CN114505079B - Preparation method of low-temperature manganese-based SCR denitration catalyst and application of low-temperature manganese-based SCR denitration catalyst in flue gas denitration - Google Patents
Preparation method of low-temperature manganese-based SCR denitration catalyst and application of low-temperature manganese-based SCR denitration catalyst in flue gas denitration Download PDFInfo
- Publication number
- CN114505079B CN114505079B CN202210413008.5A CN202210413008A CN114505079B CN 114505079 B CN114505079 B CN 114505079B CN 202210413008 A CN202210413008 A CN 202210413008A CN 114505079 B CN114505079 B CN 114505079B
- Authority
- CN
- China
- Prior art keywords
- manganese
- catalyst
- catalyst carrier
- salt
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
-
- 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
- B01D53/90—Injecting reactants
-
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
A preparation method of a low-temperature manganese-based SCR denitration catalyst and application thereof in flue gas denitration belong to the technical field of flue gas denitration, and comprise prefabrication of a catalyst carrier, micropore modification of the catalyst carrier, and dipping and calcination; dissolving cerium salt, tungstate, persulfate and zirconium sulfate in water, adding a high molecular surfactant, stirring, adding a silane coupling agent and hafnium carbide powder, and carrying out hydrothermal reaction on a colloidal solution obtained by reaction to obtain a catalyst carrier; impregnating and calcining the catalyst carrier modified by micropores, evaporating water, drying and calcining to obtain the catalyst carrierTo manganese-based SCR denitration catalyst. The invention prepares the SO resistance at low temperature2anti-H2The denitration efficiency of the manganese-based denitration catalyst with good O performance is 85.7-87.3%, 93.1-94.2%, 93.8-95.5%, 88.6-90.2% and 81.6-83.9% at 80 ℃, 110 ℃, 140 ℃, 170 ℃ and 200 ℃.
Description
Technical Field
The invention relates to a preparation method of a low-temperature manganese-based SCR denitration catalyst and application of the low-temperature manganese-based SCR denitration catalyst in flue gas denitration, and belongs to the technical field of flue gas denitration.
Background
Ammonia Selective Catalytic Reduction (SCR) technology is considered to be one of the most effective technologies for treating nitrogen oxide pollution at present. The core of SCR technology is denitration catalyst, V in recent decades2O5—WO3/TiO2The catalyst is always the mainstream of the denitration catalyst, but the reaction activity temperature range of the catalyst is higher, generally 300-400 ℃, the biotoxicity of vanadium is easy to cause secondary pollution to the environment, and in addition, TiO (titanium oxide) at high temperature is easy to cause secondary pollution to the environment2The deactivation of the catalyst by the phase transition process from anatase to rutile phase also limits the further use of this commercial catalyst, and therefore there is an urgent need to develop an environmentally friendly catalyst with high catalytic activity. The manganese-based SCR denitration catalyst is one of the most researched and reported catalysts in the field at present.
Although the manganese-based SCR denitration catalyst has low reaction temperature and high catalytic activity, the catalyst can react on N under the condition of low temperature2Is poor in selectivity to SO2And H2The O has poor resistance and is easy to inactivate in smoke. To address these shortcomings of manganese-based catalysts, a great deal of research has been done on manganese-based catalysts by those skilled in the art.
Chinese patent CN101879452A discloses a manganese-based low-temperature denitration catalyst and a preparation method thereof, the catalyst is a composite oxide of Mn, Fe, Sn and Ce, and the composite oxide catalyst has good sulfur resistance, but poor water resistance.
Chinese patent CN108031482A discloses a high-temperature type composite denitration catalyst containing phosphorus, cerium, manganese and tin, which is prepared by compounding cerium phosphate, manganese oxide and tin oxide, and has a high removal rate of nitrogen oxides at a high temperature range (300-500 ℃), and also has good water resistance, but the catalyst does not have SO resistance2And (4) performance.
As can be seen from the above, the manganese-based SCR denitration catalyst still has SO resistance under the low-temperature condition2anti-H2The problem of poor O performance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a low-temperature manganese-based SCR denitration catalyst and application thereof in flue gas denitration, and the following aims are achieved: preparing low-temperature anti-SO2anti-H2And O is a high-activity denitration catalyst with good performance.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of a low-temperature manganese-based SCR denitration catalyst and an application of the low-temperature manganese-based SCR denitration catalyst in flue gas denitration comprise prefabrication of a catalyst carrier, micropore modification of the catalyst carrier, and dipping and calcination.
