CN113477272A - Metal-doped MFI type molecular sieve catalyst, and preparation method and application thereof - Google Patents
Metal-doped MFI type molecular sieve catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 55
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
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- 239000011148 porous material Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 29
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- 239000011593 sulfur Substances 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 230000010718 Oxidation Activity Effects 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000003546 flue gas Substances 0.000 description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 17
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
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- 239000011572 manganese Substances 0.000 description 4
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Abstract
The invention provides a metal-doped MFI type molecular sieve catalyst, a preparation method and an application thereof, wherein the preparation method comprises the following steps: s1, performing ball milling on a silicon source and a metal source, and then adding alkali liquor to stir evenly to obtain sol; s2, crystallizing the sol at high temperature to obtain an intermediate product; and S3, washing the intermediate product to be neutral, performing suction filtration and separation, drying the solid product, and then performing high-temperature calcination to obtain the metal-doped MFI type molecular sieve catalyst. The invention utilizes the active metal of NO oxidation reaction as the active site to play the role of catalysis, utilizes the MFI type molecular sieve as the carrier, and utilizes the ball milling method to improve the doping amount of the active metal on the MFI type molecular sieve, so that the product has good NO catalytic oxidation activity and special effects of sulfur resistance and water resistance which are not possessed by common metal oxides.
Description
Technical Field
The invention relates to the technical field of flue gas catalytic denitration, and particularly relates to a metal-doped MFI type molecular sieve catalyst, and a preparation method and application thereof.
Background
Nitrogen oxides are typical atmospheric pollutants and are in various types, including NO and NO2、N2O3And the like, along with the rapid increase of the demand of industrial development on fossil fuels, the emission of nitrogen oxides is increasing day by day, which has great harm to human health and ecological environment, and the strengthening of the control of nitrogen oxide pollution is an important subject to be solved urgently in the air pollution control engineering.
The nitrogen oxides in the industrial flue gas are generated by NO and NO2In the form of initially emitted NOxThe NO accounts for about 95 percent, but the NO is difficult to dissolve in water, so that the wet absorption treatment mode can be used for the NOxThe removal effect of (a) is not significant. For the conventional industrial flue gas, the denitration technology mainly comprises various types such as reduction method (SCR and SNCR), liquid absorption method adsorption method, electron beam irradiation method and the like, and is promoted in engineering practiceThe method is widely applied to two typical technologies of SCR (selective catalytic reduction) and SNCR (selective non-catalytic reduction), and is respectively applied to flue gas denitration of a coal-fired power plant and flue gas denitration of a cement kiln. In recent years, the catalytic oxidation of NO (SCO) technology has attracted attention, and the NO in flue gas is converted into NO which is easily dissolved in water and can react with water by using a catalyst2Then absorbing with alkali liquor, and the technology can combine with the traditional wet desulphurization technology to realize SO2With NOxAnd (4) performing synergistic purification treatment.
At present, research is mainly devoted at home and abroad on the catalytic oxidation of NO by using supported catalysts such as activated carbon, molecular sieves, noble metals, transition metals and the like, wherein the noble metal catalysts and the transition metal catalysts have higher activity. In the prior art, a noble metal Pt-based catalyst has higher NO catalytic oxidation activity, but the preparation cost of the noble metal catalyst is obviously higher, so the industrial application and popularization of the noble metal catalyst are limited. The activated carbon also has certain NO catalytic oxidation efficiency, but the industrial application of the activated carbon is limited by the defects of NO high temperature resistance, unstable chemical properties and the like, and the molecular sieve and the transition metal catalyst have stable properties, high temperature resistance and cheap and easily available raw materials, so that the activated carbon is a research focus of NO catalytic oxidation in recent years. Therefore, how to utilize the molecular sieve as the catalyst to improve the denitration efficiency is a problem to be solved urgently at present.
Disclosure of Invention
In view of the above, the invention aims to overcome the defects of the prior art, and provides a metal-doped MFI type molecular sieve catalyst, and a preparation method and application thereof, so that the oxidation activity of NO is improved, and the catalyst has good sulfur resistance and water resistance, and is more beneficial to application under actual industrial conditions.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a metal-doped MFI type molecular sieve catalyst comprises the following steps:
s1, performing ball milling on a silicon source and a metal source, and then adding alkali liquor to stir evenly to obtain sol;
s2, crystallizing the sol at high temperature to obtain an intermediate product;
and S3, washing the intermediate product to be neutral, performing suction filtration and separation, drying the solid product, and then performing high-temperature calcination to obtain the metal-doped MFI type molecular sieve catalyst.
