CN116273027B - Sulfur-resistant flue gas ozone decomposition catalyst and preparation method and application thereof - Google Patents
Sulfur-resistant flue gas ozone decomposition catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 50
- 239000011593 sulfur Substances 0.000 title claims abstract description 50
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003546 flue gas Substances 0.000 title claims abstract description 38
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 39
- 239000013543 active substance Substances 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 23
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 23
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000003723 Smelting Methods 0.000 claims abstract description 6
- 239000004568 cement Substances 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 5
- 229920000570 polyether Polymers 0.000 claims abstract description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 17
- 238000005949 ozonolysis reaction Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 230000005764 inhibitory process Effects 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 10
- 230000002401 inhibitory effect Effects 0.000 abstract description 7
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 5
- 231100000572 poisoning Toxicity 0.000 abstract description 5
- 230000000607 poisoning effect Effects 0.000 abstract description 5
- 239000011449 brick Substances 0.000 abstract description 4
- -1 polyethylene Polymers 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 229920001155 polypropylene Polymers 0.000 abstract description 3
- 229920000428 triblock copolymer Polymers 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 230000006872 improvement Effects 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/66—Ozone
-
- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Biomedical Technology (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses an anti-sulfur type flue gas ozone decomposition catalyst and a preparation method and application thereof, and belongs to the field of atmospheric treatment. The preparation method comprises the following raw materials: the catalyst comprises an aluminum-based carrier, active carbon, a rare earth component, an active agent, an active auxiliary agent and a sulfur-inhibiting auxiliary agent, wherein the active agent is ferric sulfate and nickel sulfate, the rare earth component is lanthanum, cerium and praseodymium, the active auxiliary agent is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (polyether P123), and the sulfur-inhibiting auxiliary agent is ammonium persulfate. The preparation method comprises the following steps: preparing raw materials into catalyst raw slurry according to certain weight parts; washing, filtering and drying the catalyst primary pulp, and firing to obtain the flue gas ozone decomposition catalyst with sulfur resistance. The catalyst has the advantages of excellent long-time ozone catalytic decomposition activity, sulfur poisoning resistance, simple and easily obtained preparation and the like, and can be applied to the ozone treatment of sulfur-containing flue gas in metal smelting, glass, cement and brick industries.
Description
Technical Field
The invention discloses an anti-sulfur type flue gas ozone decomposition catalyst and a preparation method and application thereof, and belongs to the field of atmospheric treatment.
Background
In the past, the emission of a large amount of primary ozone pollutants was monitored from the fume emission ports of the metal smelting, glass, cement, brick and tile manufacturing industries. Ozone (O) of more than 40 smoke discharge ports monitored 3 ) The average concentration value is about 35500 mug/m 3 95% fraction number value is about 122000 [ mu ] g/m 3 . The smoke ozone has direct influence on the ozone observation data of the national control points around the factory, the emission of the smoke ozone is highly concerned by the government, and the environmental protection department and industrial enterprises are urgent to realize emission reduction treatment on the smoke ozone. The ozone decomposition method comprises the following steps: the catalytic decomposition method has the characteristics of small energy consumption, small waste liquid yield and the like, meets the requirements of high-efficiency ozone decomposition, safety, economy and the like, and is a common technical means for controlling ozone at present.