The following is a further improvement of the above technical scheme:
step 1 catalyst support prefabrication
Dissolving cerium salt, tungstate, persulfate and zirconium sulfate in deionized water, adding a high-molecular surfactant, adjusting the pH to be 3.5-4.5 by hydrochloric acid, stirring to a clear and transparent state, adding a silane coupling agent, slowly adding hafnium carbide powder, stirring at room temperature for reaction for 12-24 hours, transferring the obtained colloidal solution into a reaction kettle with a polytetrafluoroethylene lining, filtering after hydrothermal reaction, washing the obtained solid with deionized water until the washing liquid is neutral, washing with absolute ethyl alcohol for three times, and drying to obtain a catalyst carrier;
carrying out hydrothermal reaction at 190-240 ℃ for 3-8 hours;
the cerium salt is one of cerium sulfate, cerium nitrate and cerium chloride;
the tungstate is one of sodium tungstate, ammonium tungstate and potassium tungstate;
the persulfate is one of sodium persulfate, potassium persulfate and ammonium persulfate;
the high molecular surfactant is one of polyethylene glycol, polyoxyethylene sorbitan laurate and polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer;
the silane coupling agent is one of KH540, KH550 and KH 560;
the particle size of the hafnium carbide powder is 600-1200 nm;
the mass ratio of the cerium salt to the tungstate to the persulfate to the zirconium sulfate to the polymeric surfactant to the deionized water is 50-80: 10-18: 4-8: 10-14: 90-130: 700-850;
the adding amount of the hafnium carbide powder is 0.5-1.5% of the mass of the high molecular surfactant;
the adding amount of the silane coupling agent is 1.5-2.5% of the mass of the high molecular surfactant.
Step 2 catalyst support micropore modification
Stirring and dispersing the catalyst carrier in an alcohol ether solvent, then adding an amine compound and 2-aminoethyl phosphonic acid, stirring, refluxing, reacting, cooling, filtering, washing the obtained solid with absolute ethyl alcohol for three times, and drying in vacuum to obtain the microporous modified catalyst carrier;
the alcohol ether solvent is one of diethylene glycol butyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether;
the amine compound is one of ethylenediamine, methylamine and ethylamine;
the mass ratio of the catalyst carrier, the alcohol ether solvent, the amine compound and the 2-aminoethylphosphonic acid is 10-20: 70-90: 5-13: 1-5;
stirring reflux reaction is carried out at the temperature of 65-90 ℃, the stirring speed is 950-1300 rpm, and the reaction time is 5-10 hours.
Step 3 impregnation calcination
Dissolving manganese salt, cobalt salt and indium salt in deionized water to obtain a steeping liquor, adding the steeping liquor into a micropore-modified catalyst carrier, stirring for 10-20 hours, and evaporating, drying and calcining the filtered catalyst carrier to obtain a manganese-based SCR denitration catalyst;
the manganese salt is one of manganese nitrate, manganese acetate and manganese sulfate;
the cobalt salt is one of cobalt nitrate, cobalt sulfate and cobalt chloride;
the indium salt is indium trichloride;
the mass ratio of the manganese salt to the cobalt salt to the indium salt to the deionized water is 18-22: 3-9: 4-10: 90-100;
the addition amount of the micropore modified catalyst carrier is 50-65% of the mass of the impregnation liquid;
the water evaporation is vacuum drying for 1-2 hours at the temperature of 60-75 ℃;
the drying is drying for 1-1.5 hours at the temperature of 95-110 ℃;
the calcination is carried out at 500-600 ℃ for 3-5 hours.
The application of the low-temperature manganese-based SCR denitration catalyst in flue gas denitration comprises the step of enabling the prepared manganese-based SCR denitration catalyst to be high in purity N at 200 DEG C2And (3) pretreating for 1h, cooling to room temperature, placing into a fixed bed system in a flue gas denitration device, heating to 110-140 ℃, introducing flue gas to be treated, starting continuous flue gas denitration operation by the fixed bed system, wherein the denitration efficiency in the continuous denitration operation can reach 93.1-95.5%.