Optionally, in the above technical solution, the silicon source in step S1 includes one of ethyl silicate, fumed silica, and silica sol; the metal source comprises one of manganese, cobalt and chromium; the alkali liquor comprises one or more of sodium hydroxide solution, potassium hydroxide solution, tetrapropylammonium hydroxide solution and tetraethylammonium hydroxide solution.
Optionally, in the above technical scheme, the concentration of the alkali liquor is 1-3 mol/L.
Optionally, in the above technical solution, the ball milling in step S1 has a milling speed of 200-.
Optionally, in the above technical solution, the temperature of the high-temperature crystallization in step S2 is 80-200 ℃ and the time is 12-72 hours.
Optionally, in the above technical solution, in step S3, washing the intermediate product to be neutral, drying the solid product, and then performing high-temperature calcination, specifically includes: washing the mixture B to be neutral by using deionized water or ethanol as a solvent, then drying the solid product at 50-80 ℃ for 12-18h, and then calcining at the temperature rising rate of 1-5 ℃/min and the temperature of 400-700 ℃ for 0.5-6 h.
The second purpose of the invention is to provide a metal-doped MFI type molecular sieve catalyst, which is prepared by the preparation method of the metal-doped MFI type molecular sieve catalyst.
Optionally, in the above technical scheme, the metal-doped MFI-type molecular sieve catalyst includes 85-95% of silica, 3% -10% of MOx, and the balance of Na2O、K2O, wherein M is manganese, cobalt or chromium, and x ═ 2, 4/3 or 3/2.
Optionally, in the above technical solution, the diameter of the metal-doped MFI-type molecular sieve catalyst is 0.1-10 μm, the pore diameter is 0.1-2.0nm, and the specific surface area is 50-200m2/g。
Third object of the inventionThe method provides an application of the metal-doped MFI type molecular sieve catalyst, the metal-doped MFI type molecular sieve catalyst is used for NO oxidation, and O is utilized2Is oxidized with NO to convert it into NO2Absorbing with alkali solution for reuse.
Compared with the prior art, the metal-doped MFI type molecular sieve catalyst and the preparation method and application thereof provided by the invention have the following advantages:
(1) the invention utilizes the active metal of NO oxidation reaction as the active site to play the role of catalysis, utilizes the MFI type molecular sieve as the carrier, and utilizes the ball milling method to improve the doping amount of the active metal on the MFI type molecular sieve, so that the product has good oxidation activity and special effects of sulfur resistance and water resistance which are not possessed by common metal oxides.
(2) The metal-doped MFI type molecular sieve catalyst prepared by the invention is suitable for treating industrial flue gas containing nitrogen oxides and is subjected to steam and SO in the industrial flue gas2The adverse effects of impurity components are small, the concentration range of NOx treatment is wide, products are easy to recover, the original tail gas emission system is not required to be greatly modified in practical application, the operation is simple, the control is easy, the method accords with the actual national conditions of China, the popularization and the use are easy, and the application value is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, a brief description will be given below to the drawings required for the description of the embodiments or the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
Fig. 1 is a schematic flow chart of a preparation method of a metal-doped MFI-type molecular sieve catalyst according to an embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Referring to fig. 1, a preparation method of a metal-doped MFI type molecular sieve catalyst includes the following steps:
s1, performing ball milling on a silicon source and a metal source, and then adding alkali liquor to stir evenly to obtain sol;
s2, crystallizing the sol at high temperature to obtain an intermediate product;
and S3, washing the intermediate product to be neutral, performing suction filtration and separation, drying the solid product, and then performing high-temperature calcination to obtain the metal-doped MFI type molecular sieve catalyst.
The MFI molecular sieve is used as a frame structure, and a synthesis precursor is synthesized after being treated by a mechanical grinding method, so that the high-metal-doping-amount MFI type molecular sieve catalyst can be synthesized, is suitable for being applied to catalytic oxidation reaction of NO in waste gas in the chemical industry, has suitable micropores for limited catalytic oxidation of NO, has the capacity of chemically catalyzing and oxidizing NO by active metal, and provides conditions for subsequent treatment of flue gas.
