CN108479845B - Denitration catalyst and preparation method thereof - Google Patents

Denitration catalyst and preparation method thereof Download PDF

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CN108479845B
CN108479845B CN201810241864.0A CN201810241864A CN108479845B CN 108479845 B CN108479845 B CN 108479845B CN 201810241864 A CN201810241864 A CN 201810241864A CN 108479845 B CN108479845 B CN 108479845B
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molecular sieve
stirring
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denitration catalyst
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CN108479845A (en
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李惠林
邓国敢
沈勘力
李俊霞
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Zhejiang Zhiyuan Environmental Technology Co.,Ltd.
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/03Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333Iron group metals or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00Protection of catalysts, e.g. by coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/002Catalysts characterised by their physical properties
    • B01J35/0073Distribution of the active metal ingredient
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/209Other metals
    • B01D2255/2094Tin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/50Zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/18After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/18After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions

Abstract

The invention discloses a high-efficiency denitration catalyst and a preparation method thereof, wherein a hydrothermal method and a sol dipping method are adopted for combined treatment, a MCM-48 molecular sieve containing Sn in a framework is taken as a carrier, and a mixed solution B is obtained by mixing deionized water, sulfuric acid with the mass concentration of 98% and phosphoric acid with the mass concentration of 85wt% to carry out SO treatment on the MCM-48 molecular sieve containing Sn4 2‑And PO4 3‑And Fe is used as an active component. The denitration catalyst prepared by the invention has a high specific surface area, and can be 200-450%oHigh catalytic activity and SO resistance in the C range2Poisoning performance.

Description

Denitration catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysis, relates to a denitration catalyst, and particularly relates to a denitration catalyst and a preparation method thereof.
Background
In recent years, with the continuous and deep progress of industrialization and urbanization in China, the utilization of fossil energy and the consumption of resources are continuously increased, the situation of atmospheric pollution is further worsened, the regional atmospheric combined pollution is continuously aggravated, and the emission of multiple pollutants is in the top of the world. Among the numerous pollutants, Nitrogen Oxides (NO)x) Is one of the typical atmospheric pollutants in China, and a large amount of NO is discharged into the atmospherexCan lead to a series of air pollution problems, such asAcid rain formed by gas phase reaction, greenhouse effect caused by hydrocarbon, photochemical smog and haze generated by illumination, and the like; meanwhile, the method is dangerous to the health and ecological environment of human bodies, and further causes a series of urban and regional environmental problems.
Because the selective catalytic reduction technology has good catalytic activity, wide temperature range and low catalytic cost, NO discharged by a fixed source is eliminatedxThe SCR technology is mostly adopted. Currently commercially available V2O5-WO3(MoO3)/TiO2Although the catalyst is mature, the reaction temperature window is narrow, the activity at low temperature is poor, and N is easily generated at high temperature2O by-product and main active component V2O5Has the defects of biological toxicity and the like. Therefore, how to prepare an environmentally friendly denitration catalyst with good catalytic activity and a wide reaction temperature window becomes a hotspot of current research.
Disclosure of Invention
In order to solve the problems in the prior art, the invention discloses a denitration catalyst and a preparation method thereof, wherein an MCM-48 molecular sieve containing Sn in a framework is prepared as a carrier, and SO is carried out on the carrier4 2-And PO4 3-The catalyst has a high specific surface area, and can be in a range of 200-450oHigh catalytic activity and SO resistance in the C range2Poisoning performance.
The invention is realized by the following technologies:
on one hand, the invention discloses denitration catalysis, which takes MCM-48 molecular sieve containing Sn in a framework as a carrier and SO4 2-And PO4 3-Modifying, and taking iron as an active component.
