CN110292944B - SCR denitration catalyst with ultra-wide temperature window and preparation method thereof - Google Patents

SCR denitration catalyst with ultra-wide temperature window and preparation method thereof Download PDF

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CN110292944B
CN110292944B CN201910700653.3A CN201910700653A CN110292944B CN 110292944 B CN110292944 B CN 110292944B CN 201910700653 A CN201910700653 A CN 201910700653A CN 110292944 B CN110292944 B CN 110292944B
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molecular sieve
catalyst
stirring
denitration catalyst
scr denitration
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CN110292944A (en
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徐瑞年
陈标华
王梓洋
刘宁
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Beijing University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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

Abstract

The invention discloses an ultra-wide temperature window SCR denitration catalyst, which comprises a molecular sieve carrier and a modified element, wherein the modified element is selected from the combination of any two elements or the combination of three elements of Cu, fe and Mn. The invention also discloses a preparation method of the catalyst, which comprises the steps of mixing the Na-Y molecular sieve and the silicon source, preparing the molecular sieve carrier in situ under the guidance of the template agent, and modifying the molecular sieve carrier by an ion exchange method to obtain the catalyst. The catalyst has excellent skeleton structure and pore size, great amount of acid active sites, high modified element loading rate and simple preparation process. The catalyst has high activity and few side reactions under the reaction condition of low temperature of 100-200 ℃, has high stability and difficult inactivation under the reaction condition of medium and high temperature of 250-450 ℃, has an ultra-wide operating temperature window of 100-450 ℃, has long service life and low operation cost, and is a novel SCR denitration catalyst with the ultra-wide temperature window.

Description

SCR denitration catalyst with ultra-wide temperature window and preparation method thereof
Technical Field
The invention belongs to the technical field of environmental protection catalysts, and particularly relates to an ultra-wide temperature window SCR denitration catalyst and a preparation method thereof.
Background
With the acceleration of industrialization in China, atmospheric pollution has become an important problem facing the current environment, wherein Nitrogen Oxide (NO) x ) Is one of the important components of atmospheric pollution, NO x Caused severe weather such as acid rain, photochemical smog, increased near-ground ozone concentration, dust haze and the like causes great harm to human health and growth of animals and plants, and NO in the atmosphere X Content control has become an irrevocable reality.
Selective Catalytic Reduction (SCR) is NH 3 Selective addition of NO as a reducing agent X Reduction to N 2 And H 2 The denitration technology of O is developed into NO at home and abroad due to the efficient characteristic and mature technology x The core of the SCR denitration technology is an SCR catalyst, and the performance of the catalyst directly determines the denitration efficiency of the system. The SCR catalyst which is widely applied at present is V 2 O 5 /TiO 2 The catalyst has an active temperature window of 300-400 deg.C, and when the reaction temperature is lower than 300 deg.C, side reaction, NH, can occur on the surface of the catalyst 3 With SO 3 Reaction to form (NH) 4 ) 2 SO 4 Or NH 4 HSO 4 Reduction of catalyst and NO X The product is attached to the surface of the catalyst, so that the channel and the micropore of the catalyst are blocked, and the activity of the catalyst is reduced; when the reaction temperature is higher than the applicable temperature of the catalyst, the catalyst channels and micropores are easily deformed, thereby deactivating the catalyst. In industrial applications, the higher reaction temperature of the SCR denitration catalyst requires that the catalyst be exposed to high concentrations of SO before the SCR reaction bed is placed in a desulfurization and dust removal device in industrial applications 2 And high dust flue gas, the catalyst is easily poisoned and deactivated, the removal rate and selectivity of the catalyst are seriously influenced, the service life of the catalyst is shortened, and the operation cost is increased. Therefore, the research on developing a high-activity high-selectivity ultra-wide temperature window SCR denitration catalyst becomes a hotspot in the technical field.
The SCR denitration catalyst studied at present contains metal oxygenThe catalyst mainly comprises transition metals, mainly comprising V, ce, mn, fe, cr and the like. The metal oxide catalyst has high catalytic activity but has N 2 For example, CN101879452B discloses a manganese-based low-temperature denitration catalyst MnFeSnCeO x The molar ratio of each element in the prepared catalyst is Mn: fe: sn: ce = (35-39): (2-5): (9-35): (54-21). The catalyst is based on manganese oxide, and the low-temperature denitration catalyst with better activity is obtained by adding metal oxides of iron, tin and cerium as an auxiliary agent, but the simple composite oxide has lower specific surface area, poorer selectivity to reaction and higher temperature (a)>At 150 ℃ C.) a large amount of by-product, N, is produced 2 The selectivity of (A) is obviously reduced, and enters a middle temperature zone (>At 250 deg.C), the activity of the catalyst begins to decrease.
The molecular sieve catalyst has the characteristics of obvious pore structure and large specific surface area, has good development prospect in the technical field of SCR denitration, the reaction temperature of the relatively mature catalyst is above 300 ℃, and the development of the low-temperature SCR molecular sieve catalyst needs further research. For example, CN105833899A discloses a preparation method of an SCR catalyst for purifying nitrogen oxides in automobile exhaust, which comprises a preparation step of an SSZ-13 molecular sieve, a preparation step of a Cu-SSZ-13 catalyst and a preparation step of a monolithic SCR catalyst, wherein the catalyst has good activity only in the temperature range of 200-550 ℃, the activity is not high at the low temperature of less than 200 ℃, and the patent does not describe that the catalyst is applied to N 2 Of the cell.
