CN113600172A - Alkaline catalyst and preparation method and application thereof - Google Patents
Alkaline catalyst and preparation method and application thereof Download PDFInfo
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- CN113600172A CN113600172A CN202110970709.4A CN202110970709A CN113600172A CN 113600172 A CN113600172 A CN 113600172A CN 202110970709 A CN202110970709 A CN 202110970709A CN 113600172 A CN113600172 A CN 113600172A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 6
- IZCUOLNYELHOEC-UHFFFAOYSA-N [Eu].[Ce] Chemical compound [Eu].[Ce] IZCUOLNYELHOEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 5
- NYRAVIYBIHCEGB-UHFFFAOYSA-N [K].[Ca] Chemical compound [K].[Ca] NYRAVIYBIHCEGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 51
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 15
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 13
- 229930006000 Sucrose Natural products 0.000 claims description 13
- 239000005720 sucrose Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 10
- 229910001940 europium oxide Inorganic materials 0.000 claims description 10
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 9
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 150000000918 Europium Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 4
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical group C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 2
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 claims description 2
- SQKWGPOIVHMUNF-UHFFFAOYSA-K cerium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Ce+3] SQKWGPOIVHMUNF-UHFFFAOYSA-K 0.000 claims description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 2
- AWDWVTKHJOZOBQ-UHFFFAOYSA-K europium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Eu+3] AWDWVTKHJOZOBQ-UHFFFAOYSA-K 0.000 claims description 2
- JVYYYCWKSSSCEI-UHFFFAOYSA-N europium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JVYYYCWKSSSCEI-UHFFFAOYSA-N 0.000 claims description 2
- 229960002337 magnesium chloride Drugs 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011593 sulfur Substances 0.000 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000004821 distillation Methods 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 2
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000010453 quartz Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000006477 desulfuration reaction Methods 0.000 description 11
- 230000023556 desulfurization Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 2
- 229910016644 EuCl3 Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- 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
- B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
- B01D53/8646—Simultaneous elimination of the components
- B01D53/865—Simultaneous elimination of the components characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- 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
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
Abstract
The invention provides a method for simultaneously removing CO, NO and SO2The alkaline catalyst and the preparation method thereof utilize a precipitation method to prepare magnesium oxide as a carrier, load cerium-europium composite oxide as an active component, and add potassium-calcium composite oxide as a cocatalyst component. The catalyst has good reaction activity and strong alkalinity, and is favorable for adsorbing NO and SO on the surface of the catalyst simultaneously2And catalytic reduction of NO, SO by CO2To form CO2、N2And elemental S. Not only solves the problem of alkali poisoning of the conventional SCR denitration catalyst, but also the byproduct sulfur generated by the reaction passes through the solvent CS2Recovering CS by distillation2The solvent has low cost, no secondary pollution and high sulfur recovery rate, and solves the current situation of low sulfur yield in China.
Description
Technical Field
The invention relates to the field of air purification, and particularly relates to an alkaline catalyst and a preparation method and application thereof.
Background
China belongs to a large energy production country, and is also a large energy consumption country due to population cardinality, the energy structure of China still takes coal as a main part at present, and the annual total consumption of coal is also increased rapidly due to rapid development of economy of China, particularly rapid development of electric power and steel industry. Combustion of coal produces large amounts of SO2And NOXThe harmful gases are the main source of air pollution in China, and are also the main cause of acid rain in China, thus seriously harming human health and ecological environment.
At present, the conventional desulfurization process in China can be divided into wet desulfurization, dry desulfurization and semi-dry desulfurization. However, the desulfurization process route is single, and the disposal and consumption of desulfurization by-products, desulfurization gypsum, desulfurization ash, and the like, have not received sufficient attention. The gypsum which is the byproduct of desulfurization in part of power plants is eliminatedIn the case of storage, only a disposal mode of stacking and discarding can be adopted. A large amount of byproducts still mainly are stacked in the open air, which not only occupies land resources, but also causes secondary pollution to the environment. In addition, the desulfurization by-products are not effectively utilized, which results in resource waste. Conventional denitration technique with NH3Is a reducing agent and has the characteristics of high reaction efficiency and good selectivity, but NH3High cost of NH3The environment is polluted after escaping. In the conventional denitration SCR technology, alkali metal in fuel can volatilize in the combustion process to form submicron aerosol particles which react with a catalyst, so that the catalyst is poisoned and inactivated, the service life of the catalyst is shortened, and the cost of an SCR system is increased.