On the other hand, the invention also discloses a preparation method of denitration catalysis, which adopts a hydrothermal method and a sol impregnation method for combined treatment, and is realized by the following steps:
(1) preparing MCM-48 molecular sieve carrier with framework containing element Sn
Dissolving silicon source in anhydrousAfter ethanol, stirring and mixing the ethanol, the template agent and the tin source for 30min, then adding KOH, continuously stirring for 20min, transferring the mixture to a hydrothermal reaction kettle, carrying out crystallization treatment at 150-180 ℃ for 24-36H, taking out the product, naturally cooling the product, and then placing the product in 30% H2O2Standing for 12 hr, vacuum filtering, washing to neutrality, treating at 60 deg.C for 12 hr, and treating at 550 deg.CoC, roasting for 5 hours to obtain a Sn modified MCM-48 molecular sieve carrier; wherein the template is CTAB; the Sn source is SnCl4The silicon source is TEOS;
(2) preparation of PO4 3--SO4 2-/Sn-MCM-48
Ultrasonically dispersing the MCM-48 molecular sieve carrier modified by Sn into deionized water to obtain a mixture A; mixing deionized water, sulfuric acid with the mass concentration of 98% and phosphoric acid with the mass concentration of 85wt% to obtain a mixed solution B, wherein the molar concentration of the sulfuric acid in the mixed solution B is 0.05 moL/L-0.3 moL/L, and the molar concentration of the phosphoric acid is 0.05 moL/L-0.15 moL/L; slowly injecting the mixed solution B into the mixture A through an injection pump under the condition of violent stirring, and transferring the mixed solution B into a hydrothermal reaction kettle for 120-150 ℃ after the mixed solution B is injectedoStanding for 6-8 h under the condition of C, slowly evaporating the obtained product in a 70 ℃ water bath until powder solid is obtained, roasting the obtained powder solid for 5h at 500 ℃ in air atmosphere, grinding and screening to obtain PO (phosphorus oxide) with 40-60 meshes4 3--SO4 2-/Sn-MCM-48;
(3) Active component Fe load
Dissolving ferric acetylacetonate in absolute ethyl alcohol to prepare 0.05-0.20 moL/L solution, adding polyvinyl alcohol with the molar mass of 9000-10000 into the solution, stirring the solution at room temperature for 2 hours to obtain sol, and adding the PO prepared in the step (2)4 3--SO4 2-and/Sn-MCM-48, stirring and concentrating for 4h in a water bath at 60 ℃, drying for 12h at 110 ℃, and finally treating for 5h in air at 500 ℃ to obtain the denitration catalyst.
Wherein, the stirring in the technical scheme refers to the stirring speed of 400-600 r/min.
As a preferred embodiment, in the step (1), the ratio of the amounts of the materials of the raw materials is: n isSiO2:nSnCl4:nKOH:nCTAB:nH2O:nEthanol=1.0:(0.1~0.3):0.24:(0.1~0.2):30:30。
As a preferred embodiment, in step (2), PO4 3-The mass ratio of the MCM-48 molecular sieve carrier modified by Sn to the mass of the carrier is 8-15%, and SO4 2-The mass ratio of the MCM-48 molecular sieve carrier modified by Sn is 10-30%.
As a preferred embodiment, in the step (3), the molar ratio of the polyvinyl alcohol to the ferric acetylacetonate is 1: 1.
Compared with the prior art, the invention has the advantages that:
(1) the denitration catalyst is prepared by combining a hydrothermal method and a sol impregnation method, so that the hydrothermal method is favorable for synthesizing the Sn modified MCM-48 molecular sieve carrier with the stable structure and is favorable for PO4 3-And SO4 2-The catalyst is uniformly dispersed in the inner pore channels and the surface of the carrier, so that the whole acidic sites of the catalyst are more uniformly dispersed; on the other hand, the active component Fe can be dispersed more uniformly on the surface of the catalyst by using a sol impregnation method, and the Fe and the SO4 2-Can form solid super acid which can effectively inhibit SO in the reaction process2And H2O is sulfated on the active component, so that the anti-poisoning performance of the active component is improved, and the synergistic effect between Fe and Sn can be enhanced, so that the integral catalytic effect is enhanced;