Compared with the prior art, the invention has the following beneficial effects:
1. the method of the invention prepares the SO resistance at low temperature2anti-H2O is a high-activity manganese-based denitration catalyst with good performance;
2. the manganese-based denitration catalyst has the denitration efficiency of 85.7-87.3%, 93.1-94.2%, 93.8-95.5%, 88.6-90.2% and 81.6-83.9% at the temperature of 80 ℃, 110 ℃, 140 ℃, 170 ℃ and 200 ℃.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1: preparation method of low-temperature manganese-based SCR denitration catalyst
The method comprises the following steps:
1. catalyst support prefabrication
Dissolving cerium salt, tungstate, persulfate and zirconium sulfate in deionized water, adding a high-molecular surfactant, adjusting the pH to be =4 by hydrochloric acid, stirring to a clear and transparent state, adding a silane coupling agent, slowly adding hafnium carbide powder, stirring at room temperature for reacting for 18 hours, transferring the obtained colloidal solution into a reaction kettle with a polytetrafluoroethylene lining, filtering after hydrothermal reaction, washing the obtained solid with the deionized water until the washing liquid is neutral, washing with absolute ethyl alcohol for three times, and drying to obtain a catalyst carrier;
carrying out hydrothermal reaction at 220 ℃ for 5 hours;
the cerium salt is cerium sulfate;
the tungstate is sodium tungstate;
the persulfate is sodium persulfate;
the high molecular surfactant is polyoxyethylene sorbitan laurate;
the silane coupling agent is KH 540;
the grain size of the hafnium carbide powder is 800 nm;
the mass ratio of the cerium salt to the tungstate to the persulfate to the zirconium sulfate to the polymeric surfactant to the deionized water is 65:14:6:12:100: 800;
the adding amount of the hafnium carbide powder is 1 percent of the mass of the high molecular surfactant;
the adding amount of the silane coupling agent is 1.8 percent of the mass of the high molecular surfactant.
2. Catalyst support micropore modification
Stirring and dispersing a catalyst carrier in an alcohol ether solvent, then adding an amine compound and 2-aminoethylphosphonic acid, stirring, refluxing, reacting, cooling and filtering, washing the obtained solid with absolute ethyl alcohol for three times, and drying in vacuum to obtain a micropore modified catalyst carrier;
the alcohol ether solvent is diethylene glycol monobutyl ether;
the amine compound is ethylenediamine;
the mass ratio of the catalyst carrier, the alcohol ether solvent, the amine compound and the 2-aminoethylphosphonic acid is 14:80:9: 3;
the stirring reflux reaction is carried out, the temperature is 80 ℃, the stirring speed is 1200 r/m, and the reaction time is 8 hours.
3. Impregnation calcination
Dissolving manganese salt, cobalt salt and indium salt in deionized water to obtain a steeping liquor, adding the steeping liquor into a microporous modified catalyst carrier, stirring for 18 hours, and evaporating, drying and calcining the filtered catalyst carrier to obtain a manganese-based SCR denitration catalyst;
the manganese salt is manganese nitrate;
the cobalt salt is cobalt nitrate;
the indium salt is indium trichloride;
the mass ratio of the manganese salt to the cobalt salt to the indium salt to the deionized water is 20:7:8: 96;
the adding amount of the micropore modified catalyst carrier is 58% of the mass of the impregnation liquid;
the water evaporation is vacuum drying at 67 ℃ for 1.4 hours;
the drying is drying for 1.3 hours at 105 ℃;
the calcination is carried out at 560 ℃ for 3.6 hours.
Example 2: preparation method of low-temperature manganese-based SCR denitration catalyst
The method comprises the following steps:
1. catalyst support prefabrication
Dissolving cerium salt, tungstate, persulfate and zirconium sulfate in deionized water, adding a high-molecular surfactant, adjusting the pH to be =3.5 by using hydrochloric acid, stirring to be in a clear and transparent state, adding a silane coupling agent, slowly adding hafnium carbide powder, stirring at room temperature for reaction for 12 hours, transferring the obtained colloidal solution into a reaction kettle with a polytetrafluoroethylene lining, filtering after hydrothermal reaction, washing the obtained solid with the deionized water until the washing liquid is neutral, washing with absolute ethyl alcohol for three times, and drying to obtain a catalyst carrier;
carrying out hydrothermal reaction at 190 ℃ for 3 hours;
the cerium salt is cerium nitrate;
the tungstate is ammonium tungstate;
the persulfate is potassium persulfate;
the high molecular surfactant is polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer;
the silane coupling agent is KH 550;
the particle size of the hafnium carbide powder is 600 nm;
the mass ratio of the cerium salt to the tungstate to the persulfate to the zirconium sulfate to the polymeric surfactant to the deionized water is 50:10:4:10:90: 700;
the adding amount of the hafnium carbide powder is 0.5 percent of the mass of the high molecular surfactant;
the adding amount of the silane coupling agent is 1.5 percent of the mass of the high molecular surfactant.