CN107570205A discloses a preparation method of a modified Beta molecular sieve catalyst, which belongs to the technical field of catalysts, and the method comprises the steps of preparing Beta molecular sieve raw powder, preparing a Mn-Co-Beta molecular sieve and preparing a Sn modified Mn-Co-Beta molecular sieve, wherein the molar ratio of Mn element to Co element is 5-8, and the mass of Mn element accounts for 10-13% of the mass of the Mn-Co-Beta molecular sieve; sn element and Mn elementThe molar ratio of (A) to (B) is 1. The catalyst prepared by the method can be applied to an automobile exhaust low-temperature SCR denitration system, and has better CO resistance on the premise of keeping a better temperature operation window 2 And SO 2 The catalyst described in this patent is not so active at low temperature that at 150 ℃ the conversion is only 52% and at 200 ℃ it is only 64%, and furthermore the catalyst has a good catalytic activity towards N 2 Nor is there any detailed description of the selectivity.
However, environmental protection and energy conservation are global issues at present, and the problems of high activity and high selectivity of the SCR denitration catalyst in both low-temperature and high-temperature areas are solved, and excessive generation of byproducts is avoided, which is one of important means for improving the problems of energy waste and environmental pollution in the current SCR denitration catalysis field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a high-activity high-selectivity ultra-wide temperature window SCR denitration catalyst X Has an ultra-wide temperature window, does not deactivate in a high-temperature region, and can inhibit by-product NO during the reaction 2 And N 2 O generation, and increase of N product generated in the reaction process 2 Thereby achieving the purposes of effective denitration under the low temperature condition of the moving source and non-inactivation of the catalyst under the high temperature condition.
The invention relates to an ultra-wide temperature window SCR denitration catalyst, which comprises a molecular sieve carrier and a modified element, wherein the modified element is selected from the combination of any two elements or the combination of three elements of Cu, fe and Mn.
Further, the ultra-wide temperature window range means that the denitration catalyst has denitration activity at 100-450 ℃.
Further, the molecular sieve support is an AFX type molecular sieve, a CHA type molecular sieve or a BEA type molecular sieve.
Further, the AFX type molecular sieve is an SSZ-16 molecular sieve, an SSZ-17 molecular sieve or a SAPO-56 molecular sieve.
Further, the mass percent of the modifying element in the denitration catalyst is 5-10%, preferably 4-7%, and more preferably 6.5%, based on the mass of the carrier and the total mass of the modifying element simple substance.
Further, based on the total mass of the modified element simple substance, the mass of Cu is 0-80% of the mass of the modified element, the mass of Fe is 0-80% of the mass of the modified element, and the mass of Mn is 0-70% of the mass of the modified element.
Further, the denitration catalyst is Cu & Fe-SSZ-16, cu &Mn-SSZ-16, fe & Mn-SSZ-16 or Cu & Fe & Mn-SSZ-16, preferably Cu & Fe & Mn-SSZ-16.
Further, when the denitration catalyst is Cu & Fe & Mn-SSZ-16, the mass ratio of the modifying elements is Cu: fe: mn =1: fe: mn =2: fe: mn =1: fe: mn = 1.
The invention also provides a preparation method of the denitration catalyst, which comprises the following steps:
1) Preparation of the support
a) Adding a sodium hydroxide solution into a polytetrafluoroethylene lining of a reaction kettle, uniformly stirring, adding a template after stirring is stopped, continuously stirring, adding a Na-Y molecular sieve after stirring is stopped, continuously stirring, adding a silicon source into the lining, and continuously stirring until uniformly dispersed gel is obtained;
b) Placing the inner liner filled with the gel into a reaction kettle for sealing, and heating and synthesizing;
c) Centrifuging the material obtained by heating synthesis to obtain dry matter, washing the dry matter with deionized water for 3-5 times, and then carrying out ion exchange on the dry matter;
d) Calcining the solid material after ion exchange to obtain molecular sieve crystal powder serving as a carrier C;
2) Metal modification
Carrying out ion exchange on the carrier C obtained in the step 1) and the soluble salt solution of the modified element, and carrying out vacuum rotary evaporation after the ion exchange is sufficient to obtain a modified solid material;
and drying and roasting the modified solid material to obtain the ultra-wide temperature window SCR denitration catalyst.
Further, the stirring speed of the sodium hydroxide solution in the step a) is 100-150 r/min, and the stirring time is 20-30 min.
Further, the ratio of sodium hydroxide in the step a): template agent: na-Y molecular sieve: the mass ratio of the silicon source is 1: (4-12): (2-4): (20 to 80).
Further, the template agent in the step a) is organic amine salt or quaternary ammonium salt.
Further, the template agent in the step a) is 1,4-ditriethylenediamine butane bromide or 1,4-dibutyl dibromide.
Further, the stirring speed after the template agent is added in the step a) is 100-150 r/min, and the stirring time is 20-30 min.
Further, the silica-alumina ratio of the Na-Y molecular sieve in the step a) is 5-10.
Further, the stirring speed after the Na-Y molecular sieve is added in the step a) is 100-150 r/min, and the stirring time is 1-2 h.
Further, the silicon source in the step a) is sodium silicate, silica sol or ethyl orthosilicate.
Further, the stirring speed after the silicon source is added in the step a) is 200-300 r/min.
Further, the pressure in the reaction kettle in the step b) is 0.1MPa, and the stirring speed is 100-150 r/min. .
Further, the heating synthesis reaction temperature in the step b) is 130-160 ℃, and the reaction time is 6-8 days.
Further, the step c) is washed by deionized water until the pH value of the mother liquor is 7.
Further, said dry matter of said step C) is Na-C molecular sieve.
Further, the ion exchange of the step C) is to put the Na-C molecular sieve into 0.5-1 mol/L ammonium nitrate solution.
Further, the ion exchange reaction temperature of the step c) is 60-90 ℃, the stirring speed is 100-150 r/min, and the stirring time is 10-14 h.
Furthermore, the calcining temperature of the step d) is 500-600 ℃, and the calcining time is 7-9 h.
Further, the carrier C in the step d) is an H-C molecular sieve.
Further, the soluble salt of the modifying element in the step 2) is an inorganic salt or an organic salt, preferably an inorganic salt, and more preferably a nitrate.