(2) SO in catalyst preparation process4 2-With SnO2Formation of solid superacid, PO4 3-Solid phosphoric acid can be formed between the solid phosphoric acid and MCM-48, and the formation of the solid super acid and the solid phosphoric acid can effectively inhibit SO while adjusting the surface acid strength of the solid super acid and the solid phosphoric acid2And H2Sulfation of the carrier caused by O, so that the overall anti-poisoning performance of the catalyst is improved;
(3) catalyst active component FeO2Has excellent oxidation-reduction performance and suitable acid strength phase of solid acidThe combination can enhance the reactivity and the stability of the catalyst, and in addition, a good oxidation-reduction cycle process can be formed between the valence states of +2 and +3 of Fe and the valence states of +2 and +4 of Sn in the reaction process to further enhance the reactivity;
(4) PO on the surface of the catalyst4 3-And SO4 2-Can be preferentially combined with toxic metal compounds to protect active components from being poisoned, thereby prolonging the service life of the catalyst.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
1) Preparing a Sn modified MCM-48 molecular sieve carrier:
the template agent used in the preparation process is CTAB; SnCl4As Sn source, TEOS as silicon source; according to the molar ratio nSiO2:nSnCl4:nKOH:nCTAB:nH2O:nEthanol=1.0:0.1:0.24:0.1:30:30, weighing a certain amount of TEOS, dissolving in ethanol aqueous solution, mixing with CTAB and SnCl4Mixing the water solution, stirring, adding potassium hydroxide after 30min, stirring for 20min, and finally placing the mixture into a hydrothermal reaction kettle at 150 deg.CoC crystallizing for 36H, taking out, cooling, and placing in 30% H2O2Standing for 12h, filtering, washing to neutrality, and standing at 60 deg.CoC treating for 12h, and finally 550oC, roasting for 5 hours to obtain a Sn modified MCM-48 molecular sieve carrier;
2) preparation of PO4 3--SO4 2-/Sn-MCM-48
Weighing 5gSn modified MCM-48 molecular sieve carrier, and ultrasonically dispersing the carrier into 200mL of deionized water to obtain a mixture A; mixing deionized water, sulfuric acid with the mass concentration of 98% and phosphoric acid with the mass concentration of 85wt% to obtain a mixed solution B of sulfuric acid with the molar concentration of 0.15moL/L and phosphoric acid with the molar concentration of 0.07 moL/L; under the condition of vigorous stirring, 100mL of mixed solution B is measuredSlowly injecting into mixture A via injection pump, transferring into hydrothermal reaction kettle at 120 deg.C after solution B is injectedoStanding for 8 hours under the condition of C, slowly evaporating the obtained product in a 70 ℃ water bath until powder solid is obtained, roasting the obtained solid for 5 hours at 500 ℃ in air atmosphere, and then grinding and screening to obtain PO with the mesh size of 40-604 3--SO4 2-/Sn-MCM-48;
3) Active component Fe load
Respectively measuring a certain amount of ferric acetylacetonate to dissolve in 100mL of ethanol solution to prepare 0.05moL/L solution, then adding 0.005moL of polyvinyl alcohol, and stirring at room temperature for 2h to obtain sol; then the prepared PO is4 3--SO4 2-Putting the/Sn-MCM-48 into the sol, stirring and concentrating for 4h in a water bath at 60 ℃, then drying for 12h at 110 ℃, and finally treating for 5h in air at 500 ℃ to obtain the No. 1 catalyst.