2. Catalyst support micropore modification
Stirring and dispersing a catalyst carrier in an alcohol ether solvent, then adding an amine compound and 2-aminoethylphosphonic acid, stirring, refluxing, reacting, cooling and filtering, washing the obtained solid with absolute ethyl alcohol for three times, and drying in vacuum to obtain a micropore modified catalyst carrier;
the alcohol ether solvent is propylene glycol methyl ether;
the amine compound is methylamine;
the mass ratio of the catalyst carrier, the alcohol ether solvent, the amine compound and the 2-aminoethyl phosphonic acid is 10:70:5: 1;
the stirring reflux reaction is carried out at the temperature of 65 ℃, the stirring speed is 950 rpm, and the reaction time is 5 hours.
3. Impregnation calcination
Dissolving manganese salt, cobalt salt and indium salt in deionized water to obtain a steeping liquor, putting the steeping liquor into a microporous modified catalyst carrier, stirring for 10 hours, and evaporating, drying and calcining the filtered catalyst carrier to obtain a manganese-based SCR denitration catalyst;
the manganese salt is manganese sulfate;
the cobalt salt is cobalt chloride;
the indium salt is indium trichloride;
the mass ratio of the manganese salt to the cobalt salt to the indium salt to the deionized water is 18:3:4: 90;
the adding amount of the micropore modified catalyst carrier is 50% of the mass of the impregnation liquid;
the water evaporation is vacuum drying at 60 ℃ for 1 hour;
the drying is drying for 1 hour at 95 ℃;
the calcination is carried out at 500 ℃ for 3 hours.
Example 3: preparation method of low-temperature manganese-based SCR denitration catalyst
The method comprises the following steps:
1. catalyst support prefabrication
Dissolving cerium salt, tungstate, persulfate and zirconium sulfate in deionized water, adding a high-molecular surfactant, adjusting the pH to be =4.5 by hydrochloric acid, stirring to be in a clear and transparent state, adding a silane coupling agent, slowly adding hafnium carbide powder, stirring at room temperature for reaction for 24 hours, transferring the obtained colloidal solution into a reaction kettle with a polytetrafluoroethylene lining, filtering after hydrothermal reaction, washing the obtained solid with the deionized water until the washing liquid is neutral, washing with absolute ethyl alcohol for three times, and drying to obtain a catalyst carrier;
carrying out hydrothermal reaction at 240 ℃ for 8 hours;
the cerium salt is cerium chloride;
the tungstate is potassium tungstate;
the persulfate is ammonium persulfate;
the high molecular surfactant is polyethylene glycol;
the silane coupling agent is KH 560;
the particle size of the hafnium carbide powder is 1200 nm;
the mass ratio of the cerium salt to the tungstate to the persulfate to the zirconium sulfate to the polymeric surfactant to the deionized water is 80:18:8:14:130: 850;
the adding amount of the hafnium carbide powder is 1.5 percent of the mass of the high molecular surfactant;
the adding amount of the silane coupling agent is 2.5% of the mass of the high molecular surfactant.
2. Catalyst support micropore modification
Stirring and dispersing a catalyst carrier in an alcohol ether solvent, then adding an amine compound and 2-aminoethylphosphonic acid, stirring, refluxing, reacting, cooling and filtering, washing the obtained solid with absolute ethyl alcohol for three times, and drying in vacuum to obtain a micropore modified catalyst carrier;
the alcohol ether solvent is dipropylene glycol methyl ether;
the amine compound is ethylamine;
the mass ratio of the catalyst carrier, the alcohol ether solvent, the amine compound and the 2-aminoethylphosphonic acid is 20:90:13: 5;
the stirring reflux reaction is carried out at the temperature of 90 ℃, the stirring speed is 1300 rpm, and the reaction time is 10 hours.
3. Impregnation calcination
Dissolving manganese salt, cobalt salt and indium salt in deionized water to obtain a steeping liquor, adding the steeping liquor into the microporous modified catalyst carrier, stirring for 20 hours, and evaporating, drying and calcining the filtered catalyst carrier to obtain a manganese-based SCR denitration catalyst;
the manganese salt is manganese acetate;
the cobalt salt is cobalt sulfate;
the indium salt is indium trichloride;
the mass ratio of the manganese salt to the cobalt salt to the indium salt to the deionized water is 22: 9:10: 100;
the adding amount of the micropore modified catalyst carrier is 65 percent of the mass of the impregnation liquid;
the water evaporation is vacuum drying at 75 ℃ for 2 hours;
the drying is drying for 1.5 hours at 110 ℃;
the calcination is carried out at 600 ℃ for 5 hours.