Further, the mass ratio of the carrier to the soluble salt of the modifying element in the step 2) is 10: (3-6).
Further, the mass concentration of the soluble salt solution of the modifying element in the step 2) is 0.1-1%.
Further, the ion exchange temperature of the step 2) is 20-80 ℃, preferably 40-70 ℃, and more preferably 60 ℃.
Further, the ion exchange time of the step 2) is 3 to 9 hours, preferably 4 to 8 hours, and more preferably 7 hours.
Further, the stirring speed of the ion exchange reaction in the step 2) is 200-300/min.
Further, the vacuum rotary evaporation temperature of the step 2) is 40-90 ℃, preferably 50-70 ℃, and more preferably 60 ℃.
Further, the vacuum degree of the vacuum rotary evaporation in the step 2) is 0.6 to 1, preferably 0.8 to 1, and more preferably 0.9.
Further, the drying temperature of the step 2) is 60-80 ℃, and the drying time is 8-12 h.
Further, the roasting temperature of the step 2) is 500-600 ℃, and the roasting time is 4-8 h.
Further, the silicon-aluminum ratio of the denitration catalyst in the step 2) is 3 to 15, preferably 3 to 8, and more preferably 3 to 5.
The invention also provides application of the denitration catalyst, and the denitration catalyst is used for simulating SCR denitration reaction under the condition of flue gas, and NO is in a super wide temperature window range of 100-450 DEG C X The removal rate is optimally 100 percent, and the product N 2 The selectivity is optimally 100%.
The invention has the advantages of
1. According to the invention, a molecular sieve carrier is prepared in situ under the guidance of a template agent after mixing a Na-Y molecular sieve and a silicon source by using a crystal transformation synthesis method, the molecular sieve carrier is modified by the combination of any two elements or the combination of three elements of Cu, fe and Mn through an ion exchange method, the framework structure and the pore diameter of the SCR denitration catalyst are in a better state, the number of acid active sites is large, the loading rate of the modified elements is high, the utilization rate is close to 100%, the raw materials are cheap and easy to obtain, the preparation process is simple, no harm is caused to a human body and the environment, secondary pollution is avoided, and the SCR denitration catalyst has popularization value.
2. The SCR denitration catalyst has excellent catalytic activity and selectivity within an ultra-wide operating temperature window of 100-450 ℃, such as preferable Cu&Fe&Mn-SSZ-16 catalyst, NO at 100-450 deg.C X The conversion rate is 60.7-100%, N 2 The selectivity is 100%, the catalytic performance is obviously superior to that of the existing SCR denitration catalyst, and the catalyst has industrial application prospect.
3. The SCR denitration catalyst has high activity and few side reactions under the reaction condition of low temperature of 100-200 ℃, has high stability and difficult inactivation under the reaction condition of medium and high temperature of 250-450 ℃, has long service life and low operation cost, and is a novel SCR denitration catalyst with an ultra-wide temperature window.
Drawings
Figure 1 is a Temperature Programmed Desorption (TPD) spectrum of sample 1.
Figure 2 is a Temperature Programmed Desorption (TPD) spectrum of sample 2.
Figure 3 is a Temperature Programmed Desorption (TPD) spectrum of sample 3.
Figure 4 is a Temperature Programmed Desorption (TPD) profile of sample 4.
Fig. 5 is a Temperature Programmed Desorption (TPD) spectrum of sample 5.
Figure 6 is a Temperature Programmed Desorption (TPD) profile of sample 6.
Figure 7 is a Temperature Programmed Desorption (TPD) profile of sample 7.
Fig. 8 is a Temperature Programmed Desorption (TPD) profile of sample 8.
Fig. 9 is a Temperature Programmed Desorption (TPD) spectrum of sample 9.
Fig. 10 is a Temperature Programmed Desorption (TPD) spectrum of sample 10.
Fig. 11 is a Temperature Programmed Desorption (TPD) profile of comparative sample 1.
Fig. 12 is a Temperature Programmed Desorption (TPD) profile of comparative sample 2.
Fig. 13 is a Temperature Programmed Desorption (TPD) spectrum of comparative sample 3.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
SCR denitration catalyst sample 1 with ultra-wide temperature window
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring the mixture in a polytetrafluoroethylene lining of a reaction kettle for 30min at a stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after the stirring is stopped, continuously stirring the mixture for 30min at a stirring speed of 150r/min until the reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after the stirring is stopped, continuously stirring the mixture for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9 percent into the lining at a stirring speed of 200r/min, and continuously stirring the mixture until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is placed into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the mixture is synthesized for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and a starting temperature of room temperature, heating to 550 ℃, calcining for 8H, and naturally cooling to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5), 0.0525g of Cu (NO) 3 ) 2 ·3H 2 O, 0.2g Fe (NO) 3 ) 3 ·9H 2 O and 0.38g Mn (NO) 3 ) 2 ·4H 2 Dissolving O in an eggplant-shaped bottle filled with 100g of deionized water, and fully mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 deg.C for 6h, and performing vacuum rotary evaporation at 60 deg.C under vacuum degree of 0.9 to obtain modified solid material;
and drying the modified solid material in an oven at 80 ℃ for 8h, and calcining the dried solid material in a muffle furnace at 500 ℃ for 8h to obtain a sample 1.
The sample 1 is subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectral analysis result is shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in figure 1, and the Temperature Programmed Desorption (TPD) experimental spectrogram data analysis is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a sample 1 as the catalyst, and the method comprises the following steps: tabletting, crushing and grinding the sample 1 into particles of 40-60 meshes, weighing 0.2g of catalyst particles and filling the catalyst particles into a sealed tubular furnace; simulating NO: NH 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by gas chromatography on-line monitoring, and the analysis result is shown in tables 3 and 4.