Example 2
1) Preparing a Sn modified MCM-48 molecular sieve carrier:
the template agent used in the preparation process is CTAB; SnCl4As Sn source, TEOS as silicon source; according to the molar ratio nSiO2:nSnCl4:nKOH:nCTAB:nH2O:nEthanol=1.0:0.3:0.24:0.2:30:30, weighing a certain amount of TEOS, dissolving in ethanol aqueous solution, mixing with CTAB and SnCl4Mixing the water solution, stirring, adding potassium hydroxide after 30min, stirring for 20min, and finally placing the mixture into a hydrothermal reaction kettle at 180 deg.CoC crystallization treatment is carried out for 24 hours, the product is taken out and cooled, and then the product is placed in 30 percent H2O2Standing for 12h, filtering, washing to neutrality, and standing at 60 deg.CoC treating for 12h, and finally 550oC, roasting for 5 hours to obtain a Sn modified MCM-48 molecular sieve carrier;
2) preparation of PO4 3--SO4 2-/Sn-MCM-48
Weighing 5gSn modified MCM-48 molecular sieve carrier, and ultrasonically dispersing the carrier into 200mL of deionized water to obtain a mixture A; deionized water and waterMixing sulfuric acid with the quantitative concentration of 98% and phosphoric acid with the mass concentration of 85wt% to obtain a mixed solution B of the sulfuric acid with the molar concentration of 0.2moL/L and the phosphoric acid with the molar concentration of 0.15 moL/L; under the condition of vigorous stirring, 30mL of mixed solution B is measured and slowly injected into the mixture A through a syringe pump, and after the injection of the solution B is finished, the mixture is transferred into a hydrothermal reaction kettle at 120 DEGoStanding for 8 hours under the condition of C, slowly evaporating the obtained product in a 70 ℃ water bath until powder solid is obtained, roasting the obtained solid for 5 hours at 500 ℃ in air atmosphere, and then grinding and screening to obtain PO with the mesh size of 40-604 3--SO4 2-/Sn-MCM-48;
3) Active component Fe load
Respectively measuring a certain amount of ferric acetylacetonate, dissolving the ferric acetylacetonate in 100mL of ethanol solution to prepare 0.20moL/L solution, adding polyvinyl alcohol with the molar mass of 9000-10000 into the solution, and stirring the solution at room temperature for 2 hours to obtain sol, wherein the molar ratio of the polyvinyl alcohol to the ferric acetylacetonate is 1: 1; then the prepared PO is4 3--SO4 2-Putting the/Sn-MCM-48 into the sol, stirring and concentrating for 4h in a water bath at 60 ℃, then drying for 12h at 110 ℃, and finally treating for 5h in air at 500 ℃ to obtain the 2# catalyst.
Example 3
1) Preparing a Sn modified MCM-48 molecular sieve carrier:
the template agent used in the preparation process is CTAB; SnCl4As Sn source, TEOS as silicon source; according to the molar ratio nSiO2:nSnCl4:nKOH:nCTAB:nH2O:nEthanol=1.0:0.2:0.24:0.15:30:30, weighing a certain amount of TEOS, dissolving in ethanol aqueous solution, mixing with CTAB and SnCl4Mixing the water solution, stirring, adding potassium hydroxide after 30min, stirring for 20min, and finally placing the mixture into a hydrothermal reaction kettle at 165 deg.CoC crystallizing for 30H, taking out, cooling, and placing in 30% H2O2Standing for 12h, filtering, washing to neutrality, and standing at 60 deg.CoC treating for 12h, and finally 550oRoasting the C for 5 hours to obtain Sn modified MCM-48 moleculesScreening the carrier;
2) preparation of PO4 3--SO4 2-/Sn-MCM-48
Weighing 5gSn modified MCM-48 molecular sieve carrier, and ultrasonically dispersing the carrier into 200mL of deionized water to obtain a mixture A; mixing deionized water, sulfuric acid with the mass concentration of 98% and phosphoric acid with the mass concentration of 85wt% to obtain a mixed solution B of sulfuric acid with the molar concentration of 0.3moL/L and phosphoric acid with the molar concentration of 0.15 moL/L; under the condition of vigorous stirring, measuring 35mL of mixed solution B, slowly injecting the mixed solution B into the mixture A through a syringe pump, and after the solution B is injected, transferring the mixture into a hydrothermal reaction kettle at 140 DEGoStanding for 7 hours under the condition of C, slowly evaporating the obtained product in a 70 ℃ water bath until powder solid is obtained, roasting the obtained solid for 5 hours at 500 ℃ in air atmosphere, and then grinding and screening to obtain PO with the mesh size of 40-604 3--SO4 2-/Sn-MCM-48;
3) Active component Fe load
Respectively measuring a certain amount of ferric acetylacetonate, dissolving the ferric acetylacetonate in 100mL of ethanol solution to prepare 0.15moL/L solution, adding polyvinyl alcohol with the molar mass of 9000-10000 into the solution, and stirring the solution at room temperature for 2 hours to obtain sol, wherein the molar ratio of the polyvinyl alcohol to the ferric acetylacetonate is 1: 1; then the prepared PO is4 3--SO4 2-Putting the/Sn-MCM-48 into the sol, stirring and concentrating for 4h in a water bath at 60 ℃, then drying for 12h at 110 ℃, and finally treating for 5h in air at 500 ℃ to obtain the 3# catalyst.