Disclosure of Invention
The invention provides an alkaline catalyst, a preparation method and application thereof aiming at the technical problems.
An alkaline catalyst, which takes magnesium oxide as a carrier, cerium-europium composite oxide as a catalytic active component, potassium-calcium composite oxide as a cocatalyst component, and sucrose as a pore-forming agent of the catalyst carrier; based on the mass of the carrier, the mass percentage of the catalytic active component is 1-15%, the mass percentage of the cocatalyst component is 0.1-5%, wherein the mass ratio of cerium oxide to europium oxide in the active component is 1: (0.1-3), wherein the mass ratio of potassium oxide to calcium oxide in the cocatalyst is 1 (1-5).
In some specific embodiments: the mass percentage of the catalytic active component is 5-10%, and the mass ratio of cerium oxide to europium oxide in the active component is 1: (0.1-0.5).
In some specific embodiments: the mass percentage of the catalyst promoter component is 0.5-2%, and the mass ratio of potassium oxide to calcium oxide in the catalyst promoter component is 1 (2-3).
A preparation method of the catalyst comprises the following steps:
a. respectively dissolving magnesium chloride hexahydrate and sucrose in water, slowly dropwise adding the obtained sucrose aqueous solution into the magnesium chloride aqueous solution, and uniformly mixing to obtain a mixed solution 1;
b. dissolving cerium salt, europium salt, potassium salt and calcium salt in water, slowly adding the mixture into the mixed solution 1, and stirring for 4-6 hours at the temperature of 70-80 ℃ to obtain a mixed solution 2;
c. and adding ammonia water into the mixed solution 2, stirring for 1-3 hours at the temperature of 70-80 ℃, then placing the mixed solution into a blast drying oven for heat preservation and drying at the temperature of 100-120 ℃, and then placing the dried mixed solution into a muffle furnace for roasting for 4-5 hours at the temperature of 500-600 ℃ to obtain the catalyst.
The preparation method comprises the following steps: magnesium chloride hexahydrate in step (a): the mass ratio of the sucrose is 1: (0.2-0.25).
The preparation method comprises the following steps: the cerium salt in the step (b) is cerium nitrate hexahydrate or cerium chloride hexahydrate, the europium salt is europium nitrate hexahydrate or europium chloride hexahydrate, the potassium salt is potassium nitrate or potassium chloride, and the calcium salt is calcium nitrate tetrahydrate or calcium chloride hexahydrate.
The technical scheme of the invention is as follows: the catalyst can simultaneously remove CO, NO and SO2Application of the aspect.
The catalyst evaluation method of the present invention comprises: putting 1mL of catalyst into a 10mm quartz tube, and putting the quartz tube into a tube type electric furnace; wherein the reaction atmosphere is flue gas, the content of the flue gas is 2 to 10 percent of CO, 0.1 to 0.2 percent of NO and 0.5 to 4 percent of SO2，85.8％～97.4％N2The volume airspeed is 12000-15000 h-1(ii) a The heating rate is 5-15 ℃/min, and the reaction temperature is 300-500 ℃; the sulfur steam enters the cold trap from the air outlet of the tubular furnace through the heating belt for desublimation to form sulfur.
After the reaction is finished, adding 100-120 mL of CS into the cold trap2Shaking up and down to dissolve sulfur in CS2In the solution, the mixed solution is placed in a distillation flask, the distillation flask is placed in a water bath kettle for heating at 50-60 ℃, and CS2Heated and gasified, and the vapor enters the condensing tube through the branch tube and is condensed into the conical flask. The sulfur in the distillation flask was collected.
The invention has the beneficial effects that:
(1) CO in flue gas is utilized to simultaneously remove NO and SO2Mixing CO, NO and SO2Simultaneous conversion to CO2、N2And elemental S. Not only doThe problems of secondary pollution, waste treatment incapability, equipment corrosion, high investment and running cost in the conventional flue gas desulfurization technology at present can be solved, and the valuable resource of sulfur can be obtained;
(2) magnesium oxide is used as a carrier, and a potassium-calcium composite oxide is added as a cocatalyst component, SO that the alkalinity of the catalyst is increased, and the catalyst is favorable for adsorbing more NO and SO2The improvement of the CO as a reducing agent on NO and SO2The removal rate of (2);
(3) the sucrose is used as a pore-forming agent, so that the specific surface area of the catalyst carrier is increased, the loading capacity of the active component is improved, and meanwhile, the magnesium oxide carrier and the cerium-europium active component in the catalyst have a synergistic catalytic effect, so that the catalytic effect of the cerium-europium active component is improved;
(4) the problem of SCR alkali poisoning of the conventional denitration technology in China is solved, and the acid site center of the catalyst is neutralized by alkaline substances in an SCR system, so that the oxidation-reduction property of the catalyst is reduced.