Example 2
SCR denitration catalyst sample 2 with ultra-wide temperature window
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring in a polytetrafluoroethylene lining of a reaction kettle for 30min at the stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after stopping stirring, continuously stirring for 30min at the stirring speed of 150r/min until reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after stopping stirring, continuously stirring for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9% into the lining at the stirring speed of 200r/min, and continuously stirring until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is put into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the synthesis is carried out for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and a starting temperature of room temperature, heating to 550 ℃, calcining for 8H, and naturally cooling to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5), 0.105g of Cu (NO) 3 ) 2 ·3H 2 O, 0.1g Fe (NO) 3 ) 3 ·9H 2 O and 0.38g Mn (NO) 3 ) 2 ·4H 2 Dissolving O in an eggplant-shaped bottle filled with 100g of deionized water, and fully mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 deg.C for 6h, and performing vacuum rotary evaporation at 70 deg.C under vacuum degree of 0.8 to obtain modified solid material;
and drying the modified solid material in an oven at 80 ℃ for 8 hours, and calcining the dried solid material in a muffle furnace at 500 ℃ for 8 hours to obtain a sample 2.
The sample 2 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectroscopic analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in fig. 2, and the Temperature Programmed Desorption (TPD) spectrogram is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a sample 2 as the catalyst, and the method comprises the following steps: tabletting, crushing and grinding the sample 2 into particles of 40-60 meshes, and weighing 0.2g of catalyst particles to be filled into a sealed tubular furnace; simulating NO: NH (NH) 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by online monitoring of gas chromatography, and the analysis results are shown in tables 3 and 4.
Example 3
SCR denitration catalyst sample 3 with ultra-wide temperature window
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring in a polytetrafluoroethylene lining of a reaction kettle for 30min at the stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after stopping stirring, continuously stirring for 30min at the stirring speed of 150r/min until reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after stopping stirring, continuously stirring for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9% into the lining at the stirring speed of 200r/min, and continuously stirring until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is put into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the synthesis is carried out for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and an initial temperature of room temperature, heating the solid powder to 550 ℃, calcining the solid powder for 8 hours, and naturally cooling the solid powder to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5), 0.0525g of Cu (NO) 3 ) 2 ·3H 2 O, 0.1g Fe (NO) 3 ) 3 ·9H 2 O and 0.19g of Mn (NO) 3 ) 2 ·4H 2 Dissolving O in an eggplant-shaped bottle filled with 100g of deionized water, and fully mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 deg.C for 6h, and performing vacuum rotary evaporation at 50 deg.C under vacuum degree of 0.9 to obtain modified solid material;
and drying the modified solid material in an oven at 80 ℃ for 8h, and calcining the dried solid material in a muffle furnace at 500 ℃ for 8h to obtain a sample 3.
The sample 3 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectroscopic analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in fig. 3, and the Temperature Programmed Desorption (TPD) spectrogram is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a sample 3 as the catalyst, and the method comprises the following steps: tabletting, crushing and grinding the sample 3 into particles of 40-60 meshes, weighing 0.2g of catalyst particles and filling the catalyst particles into a sealed tube furnace; simulating NO: NH (NH) 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by online monitoring of gas chromatography, and the analysis results are shown in tables 3 and 4.
Example 4
SCR denitration catalyst sample 4 with ultra-wide temperature window
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring in a polytetrafluoroethylene lining of a reaction kettle for 30min at the stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after stopping stirring, continuously stirring for 30min at the stirring speed of 150r/min until reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after stopping stirring, continuously stirring for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9% into the lining at the stirring speed of 200r/min, and continuously stirring until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is put into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the synthesis is carried out for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and a starting temperature of room temperature, heating to 550 ℃, calcining for 8H, and naturally cooling to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5), 0.1312g of Cu (NO) 3 ) 2 ·3H 2 O and 0.2507g Fe (NO) 3 ) 3 ·9H 2 Dissolving O in an eggplant-shaped bottle filled with 100g of deionized water, and fully mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 ℃ for 6h, and performing vacuum rotary evaporation at 70 ℃ under the vacuum degree of 0.8 to obtain a modified solid material;
and drying the modified solid material in an oven at 80 ℃ for 8h, and calcining the dried solid material in a muffle furnace at 500 ℃ for 8h to obtain a sample 4.
The sample 4 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectroscopic analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in fig. 4, and the Temperature Programmed Desorption (TPD) spectrogram is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a sample 4 as the catalyst, and the method comprises the following steps: tabletting, crushing and grinding the sample 4 into particles of 40-60 meshes, weighing 0.2g of catalyst particles and filling the catalyst particles into a sealed tube furnace; simulating NO: NH (NH) 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by the online monitoring of the gas chromatography, and the analysis result is shown in the table 3 and the table 3.
Example 5
SCR denitration catalyst sample 5 with ultra-wide temperature window
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring in a polytetrafluoroethylene lining of a reaction kettle for 30min at the stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after stopping stirring, continuously stirring for 30min at the stirring speed of 150r/min until reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after stopping stirring, continuously stirring for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9% into the lining at the stirring speed of 200r/min, and continuously stirring until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is placed into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the mixture is synthesized for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and an initial temperature of room temperature, heating the solid powder to 550 ℃, calcining the solid powder for 8 hours, and naturally cooling the solid powder to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5), 0.1312g of Cu (NO) 3 ) 2 ·3H 2 O and 0.1586g Mn (NO) 3 ) 2 ·4H 2 Dissolving O in an eggplant-shaped bottle filled with 100g of deionized water, and fully mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 deg.C for 6h, and performing vacuum rotary evaporation at 70 deg.C under vacuum degree of 0.8 to obtain modified solid material;
and drying the modified solid material in an oven at 80 ℃ for 8h, and calcining the dried solid material in a muffle furnace at 500 ℃ for 8h to obtain a sample 5.