Noble metal ozonolysis catalysts, e.g. Ag-, pd-and Au-catalysts, having a higher O 3 The decomposition efficiency, but the expensive price of the noble metal, limits the application thereof in industry. The transition metal oxide has the characteristics of higher redox activity, valence state variability, better stability and the like, and the development of the transition metal oxide ozonolysis catalyst can obviously reduce the industrial application cost and is O in recent years 3 The research in the field of catalytic decomposition is focused. Manganese (Mn) metal oxides are the most widely studied and used class of ozonolysis catalysts, including supported (MnOx/AC, co-Mn/Al 2 O 3 Etc.), single manganese oxide (alpha-MnO x ) Composite metal mold (Ce-OMS, etc.), and the like. However, such catalysts are currently used for ozone decomposition of indoor air and are adaptable to high humidity environments. However, for industrial flue gas such as metal smelting, glass, cement, bricks, tiles and the like, the flue gas is subjected to desulfurization treatment before being discharged, but the discharge port still has 10-100 mg/m 3 SO of (2) 2 Residue. Experiments in practical flue gas systems have found that most of the manganese metal oxide catalysts sold on the market are difficult to decompose ozone in the flue gas environment and the catalysts hardly function. It was also found in laboratory simulation systems that the composition contained 40 mg/m compared to the high humidity environment alone 3 SO 2 Is the flue gas humidity of (2)In the environment, the ozone removal efficiency of the manganese metal oxide catalyst is obviously reduced, and the poisoning phenomenon of rapid catalyst deactivation occurs. This illustrates SO 2 Even if meeting the ultra-low emission requirement of flue gas (35 mg/m) 3 ) Discharged SO 2 Poisoning deactivation of the Mn-based ozonolysis catalyst may still result. The reason that the manganese metal oxide catalyst is not sulfur-resistant is that the manganese metal oxide catalyst is extremely easy to adsorb SO at low-temperature flue gas (< 100 ℃) 2 ，SO 2 Fast binding to the catalytically active sites of the oxides of manganese eventually leads to deactivation of the ozonolysis catalyst.
Aiming at the problems, a novel catalyst needs to be developed to replace active metal Mn, so that the catalyst can efficiently catalyze and decompose ozone in sulfur-containing flue gas for a long time, and the urgent hope of governments and enterprises on emission reduction and treatment of the flue gas ozone is met.
Disclosure of Invention
The invention aims to provide a sulfur-resistant flue gas ozone decomposition catalyst and a preparation method and application thereof, so as to solve the problems in the background technology.
In order to achieve the above object, in one aspect, the present invention provides a sulfur-resistant flue gas ozone decomposition catalyst, which comprises the following raw materials in parts by weight: 25-41 parts by weight of an aluminum-based carrier, 10-23 parts by weight of activated carbon, 5-11 parts by weight of an active agent, 2-6 parts by weight of a rare earth component, 2-6 parts by weight of an active auxiliary agent and 1-4 parts by weight of a sulfur-inhibiting auxiliary agent, wherein,
the active auxiliary agent is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (polyether P123); the sulfur inhibition auxiliary agent is ammonium persulfate.
As a further improvement of the technical scheme, the aluminum-based carrier comprises alpha-alumina and gamma-alumina, and the weight ratio of the alpha-alumina to the gamma-alumina is 1-3:6-9.
As a further improvement of the technical scheme, the active agent comprises nickel sulfate and ferric sulfate, and the weight ratio of the nickel sulfate to the ferric sulfate is 1-2:4-5.
As a further improvement of the technical scheme, the rare earth component comprises lanthanum, cerium and praseodymium, and the weight ratio of the lanthanum, the cerium and the praseodymium is 1.0-1.2:1-1.3:0.7-0.8.
On the other hand, the invention also provides a preparation method for preparing the sulfur-resistant flue gas ozone decomposition catalyst, which comprises the following steps:
s1, adding an aluminum-based carrier and active carbon into a stirring container, adding deionized water, primarily stirring uniformly, adding a rare earth component, and stirring again to generate carrier liquid;
s2, mixing the active agent and the active auxiliary agent, adding enough deionized water, mixing and stirring to generate an active liquid;
s3, fully and uniformly mixing the active liquid, the carrier liquid and the sulfur inhibition auxiliary agent to generate catalytic primary pulp;
s4, washing, filtering and drying the catalyst raw slurry, and calcining to generate catalyst powder.
As a further improvement of the technical scheme, in the S1, the ratio of the weight of the added deionized water to the total weight of the aluminum-based carrier and the activated carbon is 1.5-3.2.
As a further improvement of the technical scheme, in the S2, the stirring time period when the active agent and the active auxiliary agent are mixed is 2-6h.
As a further improvement of the technical scheme, in the step S3, the full mixing time is 3-9h.