Specifically, the silicon source in step S1 includes one of ethyl silicate, fumed silica, and silica sol; the metal source comprises one of manganese, cobalt and chromium; the alkali liquor comprises one or more of sodium hydroxide solution NaOH, potassium hydroxide solution KOH, tetrapropylammonium hydroxide solution TPAOH and tetraethylammonium hydroxide solution TEAOH.
Wherein the concentration of the alkali liquor is 1-3 mol/L.
In the step S1, a planetary ball mill is adopted for ball milling, the milling speed is 200-.
Specifically, the temperature of the high-temperature crystallization in the step S2 is 80-200 ℃, and the time is 12-72 h.
Specifically, step S3 is to wash the intermediate product to neutrality, perform suction filtration and separation, dry the solid product, and perform high-temperature calcination, specifically including: washing the mixture B to neutrality by using deionized water or ethanol as a solvent, drying the solid product at 50-80 ℃ for 12-18h after suction filtration, and calcining at the temperature rise rate of 1-5 ℃/min and the temperature of 400-700 ℃ for 0.5-6 h.
The reaction and diffusion performance of the catalyst can be improved and the comprehensive reaction performance of the catalyst can be improved by regulating the acid-base property of the molecular sieve, reducing the grain size of the molecular sieve by combination and synthesizing the metal-doped MFI type molecular sieve catalyst with a mesoporous structure.
The embodiment of the invention utilizes a ball milling method to improve the doping amount of active metal on the MFI type molecular sieve, so that the prepared metal-doped MFI type molecular sieve catalyst has good NO oxidation activity and special effects of sulfur resistance and water resistance which are not possessed by common metal oxides.
The second purpose of the invention is to provide a metal-doped MFI type molecular sieve catalyst, which is prepared by the preparation method of the metal-doped MFI type molecular sieve catalyst.
The metal-doped MFI type molecular sieve catalyst comprises 85-95% of silicon dioxide, 3-10% of MOx and the balance of Na2O、K2O, wherein M is manganese, cobalt or chromium, and x ═ 2, 4/3 or 3/2.
The metal-doped MFI type molecular sieve catalyst has a diameter of 0.1-10 μm, a pore diameter of 0.1-2.0nm as measured by nitrogen adsorption and desorption, and a specific surface area of 50-200m2/g。
The third purpose of the invention is to provide the application of the metal-doped MFI type molecular sieve catalyst, wherein the metal-doped MFI type molecular sieve catalyst is used for NO oxidation to generate NO2Alkali liquor is adopted for absorption, and the technology can be combined with the traditional wet desulphurization process to realize SO2With NOxAnd (4) performing synergistic purification treatment. The reaction temperature is 20-250 ℃, and O is utilized2Is oxidized with NO to convert it into NO2Absorbing with alkali solution for reuse.
Further, the volume fraction of NO in the flue gas is 100-1000ppm, SO2Is 200ppm by volume, O2The volume fraction of the catalyst is 10%, the metal-doped MFI type molecular sieve catalyst is used for oxidizing NO and is matched with subsequent alkali liquor absorption, and the removal rate of nitrogen oxide can reach 75-90%. The aim of high-efficiency denitration at low temperature is achieved, and the high denitration rate is ensuredAnd the effects of sulfur dioxide, oxygen and water vapor can be resisted.
It can be understood that the flue gas usually contains sulfur dioxide, which needs to be treated by a desulfurization device, otherwise the sulfur dioxide affects the catalytic performance; and then carrying out denitration treatment, wherein the temperature of the desulfurized tail gas is generally lower than 200 ℃, and if the catalyst needs to be denitrated at a temperature higher than 200 ℃, the temperature of the desulfurized flue gas also needs to be raised, which is not beneficial to industrialization and energy consumption reduction. The metal-doped MFI type molecular sieve catalyst can achieve excellent denitration effect in the presence of sulfur dioxide, and is combined with the subsequent traditional wet desulphurization process to realize SO2With NOxThe synergistic purification treatment is beneficial to industrial application.