Comparative example 1: example 1 based on the replacement of the catalyst support by activated carbon
Steps 1 and 2 are not performed;
step 3, the microporous modified catalyst carrier is changed into active carbon with equal mass, and the other operations are the same as those in the embodiment 1;
the particle size of the active carbon is 150 meshes, and the internal pore diameter is 90 nm.
Comparative example 2: example 1 based on, not carrying out the catalyst support micropore modification step
Step 1 is the same as example 1;
step 2 is not carried out;
the procedure of step 3 was the same as in example 1.
Comparative example 3: the active component of the catalyst does not contain indium element
Step 1 is the same as example 1;
step 2 is the same as example 1;
step 3 indium trichloride was replaced with an equal amount of cobalt nitrate and the other operations were the same as in example 1.
Comparative example 4: the active component of the catalyst does not contain cobalt element
Step 1 is the same as example 1;
step 2 is the same as example 1;
step 3 cobalt nitrate was replaced with an equal amount of indium trichloride and the other operations were the same as in example 1.
Evaluation of catalytic performance:
the catalysts obtained in the above examples and comparative examples were evaluated for their catalytic reaction performance on a fixed bed system in which the reaction gas was continuously flowed at a reaction space velocity of 30000mL g-1·h-1Reaction gas composition 800ppm NO, 800ppm NH3、5vol% O2、200ppm SO2、3 vol% H2O, balance gas N2. High purity N at 200 ℃ for catalyst samples before testing2After pretreatment for 1h, cooling to room temperature, and opening NO and NH3And O2Adsorbing the catalyst to saturation, heating to the target temperature, and collecting KM9106 flue gas from Kane of GermanyThe analyzer detects the concentration of inlet and outlet NOx at the temperatures of 80 ℃, 110 ℃, 140 ℃, 170 ℃ and 200 ℃ respectively, and the calculation formula of the denitration efficiency is as follows:
η(NOx)=（Cinlet concentration of NOx- COutlet concentration of NOx）/ CInlet concentration of NOx×100%
The test results are given in the following table:
Claims (2)
1. a preparation method of a low-temperature manganese-based SCR denitration catalyst is characterized by comprising the following steps: the method comprises the steps of prefabricating a catalyst carrier, modifying micropores of the catalyst carrier, and impregnating and calcining;
the preparation method comprises the steps of prefabricating a catalyst carrier, dissolving cerium salt, tungstate, persulfate and zirconium sulfate in deionized water, adding a high-molecular surfactant, adjusting the pH value to be = 3.5-4.5 by hydrochloric acid, stirring to be a clear and transparent state, adding a silane coupling agent, slowly adding hafnium carbide powder, stirring at room temperature to react for 12-24 hours to obtain a colloidal solution, carrying out hydrothermal reaction on the colloidal solution, filtering, washing the obtained solid with deionized water until the washing liquid is neutral, washing with absolute ethyl alcohol for three times, and drying to obtain the catalyst carrier;
carrying out hydrothermal reaction at 190-240 ℃ for 3-8 hours;
the cerium salt is one of cerium sulfate, cerium nitrate and cerium chloride;
the tungstate is one of sodium tungstate, ammonium tungstate and potassium tungstate;
the persulfate is one of sodium persulfate, potassium persulfate and ammonium persulfate;
the high molecular surfactant is one of polyethylene glycol, polyoxyethylene sorbitan laurate and polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer;
the silane coupling agent is one of KH540, KH550 and KH 560;
the particle size of the hafnium carbide powder is 600-1200 nm;
the mass ratio of the cerium salt to the tungstate to the persulfate to the zirconium sulfate to the polymeric surfactant to the deionized water is 50-80: 10-18: 4-8: 10-14: 90-130: 700-850;
the adding amount of the hafnium carbide powder is 0.5-1.5% of the mass of the high molecular surfactant;
the adding amount of the silane coupling agent is 1.5-2.5% of the mass of the high molecular surfactant;
carrying out micropore modification on the catalyst carrier, stirring and dispersing the catalyst carrier in an alcohol ether solvent, then adding an amine compound and 2-aminoethylphosphonic acid, carrying out stirring reflux reaction, cooling and filtering, washing the obtained solid with absolute ethyl alcohol for three times, and carrying out vacuum drying to obtain the micropore modified catalyst carrier;
the alcohol ether solvent is one of diethylene glycol butyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether;
the amine compound is one of ethylenediamine, methylamine and ethylamine;
the mass ratio of the catalyst carrier, the alcohol ether solvent, the amine compound and the 2-aminoethylphosphonic acid is 10-20: 70-90: 5-13: 1-5;
stirring reflux reaction is carried out, wherein the temperature is 65-90 ℃, the stirring speed is 950-1300 rpm, and the reaction time is 5-10 hours;
the impregnation and calcination process comprises the steps of dissolving manganese salt, cobalt salt and indium salt in deionized water to obtain an impregnation solution, placing the impregnation solution into a micropore-modified catalyst carrier, stirring for 10-20 hours, and evaporating, drying and calcining the filtered catalyst carrier to obtain the manganese-based SCR denitration catalyst;
the manganese salt is one of manganese nitrate, manganese acetate and manganese sulfate; the cobalt salt is one of cobalt nitrate, cobalt sulfate and cobalt chloride;
the indium salt is indium trichloride;
the mass ratio of the manganese salt to the cobalt salt to the indium salt to the deionized water is 18-22: 3-9: 4-10: 90-100; the addition amount of the micropore modified catalyst carrier is 50-65% of the mass of the impregnation liquid;
the water evaporation is vacuum drying for 1-2 hours at the temperature of 60-75 ℃;
the drying is drying for 1-1.5 hours at the temperature of 95-110 ℃; the calcination is carried out at 500-600 ℃ for 3-5 hours.