The sample 5 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectroscopic analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in fig. 5, and the Temperature Programmed Desorption (TPD) spectrogram is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a sample 5 as the catalyst, and the method comprises the following steps: tabletting, crushing and grinding the sample 5 into particles of 40-60 meshes, weighing 0.2g of catalyst particles and filling the catalyst particles into a sealed tube furnace; simulating NO: NH 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by online monitoring of gas chromatography, and the analysis results are shown in tables 3 and 4.
Example 6
SCR denitration catalyst sample 6 with ultra-wide temperature window
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring the mixture in a polytetrafluoroethylene lining of a reaction kettle for 30min at a stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after the stirring is stopped, continuously stirring the mixture for 30min at a stirring speed of 150r/min until the reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after the stirring is stopped, continuously stirring the mixture for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9 percent into the lining at a stirring speed of 200r/min, and continuously stirring the mixture until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is put into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the synthesis is carried out for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and an initial temperature of room temperature, heating the solid powder to 550 ℃, calcining the solid powder for 8 hours, and naturally cooling the solid powder to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5), 0.2507g of Fe (NO) 3 ) 3 ·9H 2 O and 0.1586g Mn (NO) 3 ) 2 ·4H 2 Dissolving O in an eggplant-shaped bottle filled with 100g of deionized water, and fully mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 ℃ for 6h, and performing vacuum rotary evaporation at 70 ℃ under the vacuum degree of 0.8 to obtain a modified solid material;
and drying the modified solid material in an oven at 80 ℃ for 8h, and calcining the dried solid material in a muffle furnace at 500 ℃ for 8h to obtain a sample 6.
The sample 6 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectroscopic analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in fig. 6, and the Temperature Programmed Desorption (TPD) spectrogram is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a sample 6 as the catalyst, and the method comprises the following steps: the sample 6 was tabletted,Crushing and grinding the mixture into particles of 40 to 60 meshes, and weighing 0.2g of catalyst particles and filling the catalyst particles into a sealed tubular furnace; simulating NO: NH (NH) 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by online monitoring of gas chromatography, and the analysis results are shown in tables 3 and 4.
Example 7
SCR denitration catalyst sample 7 with ultra-wide temperature window
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring in a polytetrafluoroethylene lining of a reaction kettle for 30min at the stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after stopping stirring, continuously stirring for 30min at the stirring speed of 150r/min until reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after stopping stirring, continuously stirring for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9% into the lining at the stirring speed of 200r/min, and continuously stirring until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is put into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the synthesis is carried out for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of a mother solution is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12 hours at the temperature of 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min and the pressure in the kettle of 0.1MPa, carrying out suction filtration washing for 5 times after the reaction is finished, and drying in an oven for 8 hours at the temperature of 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and an initial temperature of room temperature, heating the solid powder to 550 ℃, calcining the solid powder for 8 hours, and naturally cooling the solid powder to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5), 02507g of Fe 2 (SO 4 ) 3 And 0.1586g of MnSO 4 Dissolving in an eggplant-shaped bottle filled with 100g of deionized water, and mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 deg.C for 6h, and performing vacuum rotary evaporation at 70 deg.C under vacuum degree of 0.8 to obtain modified solid material;
the modified solid material was oven dried at 80 ℃ for 8 hours and calcined in a muffle furnace at 500 ℃ for 8 hours to obtain sample 7.
The sample 7 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectroscopic analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in fig. 7, and the Temperature Programmed Desorption (TPD) spectrogram is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a sample 7 as the catalyst, and the method comprises the following steps: tabletting, crushing and grinding the sample 7 into particles of 40-60 meshes, weighing 0.2g of catalyst particles and filling the catalyst particles into a sealed tube furnace; simulating NO: NH 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by the online monitoring of the gas chromatography, and the analysis results are shown in tables 3 and 4.
Example 8
SCR denitration catalyst sample 8 with ultra-wide temperature window
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring in a polytetrafluoroethylene lining of a reaction kettle for 30min at the stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after stopping stirring, continuously stirring for 30min at the stirring speed of 150r/min until reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after stopping stirring, continuously stirring for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9% into the lining at the stirring speed of 200r/min, and continuously stirring until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is put into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the synthesis is carried out for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and an initial temperature of room temperature, heating the solid powder to 550 ℃, calcining the solid powder for 8 hours, and naturally cooling the solid powder to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5), 0.0525g of CuSO 4 0.1g of Fe 2 (SO 4 ) 3 And 0.19g of MnSO 4 Dissolving in an eggplant-shaped bottle filled with 100g of deionized water, and mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 deg.C for 6h, and performing vacuum rotary evaporation at 50 deg.C under vacuum degree of 0.9 to obtain modified solid material;
and drying the modified solid material in an oven at 80 ℃ for 8h, and calcining the dried solid material in a muffle furnace at 500 ℃ for 8h to obtain a sample 8.
The sample 8 was analyzed for characterization, the inductively coupled plasma-atomic emission (ICP) spectroscopy results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrum is shown in fig. 8, and the Temperature Programmed Desorption (TPD) spectrum is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a sample 8 as the catalyst, and the method comprises the following steps: tabletting, crushing and grinding the sample 8 into particles of 40-60 meshes, and weighing 0.2g of catalyst particles to be filled into a sealed tubular furnace; simulating NO: NH (NH) 3 ：O 2 : the volume ratio of water vapor is 1 -1 At a reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃ and 300℃,The reaction is carried out at 350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by the online monitoring of the gas chromatography, and the analysis results are shown in tables 3 and 4.