As a further improvement of the technical scheme, in the S4, the drying temperature is 80-110 ℃, the calcination is specifically carried out by heating to the target calcination temperature at the heating rate of 2-10 ℃/min, and the calcination is carried out for 3-5 h in the nitrogen atmosphere at the calcination temperature of 300-500 ℃.
It is a further object of the present invention to provide the use of the above sulfur-resistant flue gas ozone decomposition catalyst, which can be applied to sulfur-containing flue gas ozone treatment in metal smelting, glass, cement, tile industries.
A method of decomposing ozone by a sulfur-resistant flue gas ozone decomposition catalyst comprising the steps of:
placing the catalyst in the environment of smoke and ozone, the temperature is 60-80 ℃ and the airspeed is 0-30000 h -1 。
Compared with the prior art, the invention has the following advantages:
the aluminum-based carrier comprises alpha-alumina and gamma-alumina, wherein the alpha-alumina can be used as a filler of an ozonolysis catalyst, the gamma-alumina has a mesoporous structure, the specific surface area is large, the gamma-alumina can be converted into the alpha-alumina to be used as the filler during high-temperature calcination, and the loss of the material is reduced. The aluminum-based carrier plays a key role in the aspects of component mixing uniformity, oxygen storage capacity and redox in the catalyst synthesis process. The rare earth component has certain sulfur poisoning resistance, can interact with an aluminum-based carrier to cause shrinkage and distortion of a catalyst crystal lattice, promotes formation of oxygen vacancies and improves ozone decomposition efficiency.
Because the activated carbon can adsorb SO in the flue gas 2 、O 2 And steam, through reaction to produce H 2 SO 4 Is absorbed in the micropores of the active carbon, thereby achieving the desulfurization effect. The addition of the activated carbon serves as a sacrificial site, and the introduction of the sacrificial site can promote the reaction of sulfur and the sacrificial site, so that the activity of the ozonolysis active site is maintained, and the catalyst still maintains higher ozonolysis activity in the sulfur-containing atmosphere.
The active agent is nickel sulfate and ferric sulfate, and in the preparation process of the catalyst, the interaction of the two metals of iron and nickel forms rich oxygen vacancies and stronger redox. The oxygen vacancies are enriched and the stronger redox property is conducive to the catalytic decomposition of ozone. The active auxiliary agent is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (polyether P123), and the polyether P123 can provide-OH and is dispersed in the catalyst pore canal. Gaseous O 3 The molecule will react with two-OH groups to form one O 2 Molecule and one H 2 And O molecules. Two adsorbed H 2 The O molecules react to form O 2 The molecules are reduced to four-OH groups, and the catalyst is regenerated to have the capability of resisting the moisture of the flue gas. Nickel sulfate and ferric sulfate precursors can provide SO 4 2- Ion, adding sulfur-inhibiting auxiliary agent ammonium peroxodisulfate to promote more SO in the system 4 2- Ion generation, catalyst sulfation treatment, high sulfur resistance of catalyst, and SO 4 2- Can promote livingThe sexual metal oxide is highly dispersed on the surface of the carrier, promotes the generation of oxygen vacancies and achieves the purposes of enhancing activity and sulfur resistance.
The flue gas ozone decomposition catalyst has high sulfur resistance, and can be applied to ozone treatment of sulfur-containing flue gas discharged by metal smelting, glass, cement, brick and tile industries and the like.
The catalyst has the advantages of excellent long-time ozone catalytic decomposition activity, sulfur poisoning resistance, simple and easily obtained preparation and the like, plays a positive role in preventing and controlling ozone pollution of one-time emission, and is suitable for popularization and use.