Drawings
FIG. 1 is a diagram of an apparatus used in the present invention.
Wherein: 1.N2 99.999％，2.SO299.999%, 3.CO 99.999%, 4.NO 99.999%, 5. pressure reducing valve, 6. mass flow meter, 7. mixing chamber, 8. high temperature tube furnace, 9. tube furnace, 10. catalyst fixed bed layer, 11. cold trap, 12. flue gas analyzer, 13. three-way valve, 14. gas chromatograph.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
a. 20.18g of MgCl2·6H2O and 4.04g C12H12O11Respectively dissolved in 150mL and 25mLH2In O, slowly adding the sucrose solution dropwise to MgCl2·6H2And mixing the solution O and the solution O uniformly to obtain a mixed solution 1.
b. 0.40gCe (NO)3)3·6H2O、0.10gEu(NO3)3·6H2O、0.01g KNO3、0.06g Ca(NO3)4·4H2Dissolving O in 25ml of water, slowly adding the dissolved O into the mixed solution 1, and placing the mixed solution in a magnetic stirrer to stir at a constant speed for 4 hours at 80 ℃ to obtain a mixed solution 2;
c. adding 25ml of ammonia water into the mixed solution 2, placing the mixed solution in a magnetic stirrer for 2h at 80 ℃ and stirring at a constant speed, then placing the mixed solution in a blast drying oven for heat preservation and drying at 100 ℃, and then placing the mixed solution in a muffle furnace for roasting at 600 ℃ for 4h to obtain the catalyst, wherein the mass fraction of the active component is 5 percent, the mass fraction of the cocatalyst is 0.5 percent, the mass ratio of cerium oxide to europium oxide in the active component is 1:0.25, and the mass ratio of potassium oxide to calcium oxide in the cocatalyst is 1:3, based on the mass of the carrier.
e. Crushing and sieving the catalyst prepared by pre-calcination, selecting 1.00mL of particles with 20-40 meshes, placing the particles in a 10mm quartz tube, and placing the quartz tube in a tube type electric furnace.
Example 2
a. 20.18g of MgCl2·6H2O and 5.05g C12H12O11Respectively dissolved in 150mL and 25mLH2In O, slowly adding the sucrose solution dropwise to MgCl2·6H2And mixing the solution O and the solution O uniformly to obtain a mixed solution 1.
b. 0.66g of Ce (NO)3)3·6H2O、0.33gEu(NO3)3·6H2O、0.02g KNO3、0.13g Ca(NO3)4·4H2Dissolving O in 25ml of water, slowly adding the dissolved O into the mixed solution 1, and placing the mixed solution in a magnetic stirrer to stir at a constant speed for 6 hours at 75 ℃ to obtain a mixed solution 2;
c. adding 25ml of ammonia water into the mixed solution 2, placing the mixed solution in a magnetic stirrer, stirring at 80 ℃ for 4h at a constant speed, then placing the mixed solution in a blast drying oven, keeping the temperature and drying at 120 ℃, and then placing the mixed solution in a muffle furnace for roasting at 550 ℃ for 4h to obtain the catalyst, wherein the mass fraction of the active component is 10 percent, the mass fraction of the cocatalyst is 1 percent, the mass ratio of cerium oxide to europium oxide in the active component is 1:0.5, and the mass ratio of potassium oxide to calcium oxide in the cocatalyst is 1:3 based on the mass of the carrier.
e. Crushing and sieving the catalyst prepared by pre-calcination, selecting 1.00mL of particles with 20-40 meshes, placing the particles in a 10mm quartz tube, and placing the quartz tube in a tube type electric furnace.