Example 9
SCR denitration catalyst sample 9 with ultra-wide temperature window
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring in a polytetrafluoroethylene lining of a reaction kettle for 30min at the stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after stopping stirring, continuously stirring for 30min at the stirring speed of 150r/min until reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after stopping stirring, continuously stirring for 2h, adding 40g of sodium silicate solution with the mass concentration of 99.9% into the lining at the stirring speed of 200r/min, and continuously stirring until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is put into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the synthesis is carried out for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and an initial temperature of room temperature, heating the solid powder to 550 ℃, calcining the solid powder for 8 hours, and naturally cooling the solid powder to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =8;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 8), 0.0525g of CuSO 4 0.1g of Fe 2 (SO 4 ) 3 And 0.19g of MnSO 4 Dissolving in an eggplant-shaped bottle filled with 100g of deionized water, and mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 deg.C for 6h, and performing vacuum rotary evaporation at 50 deg.C under vacuum degree of 0.9 to obtain modified solid material;
the modified solid material was oven dried at 80 ℃ for 8 hours and then calcined in a muffle furnace at 500 ℃ for 8 hours to obtain sample 9.
The sample 9 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectroscopic analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in fig. 9, and the Temperature Programmed Desorption (TPD) spectrogram is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a sample 9 as a catalyst, and the method comprises the following steps: tabletting, crushing and grinding the sample 9 into particles of 40-60 meshes, and weighing 0.2g of catalyst particles to be filled into a sealed tubular furnace; simulating NO: NH 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by online monitoring of gas chromatography, and the analysis results are shown in tables 3 and 4.
Example 10
SCR denitration catalyst sample 10 with ultra-wide temperature window
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring the mixture in a polytetrafluoroethylene lining of a reaction kettle for 30min at a stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after the stirring is stopped, continuously stirring the mixture for 30min at a stirring speed of 150r/min until the reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after the stirring is stopped, continuously stirring the mixture for 2h, adding 10g of sodium silicate solution with the mass concentration of 99.9 percent into the lining at a stirring speed of 200r/min, and continuously stirring the mixture until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is put into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the synthesis is carried out for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and a starting temperature of room temperature, heating to 550 ℃, calcining for 8H, and naturally cooling to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =3.2;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 3.2), 0.0525g of CuSO 4 0.1g of Fe 2 (SO 4 ) 3 And 0.19g of MnSO 4 Dissolving in eggplant-shaped bottle filled with 100g deionized water, and mixing at 250r/min to obtain suspension;
stirring the suspension at 60 ℃ for 6h, and performing vacuum rotary evaporation at 80 ℃ under the vacuum degree of 0.9 to obtain a modified solid material;
and drying the modified solid material in an oven at 80 ℃ for 8h, and calcining the dried solid material in a muffle furnace at 500 ℃ for 8h to obtain a sample 10.
The sample 10 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectroscopic analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrum is shown in fig. 10, and the Temperature Programmed Desorption (TPD) spectral analysis is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a sample 10 as a catalyst, and the performance evaluation experiment comprises the following steps: tabletting, crushing and grinding the sample 10 into particles of 40-60 meshes, weighing 0.2g of catalyst particles and filling the catalyst particles into a sealed tube furnace; simulating NO: NH 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by online monitoring of gas chromatography, and the analysis results are shown in tables 3 and 4.
Comparative example 1
Ultra-wide temperature window SCR denitration catalyst comparison sample 1
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring in a polytetrafluoroethylene lining of a reaction kettle for 30min at the stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after stopping stirring, continuously stirring for 30min at the stirring speed of 150r/min until reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after stopping stirring, continuously stirring for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9% into the lining at the stirring speed of 200r/min, and continuously stirring until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is placed into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the mixture is synthesized for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and an initial temperature of room temperature, heating the solid powder to 550 ℃, calcining the solid powder for 8 hours, and naturally cooling the solid powder to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5) and 0.198g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in an eggplant-shaped bottle filled with 100g of deionized water, and fully mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 deg.C for 6h, and performing vacuum rotary evaporation at 50 deg.C under vacuum degree of 0.9 to obtain modified solid material;
the modified solid material was oven-dried at 80 ℃ for 8 hours and then calcined in a muffle furnace at 500 ℃ for 8 hours to obtain comparative sample 1.
The comparative sample 1 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectroscopic analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in fig. 11, and the Temperature Programmed Desorption (TPD) spectrogram is shown in table 2.
A comparative sample 1 is used as a catalyst, and a performance evaluation experiment of a simulated flue gas denitration catalyst is carried out, and the method comprises the following steps: tabletting, crushing and grinding the comparative sample 1 into particles of 40-60 meshes, weighing 0.2g of catalyst particles and filling the catalyst particles into a sealed tube furnace; simulating NO: NH (NH) 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by online monitoring of gas chromatography, and the analysis results are shown in tables 3 and 4.
Comparative example 2
Ultra-wide temperature window SCR denitration catalyst contrast sample 2
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring in a polytetrafluoroethylene lining of a reaction kettle for 30min at the stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after stopping stirring, continuously stirring for 30min at the stirring speed of 150r/min until reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after stopping stirring, continuously stirring for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9% into the lining at the stirring speed of 200r/min, and continuously stirring until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is put into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the synthesis is carried out for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and a starting temperature of room temperature, heating to 550 ℃, calcining for 8H, and naturally cooling to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5) and 0.332g of Fe (NO) 3 ) 3 ·9H 2 Dissolving O in an eggplant-shaped bottle filled with 100g of deionized water, and fully mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 deg.C for 6h, and performing vacuum rotary evaporation at 50 deg.C under vacuum degree of 0.9 to obtain modified solid material;
the modified solid material was oven-dried at 80 ℃ for 8 hours, and then calcined in a muffle furnace at 500 ℃ for 8 hours to obtain comparative sample 2.
The comparative sample 2 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission (ICP) spectroscopic analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in fig. 12, and the Temperature Programmed Desorption (TPD) spectrogram is shown in table 2.
A performance evaluation experiment of a simulated flue gas denitration catalyst is carried out by using a comparative sample 2 as a catalyst, and the method comprises the following steps: tabletting, crushing and grinding the comparative sample 2 into particles of 40-60 meshes, weighing 0.2g of catalyst particles and filling the catalyst particles into a sealed tube furnace; simulating NO: NH (NH) 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by the online monitoring of the gas chromatography, and the analysis results are shown in tables 3 and 4.