Compared with the prior art for removing the nitrogen oxide by the wet method, the invention does not need to add reducing substances or other gas components (ammonia and alkanes), fully utilizes the oxygen in the flue gas, and effectively removes the nitrogen oxide through catalytic oxidation. In addition, the oxidized high-valence nitrogen oxide can well react with subsequent alkali liquor, and the obtained nitrite product can also be used as a preservative and an antifreezing agent, so that the aim of sustainable development of treating wastes with wastes is fulfilled, and the recycling and the effectiveness of waste treatment are realized.
The method is suitable for treating the industrial flue gas containing the nitrogen oxide, and the industrial flue gas is subjected to steam and SO2The adverse effect of impurity components is small, the concentration range of NOx treatment is wide, the original tail gas emission system does not need to be greatly modified in practical application, the operation is simple, the control is easy, the method accords with the actual national conditions of China, the popularization and the use are easy, and the application value is high.
On the basis of the above embodiment, the present invention provides the following specific examples of the preparation method and application of the metal-doped MFI type molecular sieve catalyst, and further illustrates the present invention. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
The embodiment provides a preparation method of a metal-doped MFI type molecular sieve catalyst, which comprises the following steps:
1) adding Mn2O3And gas phase silicon oxide mechanical grinding to obtain the manganese-silicon mixed oxide composite material, wherein the Mn/(Mn + Si) composition is 10 percent of Mn2O3The mixture with fumed silica was milled using a planetary ball mill (Fritsch P6) with a silicon nitride milling pot at 600 revolutions per minute.
2) Adding 5g of ball-milled solid into 50mL of mixed alkali liquor (NaOH, TPAOH and TEAOH) with the pH value of 10, stirring for 4h, adding the stirred sol into a 100mL reaction kettle, crystallizing at 200 ℃ for 12h, washing the obtained product to be neutral, performing suction filtration and separation, drying the obtained solid at 70 ℃ overnight, calcining the obtained solid at 500 ℃ for 24h to remove the template agent, and heating at the rate of 5 ℃/min to obtain the metal-doped MFI type molecular sieve catalyst # 1.
Example 2
The embodiment provides a preparation method of a metal-doped MFI type molecular sieve catalyst, which comprises the following steps:
1) adding Mn2O3And gas phase silicon oxide mechanical grinding to obtain the manganese-silicon mixed oxide composite material, wherein the Mn/(Mn + Si) composition is 20 percent of Mn2O3The mixture with fumed silica was milled using a planetary ball mill (Fritsch P6) with a silicon nitride milling pot at 600 revolutions per minute.
2) Adding 5g of ball-milled solid into 50mL of mixed alkali liquor (NaOH, TPAOH and TEAOH) with the pH value of 10, stirring for 4h, adding the stirred sol into a 100mL reaction kettle, crystallizing at 200 ℃ for 12h, washing the obtained product to be neutral, performing suction filtration and separation, drying the obtained solid at 70 ℃ overnight, calcining the obtained solid at 500 ℃ for 24h to remove the template agent, and heating at the rate of 5 ℃/min to obtain the metal-doped MFI type molecular sieve catalyst # 2.
Test example 1
And (3) activity test: testing by using a normal pressure fixed bed reactor0.05g of dry catalysts #1 and #2(40-60 mesh) were placed in the center of the reactor with the reaction gas consisting of 500ppm NO, 8% O2，N2Balance, total flow rate set to 300mL min-1. The reaction gas enters the reactor and is continuously measured by a flue gas analyzer.
Finally, the NO catalytic oxidation conversion rate of the #1 catalyst at 150 ℃ is 40% and the NO catalytic oxidation conversion rate of the #2 catalyst is 52%; the NO catalytic oxidation conversion rate of the #1 catalyst is 70% at 200 ℃, and the NO catalytic oxidation conversion rate of the #2 catalyst is 76%; the NO catalytic oxidation conversion rate of the #1 catalyst at 250 ℃ is 88 percent, and the NO catalytic oxidation conversion rate of the #2 catalyst is 92 percent.
Test example 2
And (3) water resistance test: using an atmospheric fixed bed reactor test, 0.05g of dry catalysts #1 and #2(40-60 mesh) were placed in the center of the reactor with the reaction gas consisting of 500ppm NO, 8% O2，10％H2O，N2Balance, total flow rate set to 300mL min-1. The reaction gas enters the reactor and is continuously measured by a flue gas analyzer.