2. The application of the low-temperature manganese-based SCR denitration catalyst prepared by the method of claim 1 in flue gas denitration is characterized in that: when the low-temperature manganese-based SCR denitration catalyst is used for denitration reaction on a continuous flowing fixed bed system, the denitration efficiency can reach 93.1-95.5% at the reaction temperature of 110-140 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210413008.5A CN114505079B (en) | 2022-04-20 | 2022-04-20 | Preparation method of low-temperature manganese-based SCR denitration catalyst and application of low-temperature manganese-based SCR denitration catalyst in flue gas denitration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210413008.5A CN114505079B (en) | 2022-04-20 | 2022-04-20 | Preparation method of low-temperature manganese-based SCR denitration catalyst and application of low-temperature manganese-based SCR denitration catalyst in flue gas denitration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114505079A CN114505079A (en) | 2022-05-17 |
| CN114505079B true CN114505079B (en) | 2022-06-24 |
Family
ID=81555546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210413008.5A Active CN114505079B (en) | 2022-04-20 | 2022-04-20 | Preparation method of low-temperature manganese-based SCR denitration catalyst and application of low-temperature manganese-based SCR denitration catalyst in flue gas denitration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114505079B (en) |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314127A (en) * | 2007-05-31 | 2008-12-03 | 中国科学院大连化学物理研究所 | Oxide catalyst for selective reduction of nitrogen oxide, preparation and uses thereof |
| CN101637721A (en) * | 2009-08-18 | 2010-02-03 | 上海华明高技术（集团）有限公司 | Porous yttrium-cerium-zirconium solid solution and preparation method thereof |
| CN101730575A (en) * | 2007-04-26 | 2010-06-09 | 约翰逊马西有限公司 | transition metal/zeolite scr catalysts |
| CN102019187A (en) * | 2010-11-25 | 2011-04-20 | 浙江工业大学 | Low-temperature flue gas SCR (Selective Catalytic Reduction) denitrating catalyst and preparation method and application thereof |
| CN102166522A (en) * | 2011-03-07 | 2011-08-31 | 山东众禾环保科技股份有限公司 | Flue gas denitration catalyst and preparation method and application thereof |
| CN102513150A (en) * | 2011-11-14 | 2012-06-27 | 天津大学 | SAPO (Silicoaluminophosphate) molecular sieve SCR (Selective Catalytic Reduction) catalyst, preparation thereof and application thereof in removal of acrylonitrile tail gas NOx |
| CN102580728A (en) * | 2011-01-07 | 2012-07-18 | 通用电气公司 | Catalyst and preparation method |
| CN103007952A (en) * | 2012-11-23 | 2013-04-03 | 中安和谐科技发展集团有限公司 | Low-temperature SCR (selective catalytic reduction) catalyst for flue gas denitrification and application thereof |
| CN103240079A (en) * | 2013-05-30 | 2013-08-14 | 中国科学院生态环境研究中心 | Cerium-zirconium-tungsten composite oxide catalyst as well as preparation method and usage thereof |
| CN103263911A (en) * | 2013-05-14 | 2013-08-28 | 上海大学 | Preparation method of denitration catalyst with nanoscale ordered honeycomb structure |
| EP2783741A2 (en) * | 2011-01-26 | 2014-10-01 | Ford Global Technologies, LLC | SCR and LNT catalysts for combined LNT-SCR applications |
| CN106111183A (en) * | 2016-06-24 | 2016-11-16 | 碗海鹰 | A kind of catalyst of selective catalyst reduction of nitrogen oxides and preparation method thereof |
| CN106423148A (en) * | 2016-11-07 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Zirconium-doped cerium-manganese oxide catalyst as well as preparation and application |
| CN106799234A (en) * | 2016-12-30 | 2017-06-06 | 包头稀土研究院 | A kind of diesel vehicle rare earth base SCR catalyst and preparation method |
| CN106865610A (en) * | 2017-02-26 | 2017-06-20 | 桂林理工大学 | A kind of chondritic CexZr1‑xO2Raw powder's production technology |