Drawings
FIG. 1 is a flow chart of the catalyst preparation of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, the embodiment of the invention provides a method for preparing the sulfur-resistant flue gas ozone decomposition catalyst, which comprises the following specific steps:
s1, adding 25-41 parts by weight of an aluminum-based carrier and 10-23 parts by weight of activated carbon into a stirring container, adding deionized water, primarily stirring uniformly, adding 2-6 parts by weight of rare earth components, and stirring again to generate carrier liquid, wherein the ratio of the weight of the added deionized water to the total weight of the aluminum-based carrier and the activated carbon is 1.5-3.2, and adding a proper amount of deionized water so as to generate uniform carrier liquid when the rare earth components are added subsequently;
s2, mixing and stirring 5-11 parts by weight of active agent and 2-6 parts by weight of active auxiliary agent, and adding enough deionized water for mixing and stirring to generate active liquid. Wherein, the stirring time period when the active agent and the active auxiliary agent are mixed is 2-6h, and the long-time stirring is beneficial to the premixing of the active agent and the active auxiliary agent;
s3, fully and uniformly mixing the active liquid, the carrier liquid and 1-4 parts by weight of sulfur inhibition auxiliary agent to generate catalytic primary pulp. Wherein, the time of full mixing is 3-9h;
s4, washing with deionized water, filtering, drying the catalyst primary pulp at the temperature of 80-110 ℃, specifically heating to the target calcination temperature at the heating rate of 2-10 ℃/min, and roasting for 3-5 h in nitrogen atmosphere at the calcination temperature of 300-500 ℃ to produce catalyst powder.
The present invention will be described in further detail with reference to the following embodiments.
In example 1, the aluminum-based carrier is 28 parts by weight, the activated carbon is 15 parts by weight, the rare earth component is 4 parts by weight, and the weight ratio of the alpha-alumina to the gamma-alumina is 1:9, 5 parts by weight of an active agent and 2 parts by weight of an active auxiliary agent, wherein the specific process is as follows:
s1, adding 28 parts by weight of an aluminum-based carrier and 15 parts by weight of activated carbon into a stirring container, adding deionized water, primarily stirring uniformly, adding 4 parts by weight of a rare earth component, and stirring to generate carrier liquid, wherein the weight ratio of alpha-alumina to gamma-alumina is 1:9, the ratio of the weight of deionized water to the total weight of the aluminum-based carrier and the activated carbon is 2, and the weight ratio of rare earth components lanthanum, cerium and praseodymium is 1.2:1:0.8;
s2, mixing and stirring 5 parts by weight of active agent and 2 parts by weight of active auxiliary agent, and adding enough deionized water to mix and stir to generate active liquid. Wherein, the weight ratio of the active agent nickel sulfate to the ferric sulfate is 1:5, mixing the active agent and the active auxiliary agent for 3 hours;
s3, fully and uniformly mixing the active liquid, the carrier liquid and 1 part by weight of sulfur inhibition auxiliary agent to generate catalytic primary pulp. Wherein, the full mixing time is 3h;
s4, washing with deionized water, filtering, drying the catalyst primary pulp at the temperature of 80 ℃, specifically heating to the target calcination temperature at the heating rate of 10 ℃/min, and roasting for 3 hours in a nitrogen atmosphere at the calcination temperature of 300 ℃ to produce catalyst powder.
In example 2, in this example, the aluminum-based carrier was 30 parts by weight, the activated carbon was 15 parts by weight, the rare earth component was 4 parts by weight, and the weight ratio of α -alumina to γ -alumina was 2:8, 10 parts of active agent and 2 parts of active auxiliary agent, wherein the specific process is as follows:
s1, adding 30 parts by weight of an aluminum-based carrier and 15 parts by weight of activated carbon into a stirring container, adding deionized water, primarily stirring uniformly, adding 4 parts by weight of a rare earth component, and stirring to generate carrier liquid, wherein the weight ratio of alpha-alumina to gamma-alumina is 2:8, the ratio of the weight of deionized water to the total weight of the aluminum-based carrier and the activated carbon is 3, and the weight ratio of rare earth components lanthanum, cerium and praseodymium is 1.0:1.2:0.8;
s2, 10 parts by weight of active agent and 2 parts by weight of active auxiliary agent are mixed and stirred, and then enough deionized water is added for mixing and stirring to generate active liquid. Wherein, the weight ratio of the active agent nickel sulfate to the ferric sulfate is 1:5, mixing the active agent and the active auxiliary agent for 4 hours;
s3, fully and uniformly mixing the active liquid, the carrier liquid and 2 parts by weight of sulfur inhibition auxiliary agent to generate catalytic primary pulp. Wherein, the time of full mixing is 4 hours;
s4, washing with deionized water, filtering, drying the catalyst primary pulp at the temperature of 90 ℃, specifically heating to the target calcination temperature at the heating rate of 10 ℃/min, and roasting for 3 hours in a nitrogen atmosphere at the calcination temperature of 500 ℃ to produce catalyst powder.