Example 4
1) Preparing a Sn modified MCM-48 molecular sieve carrier:
the preparation procedure is the same as example 1;
2) preparation of PO4 3-/Sn-MCM-48
Weighing 5gSn modified MCM-48 molecular sieve carrier, and ultrasonically dispersing the carrier into 200mL of deionized water to obtain a mixture A; mixing deionized water and 85wt% phosphoric acid to obtain a phosphoric acid solution B with a molar concentration of 0.07 moL/L; under the condition of vigorous stirring, 100mL of the mixed solution B is measured and injectedInjecting the mixture into the mixture A slowly by a jet pump, transferring the mixture into a hydrothermal reaction kettle at 120 ℃ after the solution B is injectedoStanding for 8 hours under the condition of C, slowly evaporating the obtained product in a 70 ℃ water bath until powder solid is obtained, roasting the obtained solid for 5 hours at 500 ℃ in air atmosphere, and then grinding and screening to obtain PO with the mesh size of 40-604 3/Sn-MCM-48;
3) Active component Fe load
Respectively measuring a certain amount of ferric acetylacetonate to dissolve in 100mL of ethanol solution to prepare 0.05moL/L solution, then adding 0.005moL of polyvinyl alcohol, and stirring at room temperature for 2h to obtain sol; then the prepared PO is4 3-Putting the/Sn-MCM-48 into the sol, stirring and concentrating for 4h in a water bath at 60 ℃, then drying for 12h at 110 ℃, and finally treating for 5h in air at 500 ℃ to obtain the 4# catalyst.
Example 5
1) Preparing a Sn modified MCM-48 molecular sieve carrier:
the preparation procedure is the same as example 1;
2) preparation of SO4 2-/Sn-MCM-48
Weighing 5gSn modified MCM-48 molecular sieve carrier, and ultrasonically dispersing the carrier into 200mL of deionized water to obtain a mixture A; mixing deionized water and sulfuric acid with the mass concentration of 98% to obtain a sulfuric acid solution B with the molar concentration of 0.15moL L/L; under the condition of vigorous stirring, 100mL of mixed solution B is measured and slowly injected into the mixture A through a syringe pump, and after the injection of the solution B is finished, the mixture is transferred into a hydrothermal reaction kettle at 120 DEGoStanding for 8 hours under the condition of C, slowly evaporating the obtained product in a 70 ℃ water bath until powder solid is obtained, roasting the obtained solid for 5 hours at 500 ℃ in air atmosphere, and then grinding and screening to obtain 40-60-mesh SO4 2-/Sn-MCM-48;
3) Active component Fe load
Respectively measuring a certain amount of ferric acetylacetonate to be dissolved in 100mL of ethanol solution to prepare 0.05moL/L solution, then adding 0.005moL of polyvinyl alcohol, and at room temperatureStirring for 2h to obtain sol; then the prepared SO4 2-Putting the/Sn-MCM-48 into the sol, stirring and concentrating for 4h in a water bath at 60 ℃, then drying for 12h at 110 ℃, and finally treating for 5h in air at 500 ℃ to obtain the 5# catalyst.
The performance test of the catalyst obtained in the above examples 1 to 5 was carried out in a fixed bed reactor, and the simulated flue gas composition was: 600ppmNH3,600ppm NO,5% O2, N2For balance gas, the total flow is 600mL/min, and the reaction space velocity is 50,000h-1The reaction temperature is 150-450 ℃, and NO in the reaction product2The content was analyzed and determined by a smoke analyzer KM9106, and the specific test results are shown in Table 1.1 below.
TABLE 1.1
Example 6
The catalyst # 1 prepared in example 1 was examined for SO on a fixed bed reactor2And H2The effect of O on catalytic activity. The composition of the reaction mixture gas is [ NH ]3]=[NO]=600ppm,[O2]=5%,[SO2]=200ppm,[H2O]=10vol%,N2The reaction space velocity is 50,000h for the balance gas-1Reaction temperature of 300 deg.CoC. The experimental results show that: while introducing SO2And H2After O12 h, NOxThe conversion rate of the catalyst is slightly reduced by 2-5%, the catalyst is still maintained at more than 94%, the catalyst is basically kept stable within 120 hours of experimental investigation, and when SO is generated2And H2NO with catalytic activity substantially restored to 99% after O removalxAnd (4) conversion rate.