Example 3
a. 20.18g of MgCl2·6H2O and 4.04g C12H12O11Respectively dissolved in 150mL and 25mLH2In O, slowly adding the sucrose solution dropwise to MgCl2·6H2And mixing the solution O and the solution O uniformly to obtain a mixed solution 1.
b. 0.33g of CeCl3·6H2O、0.08g EuCl3·6H2O、0.01g KCl、0.03g CaCl2Dissolving in 25ml of water, slowly adding into the mixed solution 1, and placing in a magnetic stirrer to stir at 80 ℃ for 4h at uniform speed to obtain a mixed solution 2;
c. adding 25ml of ammonia water into the mixed solution 2, placing the mixed solution in a magnetic stirrer for 2h at 80 ℃ and stirring at a constant speed, then placing the mixed solution in a blast drying oven for heat preservation and drying at 100 ℃, and then placing the mixed solution in a muffle furnace for roasting at 600 ℃ for 4h to obtain the catalyst, wherein the mass fraction of the active component is 5 percent, the mass fraction of the cocatalyst is 0.5 percent, the mass ratio of cerium oxide to europium oxide in the active component is 1:0.25, and the mass ratio of potassium oxide to calcium oxide in the cocatalyst is 1:3, based on the mass of the carrier.
e. Crushing and sieving the catalyst prepared by pre-calcination, selecting 1.00mL of particles with 20-40 meshes, placing the particles in a 10mm quartz tube, and placing the quartz tube in a tube type electric furnace.
Example 4
a. 20.18g of MgCl2·6H2O and 5.05g C12H12O11Respectively dissolved in 150mL and 25mLH2In O, slowly adding the sucrose solution dropwise to MgCl2·6H2And mixing the solution O and the solution O uniformly to obtain a mixed solution 1.
b. 0.53g of CeCl3·6H2O、0.27g EuCl3·6H2O、0.02g KCl、0.06g CaCl2Dissolving in 25ml of water, slowly adding into the mixed solution 1, and placing in a magnetic stirrer to stir at 80 ℃ for 4h at uniform speed to obtain a mixed solution 2;
c. adding 25ml of ammonia water into the mixed solution 2, placing the mixed solution in a magnetic stirrer for stirring at a constant speed for 2h at 80 ℃, then placing the mixed solution in a blast drying oven for heat preservation and drying at 100 ℃, and then placing the mixed solution in a muffle furnace for roasting at 600 ℃ for 4h to obtain the catalyst, wherein the mass fraction of the active component is 10 percent, the mass fraction of the cocatalyst is 1 percent, the mass ratio of cerium oxide to europium oxide in the active component is 1:0.5, and the mass ratio of potassium oxide to calcium oxide in the cocatalyst is 1:3 based on the mass of the carrier.
e. Crushing and sieving the catalyst prepared by pre-calcination, selecting 1.00mL of particles with 20-40 meshes, placing the particles in a 10mm quartz tube, and placing the quartz tube in a tube type electric furnace.
Comparative example 1
The other conditions were the same as in example 1, wherein step b was as follows:
b. 0.40gCe (NO)3)3·6H2O、0.01g KNO3、0.06g Ca(NO3)4·4H2And adding O into 25ml of water slowly into the mixed solution 1, and placing the mixture into a magnetic stirrer to stir at a constant speed for 4 hours at 80 ℃ to obtain a mixed solution 2.
Comparative example 2
The other conditions were the same as in example 1, wherein step b was as follows:
b. 0.10gEu (NO)3)3·6H2O、0.01g KNO3、0.06g Ca(NO3)4·4H2And adding O into 25ml of water slowly into the mixed solution 1, and placing the mixture into a magnetic stirrer to stir at a constant speed for 4 hours at 80 ℃ to obtain a mixed solution 2.