| CN110605141A (en) * | 2018-06-15 | 2019-12-24 | 定州市荣鼎水环境生化技术有限公司 | Phosphorus-doped Cu-SSZ-13 catalyst and preparation method and application thereof |
| CN110732320A (en) * | 2019-10-13 | 2020-01-31 | 苏州倍友环保科技有限公司 | diesel engine tail gas oxidation catalyst and preparation method and application thereof |
| CN112156808A (en) * | 2020-09-30 | 2021-01-01 | 中汽研（天津）汽车工程研究院有限公司 | Preparation method and application of molecular sieve SCR catalyst with low ammonia escape rate |
| CN113318728A (en) * | 2021-06-25 | 2021-08-31 | 北京化工大学 | Three-dimensional ordered macroporous tungsten-cerium-zirconium composite oxide catalyst and preparation method and application thereof |
-
2022
- 2022-04-20 CN CN202210413008.5A patent/CN114505079B/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101730575A (en) * | 2007-04-26 | 2010-06-09 | 约翰逊马西有限公司 | transition metal/zeolite scr catalysts |
| CN101314127A (en) * | 2007-05-31 | 2008-12-03 | 中国科学院大连化学物理研究所 | Oxide catalyst for selective reduction of nitrogen oxide, preparation and uses thereof |
| CN101637721A (en) * | 2009-08-18 | 2010-02-03 | 上海华明高技术（集团）有限公司 | Porous yttrium-cerium-zirconium solid solution and preparation method thereof |
| CN102019187A (en) * | 2010-11-25 | 2011-04-20 | 浙江工业大学 | Low-temperature flue gas SCR (Selective Catalytic Reduction) denitrating catalyst and preparation method and application thereof |
| CN102580728A (en) * | 2011-01-07 | 2012-07-18 | 通用电气公司 | Catalyst and preparation method |
| EP2783741A2 (en) * | 2011-01-26 | 2014-10-01 | Ford Global Technologies, LLC | SCR and LNT catalysts for combined LNT-SCR applications |
| CN102166522A (en) * | 2011-03-07 | 2011-08-31 | 山东众禾环保科技股份有限公司 | Flue gas denitration catalyst and preparation method and application thereof |
| CN102513150A (en) * | 2011-11-14 | 2012-06-27 | 天津大学 | SAPO (Silicoaluminophosphate) molecular sieve SCR (Selective Catalytic Reduction) catalyst, preparation thereof and application thereof in removal of acrylonitrile tail gas NOx |
| CN103007952A (en) * | 2012-11-23 | 2013-04-03 | 中安和谐科技发展集团有限公司 | Low-temperature SCR (selective catalytic reduction) catalyst for flue gas denitrification and application thereof |
| CN103263911A (en) * | 2013-05-14 | 2013-08-28 | 上海大学 | Preparation method of denitration catalyst with nanoscale ordered honeycomb structure |
| CN103240079A (en) * | 2013-05-30 | 2013-08-14 | 中国科学院生态环境研究中心 | Cerium-zirconium-tungsten composite oxide catalyst as well as preparation method and usage thereof |
| CN106111183A (en) * | 2016-06-24 | 2016-11-16 | 碗海鹰 | A kind of catalyst of selective catalyst reduction of nitrogen oxides and preparation method thereof |
| CN106423148A (en) * | 2016-11-07 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Zirconium-doped cerium-manganese oxide catalyst as well as preparation and application |
| CN106799234A (en) * | 2016-12-30 | 2017-06-06 | 包头稀土研究院 | A kind of diesel vehicle rare earth base SCR catalyst and preparation method |
| CN106865610A (en) * | 2017-02-26 | 2017-06-20 | 桂林理工大学 | A kind of chondritic CexZr1‑xO2Raw powder's production technology |
| CN110605141A (en) * | 2018-06-15 | 2019-12-24 | 定州市荣鼎水环境生化技术有限公司 | Phosphorus-doped Cu-SSZ-13 catalyst and preparation method and application thereof |
| CN110732320A (en) * | 2019-10-13 | 2020-01-31 | 苏州倍友环保科技有限公司 | diesel engine tail gas oxidation catalyst and preparation method and application thereof |
| CN112156808A (en) * | 2020-09-30 | 2021-01-01 | 中汽研（天津）汽车工程研究院有限公司 | Preparation method and application of molecular sieve SCR catalyst with low ammonia escape rate |
| CN113318728A (en) * | 2021-06-25 | 2021-08-31 | 北京化工大学 | Three-dimensional ordered macroporous tungsten-cerium-zirconium composite oxide catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Mn-Ce 系列低温SCR催化剂抗硫性研究进展;张呈祥等;《化工进展》;20150731;第34卷(第7期);第1866-1871页 * |