In example 3, in this example, the aluminum-based carrier was 30 parts by weight, the activated carbon was 20 parts by weight, the rare earth component was 3 parts by weight, and the weight ratio of α -alumina to γ -alumina was 1:9, 5 parts of active agent and 4 parts of active auxiliary agent, wherein the specific process is as follows:
s1, adding 30 parts by weight of an aluminum-based carrier and 20 parts by weight of activated carbon into a stirring container, adding deionized water, primarily stirring uniformly, adding 3 parts by weight of a rare earth component, and stirring to generate carrier liquid, wherein the weight ratio of alpha-alumina to gamma-alumina is 1:9, the ratio of the weight of deionized water to the total weight of the aluminum-based carrier and the activated carbon is 3, and the weight ratio of rare earth components lanthanum, cerium and praseodymium is 1.1:1.0:0.9;
s2, mixing and stirring 5 parts by weight of active agent and 4 parts by weight of active auxiliary agent, and adding enough deionized water to mix and stir to generate active liquid. Wherein, the weight ratio of the active agent nickel sulfate to the ferric sulfate is 2:4, mixing the active agent and the active auxiliary agent for 4 hours;
s3, fully and uniformly mixing the active liquid, the carrier liquid and 2 parts by weight of sulfur inhibition auxiliary agent to generate catalytic primary pulp. Wherein, the time of full mixing is 4 hours;
s4, washing with deionized water, filtering, drying the catalyst primary pulp at the temperature of 100 ℃, specifically heating to the target calcination temperature at the heating rate of 10 ℃/min, and roasting for 3 hours in the nitrogen atmosphere at the calcination temperature of 500 ℃ to produce catalyst powder.
Comparative example 1
This comparative example was the same as in example 2, except that no aluminum-based carrier was added.
Comparative example 2
This comparative example was the same as in example 2, except that activated carbon was not added.
Comparative example 3
This comparative example was the same as example 2, except that no active agent was added.
Comparative example 4
This comparative example was the same as example 2, except that the rare earth component was not added.
Comparative example 5
This comparative example was the same as example 2, except that no active auxiliary was added.
Comparative example 6
This comparative example was the same as in example 2, except that no sulfur-inhibiting auxiliary was added.
Performance testing
Table 1 shows the catalysts obtained in the examples and comparative examples and their properties, the reaction conditions being O 3 =80 ppm，SO 2 =30 ppm，H 2 O=5 vol.%, total flow 1L/min, normal pressure, temperature 60 ℃, space velocity 0%30000 h −1 。
TABLE 1
| Aluminum-based carrier/part | Activated carbon/serving | Active agent/part | Rare earth component/part | Active auxiliary agent/part | Sulfur-inhibiting adjuvant | Ozone decomposition efficiency/% | |
| Example 1 | 28 | 15 | 5 | 4 | 2 | 1 | 82.6 |
| Example 2 | 30 | 15 | 10 | 4 | 2 | 2 | 87.2 |
| Example 3 | 30 | 20 | 5 | 3 | 4 | 2 | 84.1 |
| Comparative example 1 | / | 15 | 10 | 4 | 2 | 2 | 65.1 |
| Comparative example 2 | 30 | / | 10 | 4 | 2 | 2 | 57.8 |
| Comparative example 3 | 30 | 15 | / | 4 | 2 | 2 | 30.1 |
| Comparative example 4 | 30 | 15 | 10 | / | 2 | 2 | 50.2 |
| Comparative example 5 | 30 | 15 | 10 | 4 | / | 2 | 70.2 |
| Comparative example 6 | 30 | 15 | 10 | 4 | 2 | / | 69.4 |
( And (3) injection: ozone decomposition efficiency is (inlet ozone concentration-outlet ozone concentration)/inlet ozone concentration )
As can be seen from Table 1, the prepared catalysts of examples 1-3 all show better ozone decomposition activity of flue gas by controlling the weight parts of the aluminum-based carrier, the activated carbon, the active agent, the rare earth component, the active auxiliary agent and the sulfur-inhibiting auxiliary agent, and the ozone conversion rate is more than 80% under the test condition of sulfur-containing flue gas. Wherein the catalyst of example 2 exhibits optimal flue gas ozone decomposing activity.