Comparative example 3
The other conditions were the same as in example 1, wherein step b was as follows:
b. 0.40gCe (NO)3)3·6H2O、0.10gEu(NO3)3·6H2Dissolving O in 25ml of water, slowly adding the dissolved O into the mixed solution 1, and placing the mixed solution in a magnetic stirrer to stir at a constant speed for 4 hours at 80 ℃ to obtain a mixed solution 2;
performance testing
The performance of the catalyst was tested using the apparatus of FIG. 1, 1mL of the catalyst was placed in a 10mm quartz tube 9 and fixed to a catalyst fixed bed 10, and the quartz tube 9 was held highA warm tube electric furnace 8. The reaction atmosphere is flue gas containing 0.2% of NO and 1% of SO2，2.2％CO，96.4％N2The volume space velocity is 12000h-1. The heating rate is 10 ℃/min, and the reaction temperature is 300 ℃, 350 ℃, 400 ℃, 450 ℃ and 500 ℃ in sequence. The high-temperature tube furnace 8 is heated to the target temperature by a program and is insulated, and the tail gas is detected after the tail gas is stabilized; testing of CO Using flue gas Analyzer 122、NO、SO2Concentration; the COS concentration was measured by gas chromatography (semer feishell technologies ltd) 14. The sulfur steam enters the cold trap 11 from the air outlet of the high-temperature tubular furnace 8 through the heating zone for desublimation to be sulfur. After the reaction is finished, 100 mL-120 mL CS is added into the cold trap 112Shaking up and down to dissolve sulfur in CS2In solution. Placing the mixed solution in a distillation flask, placing the distillation flask in a water bath kettle, heating at 50 deg.C, and placing CS2Heated and gasified, and the vapor enters the condensing tube through the branch tube and is condensed into the conical flask. After the distillation was completed, sulfur in the distillation flask was collected.
And (3) testing results:
TABLE 1 product Performance testing of examples 1-4
TABLE 2 product performance test of comparative examples 1-3
Compared with the example 1, the comparative example 1 does not add the active component europium oxide, and the catalyst activity of the single-active component cerium oxide is lower than that of the double-active component catalyst, so that the oxidation-reduction property of the catalyst is reduced; compared with the example 1, the catalyst of the comparative example 2 has the advantages that the cerium oxide serving as the active component is not added, the catalyst activity of the europium oxide serving as the single active component is lower than that of the catalyst serving as the double active components, and the oxidation-reduction property of the catalyst is reduced; comparative example 3 compared with example 1, calcium oxide and potassium oxide which are catalyst assistants are not added, the alkalinity of the catalyst is reduced, and the SO on the surface of the catalyst is reduced2And adsorption of NO.
Claims (7)
1. A basic catalyst characterized by: the catalyst takes magnesium oxide as a carrier, a cerium-europium composite oxide as a catalytic active component, a potassium-calcium composite oxide as a cocatalyst component, and sucrose as a pore-forming agent of the catalyst carrier; based on the mass of the carrier, the mass percentage of the catalytic active component is 1-15%, the mass percentage of the cocatalyst component is 0.1-5%, wherein the mass ratio of cerium oxide to europium oxide in the active component is 1: (0.1-3), wherein the mass ratio of potassium oxide to calcium oxide in the cocatalyst is 1 (1-5).
2. The basic catalyst according to claim 1, characterized in that: the mass percentage of the catalytic active component is 5-10%, and the mass ratio of cerium oxide to europium oxide in the active component is 1: (0.1-0.5).
3. The basic catalyst according to claim 1, characterized in that: the mass percentage of the catalyst promoter component is 0.5-2%, and the mass ratio of potassium oxide to calcium oxide in the catalyst promoter component is 1 (2-3).
4. A method of preparing the catalyst of claim 1, wherein: the preparation method comprises the following steps:
a. respectively dissolving magnesium chloride hexahydrate and sucrose in water, slowly dropwise adding the obtained sucrose aqueous solution into the magnesium chloride aqueous solution, and uniformly mixing to obtain a mixed solution 1;
b. dissolving cerium salt, europium salt, potassium salt and calcium salt in water, slowly adding the mixture into the mixed solution 1, and stirring for 4-6 hours at the temperature of 70-80 ℃ to obtain a mixed solution 2;
c. and adding ammonia water into the mixed solution 2, stirring for 1-3 hours at the temperature of 70-80 ℃, then placing the mixed solution into a blast drying oven for heat preservation and drying at the temperature of 100-120 ℃, and then placing the dried mixed solution into a muffle furnace for roasting for 4-5 hours at the temperature of 500-600 ℃ to obtain the catalyst.
5. The method of claim 4, wherein: magnesium chloride hexahydrate in step (a): the mass ratio of the sucrose is 1: (0.2-0.25).
6. The method of claim 5, wherein: the cerium salt in the step (b) is cerium nitrate hexahydrate or cerium chloride hexahydrate, the europium salt is europium nitrate hexahydrate or europium chloride hexahydrate, the potassium salt is potassium nitrate or potassium chloride, and the calcium salt is calcium nitrate tetrahydrate or calcium chloride hexahydrate.
7. The catalyst of claim 1 for the simultaneous removal of CO, NO and SO2Application of the aspect.
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