Example 7
The No. 1 catalyst prepared in the example 1 is loaded with lead nitrate in the catalyst by an impregnation method, the loading amount of PbO is 7.45wt% after roasting for 5h at 400 ℃, and the activity of the catalyst is tested, wherein the reaction temperature of the catalyst is 250-400 ℃, and the reaction space velocity of the catalyst is 50,000h-1Under the condition (2), the denitration efficiency is stabilized to be more than 90%.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (3)

1. A denitration catalyst is characterized in that: MCM-48 molecular sieve with Sn in the skeleton as carrier and SO4 2-And PO4 3-Modifying, and taking iron as an active component;
the denitration catalyst is realized by the following steps:
(1) preparing MCM-48 molecular sieve carrier with framework containing element Sn
Dissolving a silicon source in absolute ethyl alcohol, stirring and mixing the silicon source, a template agent and a tin source for 30min, adding KOH, continuously stirring for 20min, transferring the mixture to a hydrothermal reaction kettle, carrying out crystallization treatment at 150-180 ℃ for 24-36H, taking out, naturally cooling, and then placing the mixture in 30% H2O2Standing for 12 hr, vacuum filtering, washing to neutrality, treating at 60 deg.C for 12 hr, and treating at 550 deg.CoC, roasting for 5 hours to obtain a Sn modified MCM-48 molecular sieve carrier; wherein the template is CTAB; the Sn source is SnCl4The silicon source is TEOS; wherein the mass ratio of each raw material is as follows: n isSiO2:nSnCl4:nKOH:nCTAB:nH2O:nEthanol=1.0:(0.1~0.3):0.24:(0.1~0.2):30:30;
(2) Preparation of PO4 3--SO4 2-/Sn-MCM-48
Ultrasonically dispersing the MCM-48 molecular sieve carrier modified by Sn into deionized water to obtain a mixture A; mixing deionized water, sulfuric acid with the mass concentration of 98% and phosphoric acid with the mass concentration of 85wt% to obtain a mixed solution B, wherein the molar concentration of the sulfuric acid in the mixed solution B is 0.05 mol/L-0.3moL/L, wherein the molar concentration of phosphoric acid is 0.05 moL/L-0.15 moL/L; slowly injecting the mixed solution B into the mixture A through an injection pump under the condition of violent stirring, and transferring the mixed solution B into a hydrothermal reaction kettle for 120-150 ℃ after the mixed solution B is injectedoStanding for 6-8 h under the condition of C, slowly evaporating the obtained product in a 70 ℃ water bath until powder solid is obtained, roasting the obtained powder solid for 5h at 500 ℃ in air atmosphere, grinding and screening to obtain PO (phosphorus oxide) with 40-60 meshes4 3--SO4 2-/Sn-MCM-48;
(3) Active component Fe load
Dissolving ferric acetylacetonate in absolute ethyl alcohol to prepare 0.05-0.20 moL/L solution, adding polyvinyl alcohol with the molar mass of 9000-10000 into the solution, stirring the solution at room temperature for 2 hours to obtain sol, and adding the PO prepared in the step (2)4 3--SO4 2-and/Sn-MCM-48, stirring and concentrating for 4h in a water bath at 60 ℃, drying for 12h at 110 ℃, and finally treating for 5h in air at 500 ℃ to obtain the denitration catalyst.
2. The denitration catalyst as set forth in claim 1, wherein: PO in step (2)4 3-The mass ratio of the MCM-48 molecular sieve carrier modified by Sn to the mass of the carrier is 8-15%, and SO4 2-The mass ratio of the MCM-48 molecular sieve carrier modified by Sn is 10-30%.
3. The denitration catalyst as set forth in claim 1, wherein: in the step (3), the molar ratio of the polyvinyl alcohol to the ferric acetylacetonate is 1: 1.
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