The results of the activity tests of the comparative example and the example show that the aluminum-based carrier, the activated carbon, the active agent, the rare earth component, the activity auxiliary agent and the sulfur inhibition auxiliary agent play a key role in the ozonolysis catalyst of the invention, influence the ozonolysis efficiency, and obviously reduce the ozonolysis efficiency in sulfur-containing flue gas when any catalyst raw material is absent.
The foregoing has shown and described the basic principles, principal 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 above-described embodiments, and that the above-described embodiments and descriptions are only preferred embodiments of the present invention, and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The preparation method of the sulfur-resistant flue gas ozone decomposition catalyst is characterized by comprising the following steps of:
s1, adding 25-41 parts by weight of an aluminum-based carrier and 10-23 parts by weight of activated carbon into a stirring container, adding deionized water, primarily stirring uniformly, then adding 2-6 parts by weight of a rare earth component, and stirring again to generate carrier liquid;
s2, mixing 5-11 parts by weight of active agent and 2-6 parts by weight of active auxiliary agent, adding enough deionized water, mixing and stirring to generate active liquid;
s3, fully and uniformly mixing the active liquid, the carrier liquid and 1-4 parts by weight of sulfur inhibition auxiliary agent to generate catalyst primary pulp;
s4, washing, filtering, drying the catalyst primary pulp, and calcining to generate the catalyst powder;
the active agent comprises nickel sulfate and ferric sulfate, and the weight ratio of the nickel sulfate to the ferric sulfate is (1-2): (4-5); the rare earth components comprise lanthanum, cerium and praseodymium, and the weight ratio of the lanthanum, the cerium and the praseodymium is 1.2:1:0.8;
the active auxiliary agent is polyether P123;
the sulfur inhibition auxiliary agent is ammonium persulfate;
the aluminum-based carrier comprises alpha-alumina and gamma-alumina, and the weight ratio of the alpha-alumina to the gamma-alumina is (1-3): (6-9).
2. The method for preparing the sulfur-resistant flue gas ozone decomposition catalyst according to claim 1, wherein: in the step S1, the weight ratio of the deionized water to the total weight of the aluminum-based carrier and the activated carbon is 1.5-3.2.
3. The method for preparing the sulfur-resistant flue gas ozone decomposition catalyst according to claim 1, wherein: in the step S2, the stirring time of mixing the active agent and the active auxiliary agent is 2-6h.
4. The method for preparing the sulfur-resistant flue gas ozone decomposition catalyst according to claim 1, wherein: in the step S3, the time length of full mixing is 3-9h.
5. The method for preparing the sulfur-resistant flue gas ozone decomposition catalyst according to claim 1, wherein: in the step S4, the drying temperature is 80-110 ℃, the calcination is specifically carried out by heating to the target calcination temperature of 300-500 ℃ at the heating rate of 2-10 ℃/min, and the calcination is carried out in nitrogen atmosphere for 3-5 h.
6. The sulfur-resistant flue gas ozonolysis catalyst prepared by the preparation method according to any one of claims 1 to 5.
7. Use of the sulfur-resistant flue gas ozonolysis catalyst according to claim 6 in sulfur-containing flue gas ozone treatment in metal smelting, glass, cement or tile industry.
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