| Selective catalytic reduction of NOx with methane over indium supported on tungstated zirconia;Yang D. et al.;《Catalysis Communications》;20070508;第8卷(第12期);第2243-2247页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114505079A (en) | 2022-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11673128B2 (en) | Method for preparing molecular sieve SCR catalyst, and catalyst prepared therethrough | |
| CN107824177B (en) | CeO taking Ce-MOF as cerium precursor2/TiO2Preparation method of low-temperature SCR catalyst | |
| CN105561983A (en) | Mn-Ce supported low temperature denitration catalyst and preparation method thereof | |
| CN107362807A (en) | A kind of Mn/Co bases low temperature SCO catalyst and preparation method thereof | |
| CN108579728B (en) | Catalyst for high-thermal-stability selective reduction of nitrogen oxide by ammonia and preparation method | |
| CN111013597A (en) | Preparation method of cerium-based composite oxide low-temperature SCR catalyst with Ce-MOF as precursor | |
| CN112275314A (en) | Manganese-cerium-based molecular sieve SCR denitration catalyst and preparation method thereof | |
| CN108704650A (en) | Preparation method of low temperature porous composite oxide denitrating catalyst and products thereof and application | |
| CN114505079B (en) | Preparation method of low-temperature manganese-based SCR denitration catalyst and application of low-temperature manganese-based SCR denitration catalyst in flue gas denitration | |
| CN113877611B (en) | Phosphoric acid modified manganese oxide supported catalyst and preparation method thereof | |
| CN112264032B (en) | Catalyst for catalyzing furfural hydrodeoxygenation to prepare 2-methylfuran | |
| CN113244908A (en) | Vanadium-based SCR catalyst and preparation method and application thereof | |
| CN108993586B (en) | Preparation method of Beta type molecular sieve for resisting propylene poisoning | |
| CN116139861B (en) | Catalyst applicable to storage reduction of nitrogen oxides of gas turbine as well as preparation and application thereof | |
| CN109046324B (en) | Medium-low temperature denitration catalyst with mesoporous cerium oxide as carrier and preparation method thereof | |
| CN111013636A (en) | Preparation method of low-temperature denitration catalyst based on municipal sludge | |
| CN109603889A (en) | A kind of catalyst and preparation method thereof for formaldehyde low-temperature catalytic oxidation | |
| CN113842888B (en) | SBA-15 molecular sieve adsorbent loaded with amino acid ionic liquid and preparation method and application thereof | |
| CN117399056A (en) | Denitration catalyst and preparation method thereof | |
| CN112570023B (en) | Ionic liquid modified CuY molecular sieve catalyst and preparation method and application thereof | |
| CN115888750B (en) | Hollow porous and non-hollow porous spherical CoMn2O4Preparation method and application of low-temperature denitration catalyst | |
| CN115518640B (en) | Preparation method and application of zinc-iron loaded modified carbon composite material | |
| CN113070072B (en) | Catalyst for desulfurization and denitrification and preparation method thereof | |
| CN116689023A (en) | Composite manganese-based catalyst and preparation method and application thereof | |
| CN116550376A (en) | Preparation method and application of Cu-SSZ-13 composite catalyst loaded with rare earth metal oxide or transition metal oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of low temperature manganese based SCR denitration catalyst and its application in flue gas denitration Effective date of registration: 20220720 Granted publication date: 20220624 Pledgee: Shandong Linqu Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG WANDA ENVIRONMENTAL TECHNOLOGY CO.,LTD. Registration number: Y2022980010708 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230714 Granted publication date: 20220624 Pledgee: Shandong Linqu Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG WANDA ENVIRONMENTAL TECHNOLOGY CO.,LTD. Registration number: Y2022980010708 |