Comparative example 3
Ultra-wide temperature window SCR denitration catalyst contrast sample 3
1) Preparation of the support
a) Dissolving 0.5g of sodium hydroxide in 30mL of deionized water, stirring in a polytetrafluoroethylene lining of a reaction kettle for 30min at the stirring speed of 150r/min, adding 4.27g of 1,4-ditriethylenediamine butane bromide after stopping stirring, continuously stirring for 30min at the stirring speed of 150r/min until reactants are uniformly mixed, adding 1.5g of Na-Y (Si/Al = 5) after stopping stirring, continuously stirring for 2h, adding 20g of sodium silicate solution with the mass concentration of 99.9% into the lining at the stirring speed of 200r/min, and continuously stirring until uniformly dispersed gel is obtained;
b) The inner liner filled with the gel is put into a reaction kettle for sealing, the pressure in the kettle is 0.1MPa, the stirring speed is 120r/min, and the synthesis is carried out for 7 days at 150 ℃;
c) Carrying out centrifugal separation on the material obtained by heating synthesis to obtain a Na-SSZ-16 molecular sieve, washing the Na-SSZ-16 molecular sieve with deionized water until the pH value of mother liquor is 7, mixing the Na-SSZ-16 molecular sieve with 500mL of 0.5mol/L ammonium nitrate solution, carrying out sealed reaction for 12h at 80 ℃ in a reaction kettle, carrying out stirring at the rotating speed of 150r/min, carrying out suction filtration and washing for 5 times after the reaction is finished, and drying in an oven for 8h at 80 ℃ to obtain solid powder;
d) Placing the solid powder in a muffle furnace, setting a program for heating the muffle furnace at a heating rate of 5 ℃/min and a starting temperature of room temperature, heating to 550 ℃, calcining for 8H, and naturally cooling to obtain an H-SSZ-16 molecular sieve carrier, wherein Si/Al =5;
2) Metal modification
1g of H-SSZ-16 molecular sieve (Si/Al = 5) and 0.24g of Mn (NO) 3 ) 2 ·4H 2 Dissolving O in an eggplant-shaped bottle filled with 100g of deionized water, and fully mixing at 250r/min to obtain a suspension;
stirring the suspension at 60 deg.C for 6h, and performing vacuum rotary evaporation at 50 deg.C under vacuum degree of 0.9 to obtain modified solid material;
the modified solid material was oven-dried at 80 ℃ for 8 hours and then calcined in a muffle furnace at 500 ℃ for 8 hours to obtain comparative sample 3.
The comparative sample 3 was subjected to performance characterization analysis, the inductively coupled plasma-atomic emission spectroscopy (ICP) analysis results are shown in table 1, the Temperature Programmed Desorption (TPD) experimental spectrogram is shown in fig. 13, and the Temperature Programmed Desorption (TPD) spectrogram analysis is shown in table 2.
Performance evaluation of simulated flue gas denitration catalyst with comparative sample 3 as catalystThe test comprises the following steps: tabletting, crushing and grinding the comparative sample 3 into particles of 40-60 meshes, weighing 0.2g of catalyst particles and filling the catalyst particles into a sealed tube furnace; simulating NO: NH 3 ：O 2 : the volume ratio of water vapor is 1 -1 The reaction is carried out at the reactant temperature of 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃ and 450 ℃, the obtained product is analyzed by online monitoring of gas chromatography, and the analysis results are shown in tables 3 and 4.
TABLE 1 modified element content (ppm) by ICP measurement
Figure BDA0002150688320000201
Table 1 shows the content of the modifying element in the SCR denitration catalyst measured by ICP, and the total content of the modifying element is 6.027-7.390 ppm in samples 1, 2, 3, 8, 9 and 10, which are made of the combination of three elements, cu, fe and Mn; the total content of the modified elements of the samples 4, 5, 6 and 7 prepared by combining any two elements of Cu, fe and Mn is 5.531-5.851 ppm; the total content of the modified elements of the comparative samples 1, 2 and 3 prepared from any single element of Cu, fe and Mn is 5.234-5.435 ppm. The SCR denitration catalyst prepared by the combination of any two elements or the combination of three elements of Cu, fe and Mn has higher modified element loading than the SCR denitration catalyst prepared by any single element of Cu, fe and Mn, high raw material utilization rate and better catalyst activity.
TABLE 2 Peak area and acid number of TPD spectra
Figure BDA0002150688320000202
Figure BDA0002150688320000211
TABLE 3 NO of denitration catalyst X Conversion (%)
Figure BDA0002150688320000212
Figure BDA0002150688320000221
TABLE 4N of denitration catalyst 2 Selectivity (%)
Figure BDA0002150688320000222
Table 3 NO for denitration catalyst X The conversion rate and the denitration catalyst have high activity at a low temperature range of 100-200 ℃: NO of samples 1 to 10 at 100 deg.C X The conversion rate is 21.2-61.2%, NO of sample 1-sample 10 at 150 ℃ X The conversion rate is 30.5-80.3%, and NO of sample 1-sample 10 at 200 DEG C X The conversion rate is 40.7-100%.
As can be seen from table 3, the denitration catalyst has high reaction stability and is not easily deactivated at a medium-high temperature of 250 to 450 ℃: NO of samples 1 to 10 at 250 deg.C X The conversion rate is 50.8-100%, and NO of sample 1-sample 10 at 300 DEG C X The conversion rate is 60.2-100%, and NO of sample 1-sample 10 at 350 DEG C X The conversion rate is 70.3-100%, NO of sample 1-sample 10 at 400 deg.C X The conversion rate is 80.9-100%, and NO of sample 1-sample 10 at 450 DEG C X The conversion rates were all 100%. The denitration catalyst prepared by the invention has excellent catalytic activity within an ultra-wide operation temperature window of 100-450 ℃.