Finally, the NO catalytic oxidation conversion rate of the #1 catalyst at 150 ℃ is 30%, and the NO catalytic oxidation conversion rate of the #2 catalyst is 32%; the NO catalytic oxidation conversion rate of the #1 catalyst is 65% at 200 ℃, and the NO catalytic oxidation conversion rate of the #2 catalyst is 70%; the NO catalytic oxidation conversion rate of the #1 catalyst at 250 ℃ is 83 percent, and the NO catalytic oxidation conversion rate of the #2 catalyst is 86 percent.
Test example 3
And (3) sulfur resistance test: using an atmospheric fixed bed reactor test, 0.05g of dry catalysts #1 and #2(40-60 mesh) were placed in the center of the reactor with the reaction gas consisting of 500ppm NO, 8% O2，200ppm SO2，N2Balance, total flow rate set to 300mL min-1. The reaction gas enters the reactor and is continuously measured by a flue gas analyzer.
Finally, the NO catalytic oxidation conversion rate of the #1 catalyst at 150 ℃ is 17% and the NO catalytic oxidation conversion rate of the #2 catalyst is 20%; the NO catalytic oxidation conversion rate of the #1 catalyst is 50% at 200 ℃, and the NO catalytic oxidation conversion rate of the #2 catalyst is 55%; the NO catalytic oxidation conversion rate of the #1 catalyst at 250 ℃ is 72 percent, and the NO catalytic oxidation conversion rate of the #2 catalyst is 77 percent.
The combination of the above test results shows that: the catalyst has high NOx removing rate and good sulfur and water resistance under the condition of simulating industrial waste gas at 250 ℃, does not need to greatly modify the original tail gas emission system in practical application, is simple to operate and easy to control, can recover products, accords with the actual national conditions of China, is easy to popularize and use, and has high application value.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of a metal-doped MFI type molecular sieve catalyst is characterized by comprising the following steps:
s1, performing ball milling on a silicon source and a metal source, and then adding alkali liquor to stir evenly to obtain sol;
s2, crystallizing the sol at high temperature to obtain an intermediate product;
and S3, washing the intermediate product to be neutral, performing suction filtration and separation, drying the solid product, and then performing high-temperature calcination to obtain the metal-doped MFI type molecular sieve catalyst.
2. The method according to claim 1, wherein the silicon source in step S1 includes one of ethyl silicate, fumed silica, and silica sol;
the metal source comprises one of manganese, cobalt and chromium;
the alkali liquor comprises one or more of sodium hydroxide solution, potassium hydroxide solution, tetrapropylammonium hydroxide solution and tetraethylammonium hydroxide solution.
3. The method according to claim 2, wherein the concentration of the alkali solution is 1 to 3 mol/L.
4. The method as claimed in any one of claims 1 to 3, wherein the ball milling speed of step S1 is 200-.
5. The method as claimed in claim 4, wherein the high temperature crystallization in step S2 is performed at 80-200 ℃ for 12-72 hours.
6. The preparation method according to claim 4, wherein the intermediate product is washed to be neutral, separated by suction filtration, dried to obtain a solid product, and then calcined at a high temperature in step S3, and specifically comprises:
washing the intermediate product to neutrality with deionized water or ethanol as solvent, suction filtering, drying the solid product at 50-80 deg.c for 12-18 hr, and calcining at 400-700 deg.c for 0.5-6 hr at 1-5 deg.c/min.
7. A metal-doped MFI-type molecular sieve catalyst, characterized by being prepared by the method of any of claims 1-6.
8. The metal-doped MFI-type molecular sieve catalyst of claim 7, wherein said metal-doped MFI-type molecular sieve catalyst comprises 85-95% silica, 3-10% MOxThe balance being Na2O、K2O, wherein M is manganese, cobalt or chromium, and x ═ 2, 4/3 or 3/2.
9. The metal-doped MFI-type molecular sieve catalyst of claim 7, wherein said metal-doped MFI-type molecular sieve catalyst has a diameter of 0.1-10 μm, a pore diameter of 0.1-2.0nm, and a specific surface area of 50-200m2/g。
10. The metal-doped MFI-type molecular sieve of any of claims 7-9The application of the catalyst is characterized in that the metal-doped MFI type molecular sieve catalyst is used for NO oxidation, and O is utilized2Is oxidized with NO to convert it into NO2Absorbing with alkali solution for reuse.
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