5A patent/CN112427033B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1256640A (en) * | 1997-05-17 | 2000-06-14 | 韩国电力技术株式会社 | Method for removing nitrogen oxides using natural manganese ores |
| CN101300068A (en) * | 2005-09-27 | 2008-11-05 | 韩国电力技术株式会社 | Vanadium/titania catalyst comprising natural manganese ore for removing nitrogen oxides and dioxin in wide operating temperature range and method of using the same |
| CN108855124A (en) * | 2018-07-11 | 2018-11-23 | 武汉理工大学 | A method of SCR denitration is prepared with manganese ore using steel-making sintering ash |
| CN111589442A (en) * | 2020-06-07 | 2020-08-28 | 四川大学 | Application of natural manganese ore in preparation of denitration catalyst, denitration catalyst and preparation method of denitration catalyst |
| CN111729666A (en) * | 2020-06-18 | 2020-10-02 | 北京科技大学 | Method for preparing denitration catalyst from vanadium titano-magnetite |
Non-Patent Citations (2)
| Title |
|---|
| 徐永鹏 等: "酸浸天然锰矿石低温氧化脱硝性能研究", 《合肥工业大学学报（自然科学版）》 * |
| 王运正 等: "《现代锰冶金》", 30 September 2015, 冶金工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115501748A (en) * | 2021-08-31 | 2022-12-23 | 嘉兴沃特泰科环保科技股份有限公司 | Denitration agent and preparation method thereof |
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