As can be seen from Table 3, the NO of samples 1 to 10 obtained by modifying the combination of any two or three of the elements Cu, fe and Mn X The conversion rate is obviously higher than that of NO of comparative samples 1 to 3 prepared by any single element of Cu, fe and Mn X And (4) conversion rate.
Table 4 is N of denitration catalyst 2 Selectivity, N of samples 1 to 10 at 100 ℃ 2 The selectivity is 81.2-100%, and the N of the samples 1-10 is at 150 DEG C 2 Selectivity is 83.4-100%, N of sample 1-sample 10 at 200 deg.C 2 The selectivity is 85.6-100%, and the N of the samples 1-10 at 250 DEG C 2 The selectivity is 89.7-100%, and the N of the sample 1-10 at 300 DEG C 2 The selectivity is 91.2-100%, and the N of the samples 1-10 at 350 DEG C 2 The selectivity is 93.5-100%, and the N of the samples 1-10 at 400 DEG C 2 Selectivity 91.2-100%, N of sample 1-sample 10 at 450 deg.C 2 The selectivity is 90.5-100%. As can be seen from Table 4, the modification of the N content in the samples 1 to 10, which are obtained by modifying the combination of any two or three of the elements Cu, fe and Mn 2 The selectivity is obviously higher than that of N of comparative samples 1 to 3 prepared by using any single element of Cu, fe and Mn 2 And (4) selectivity. The denitration catalyst prepared by the invention has excellent N within an ultra-wide operation temperature window of 100-450 DEG C 2 And (4) selectivity.
FIG. 1 is a Temperature Programmed Desorption (TPD) spectrum of samples 1-10 and comparative samples 1-3, and it can be seen from the analysis in Table 2 that the peak areas of samples 1-10 are 41382.340-44419.297, the acid amount is 2.836-2.986 ppm, the peak areas of comparative samples 1-3 are 41234.687-41918.234, the acid amount is 2.772-2.818 ppm, the peak areas and the acid amounts of samples 1-10 are all higher than those of comparative samples 1-3, which illustrates that the SCR denitration catalyst prepared from the combination of any two or three elements of the modified elements Cu, fe and Mn can react with NH to NH 3 The adsorption capacity of the SCR denitration catalyst is stronger, more acidic active sites are provided, the catalytic activity of the SCR denitration catalyst is higher, and the performance is better.
The template agent in the embodiment of the invention is 1,4-ditriethylenediamine butane bromide, and the preparation method comprises the following steps: mixing 20g of triethylene diamine and 20g of methanol, and placing the solution into a three-neck flask; 12.83g of 1,4-dibromobutane were mixed with 6.6g of methanol and the solution placed in a constant pressure separatory funnel; placing a reaction device in an ice bath, dropwise adding the 1,4-dibromobutane mixed solution into the triethylene diamine mixed solution at the speed of 5-10 drops/min under the condition of rapid stirring, and continuously stirring for 2 hours after dropwise adding; 100mL of diethyl ether was added to the mixed solution, and the mixture was further stirred for 12 hours, washed by suction filtration, and dried in a vacuum oven at 25 ℃ for 24 hours to obtain 1,4-ditriethylenediamine butane bromide. The template agent autonomously synthesized by the method has better performance than a commercial template agent, has better space structure guiding effect on the framework structure, the pore structure and the aperture of a molecular sieve carrier, and the prepared catalyst has better performance and higher activity.
All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.

Claims (6)

1. The SCR denitration catalyst with the ultra-wide temperature window is characterized by comprising a molecular sieve carrier and a modification element, wherein the modification element is a combination of three modification elements of Cu, fe and Mn, namely Cu & Fe & Mn-SSZ-16;
based on the mass of the molecular sieve carrier SSZ-16, the mass percentage of the modified element in the denitration catalyst is 5-10% based on the total mass of the modified element;
the mass ratio of the modified elements is Cu: fe: mn =1: fe: mn =2 or Cu: fe: 2, mn = 1;
the ultra-wide temperature window range means that the denitration catalyst has denitration activity at 100-450 ℃.
2. The preparation method of the ultra-wide temperature window SCR denitration catalyst as recited in claim 1, wherein the preparation method comprises the following steps:
1) Preparation of the support
a) Adding a sodium hydroxide solution into a polytetrafluoroethylene lining of a reaction kettle, uniformly stirring, adding a template after stirring is stopped, continuously stirring, adding a Na-Y molecular sieve after stirring is stopped, continuously stirring, adding a silicon source into the lining, and continuously stirring until uniformly dispersed gel is obtained;
b) Placing the liner filled with the gel into a reaction kettle for sealing, and heating and synthesizing;
c) Centrifuging the material obtained by heating synthesis to obtain dry matter, washing the dry matter with deionized water for 3-5 times, and then carrying out ion exchange on the dry matter;
d) Calcining the solid material after ion exchange to obtain molecular sieve crystal powder serving as a carrier C;
2) Metal modification
Carrying out ion exchange on the carrier C obtained in the step 1) and the soluble salt solution of the modified element, and carrying out vacuum rotary evaporation after the ion exchange is sufficient to obtain a modified solid material;
and drying and roasting the modified solid material to obtain the ultra-wide temperature window SCR denitration catalyst.
3. The method of claim 2, wherein the ratio of sodium hydroxide: template agent: na-Y molecular sieve: the mass ratio of the silicon source is 1: (4-12): (2-4): (20 to 80).
4. The method according to claim 3, wherein the mass ratio of the carrier to the soluble salt of the modifying element in step 2) is 10: (3-6).
5. The production method according to claim 4, wherein the SCR denitration catalyst of the step 2) has a silicon-aluminum ratio of 3 to 15.
6. The use of the SCR denitration catalyst prepared by the preparation method of claim 2 is characterized in that the SCR denitration catalyst is used for simulating SCR denitration reaction under flue gas conditions.
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