CN115041195B - Composite catalyst for flue gas treatment and preparation method and application thereof - Google Patents
Composite catalyst for flue gas treatment and preparation method and application thereof Download PDFInfo
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000003546 flue gas Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000011790 ferrous sulphate Substances 0.000 claims description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000006477 desulfuration reaction Methods 0.000 claims description 11
- 230000023556 desulfurization Effects 0.000 claims description 11
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 9
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 8
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims description 7
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229940093476 ethylene glycol Drugs 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 abstract description 2
- 229940095991 ferrous disulfide Drugs 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 235000010269 sulphur dioxide Nutrition 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052815 sulfur oxide Inorganic materials 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 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
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention belongs to the technical field of catalysts, and discloses a composite catalyst for flue gas treatment and a preparation method and application thereof. FeS is prepared by the invention 2 And CoS 2 Then CoS is carried out 2 Performing defect treatment to obtain CoS 2‑x By combining FeS 2 And CoS 2 Or CoS 2‑x Ball milling is carried out to obtain the composite catalyst. After the defect cobalt disulfide is combined with ferrous disulfide, surface defects are introduced, so that FeS 2 Fe of (3) 2+ Double active sites with sulfur vacancies can promote H 2 O 2 Generates a large amount of OH with strong oxidability, oxidizes pollutant SO 2 The sulfuric acid with economic benefit is obtained. The removal rate of sulfur dioxide in the flue gas after the composite catalyst is used for treating the flue gas for 8min can reach 100%, the composite catalyst has higher catalytic efficiency, and the preparation process is simple and is suitable for industrial mass production.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a composite catalyst for flue gas treatment and a preparation method and application thereof.
Background
With the rapid development of economy, the energy demand has been continuously increased in recent years, and the total energy consumption has also been in a trend of rising year by year. However, a large amount of smoke is generated during the energy consumption process, such as Sulfur Oxides (SO) x ) It can cause haze, acid rain, photochemical pollution and serious problems such as ozone layer destruction, and the like, and has very severe influence on the environment. For this reason, researchers have developed various technologies to reduce the large amount of emissions of coal-fired pollutants.
The existing flue gas treatment technology mostly has the problems of large occupied area, complex equipment, high investment and operation cost and the like, and the treatment of flue gas and waste gas of a power plant is a difficult problem of pollutant treatment for a long time. There are several desulfurizing techniques in the market, ammonia flue gas desulfurization means to use ammonia waterOr liquid ammonia absorbs SO in flue gas 2 Generated (NH) 4 ) 2 SO 3 Oxidized by air to (NH) 4 ) 2 SO 4 After treatment, a solid (NH) 4 ) 2 SO 4 The product is characterized in that ammonia water is added to adjust the pH of the absorption liquid to ensure desulfurization, but a large amount of ammonium sulfite can cause low crystallization rate of ammonium sulfate and low product quality, and the ammonium sulfite is heated to be decomposed easily to generate NH 3 And SO 2 Resulting in ammonia slip and evaporation. However, the absorbent ammonia water for flue gas desulfurization by the ammonia method is not easy to obtain, the required cost is high, the crystallization process has the problems of low crystallization rate, unstable nucleation, poor crystal quality and the like, the separation effect is poor, the operation is unstable, and the economic benefit of enterprises is seriously influenced.
Therefore, how to provide a catalyst for high-efficiency flue gas desulfurization has great significance for treating the atmospheric pollutants.
Disclosure of Invention
The invention aims to provide a composite catalyst for flue gas treatment, a preparation method and application thereof, and solves the problems of poor flue gas desulfurization effect and high cost in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a composite catalyst for flue gas treatment, which comprises the following steps:
(1)FeS 2 is prepared from the following steps: grinding ferrous sulfate, sodium thiosulfate pentahydrate and sulfur powder, and reacting with water to obtain FeS 2 ；
(2)CoS 2 Is prepared from the following steps: mixing cobalt chloride hexahydrate, sodium sulfide nonahydrate and ethylene glycol, and reacting to obtain CoS 2 ；
CoS 2-x Is prepared from the following steps: will CoS 2 Mixing with water, sequentially performing ultrasonic treatment, centrifuging, washing the product with alcohol solution, and drying to obtain CoS 2-x ；
(3)FeS 2 @CoS 2 Or FeS 2 @CoS 2-x Is prepared from the following steps: feS of step (1) 2 And CoS of step (2) 2 Or CoS 2-x Ball milling is carried out to obtain FeS 2 @CoS 2 Or FeS 2 @CoS 2-x A composite catalyst;
wherein x is more than 0 and less than 2.
Preferably, in the preparation method of the composite catalyst for flue gas treatment, the mass ratio of ferrous sulfate, sodium thiosulfate pentahydrate and sulfur powder in the step (1) is 2-4: 1 to 4:0.1 to 1; the mass volume ratio of ferrous sulfate to water is 2-4 g: 50-100 mL.
Preferably, in the preparation method of the composite catalyst for flue gas treatment, the reaction temperature in the step (1) is 200-230 ℃; the reaction time is 20-30 h.
Preferably, in the preparation method of the composite catalyst for flue gas treatment, the mass volume ratio of cobalt chloride hexahydrate, sodium sulfide nonahydrate and ethylene glycol in the step (2) is 1-3 g: 5-10 g:50mL.
Preferably, in the above preparation method of a composite catalyst for flue gas treatment, the temperature of the reaction in the step (2) is 160-200 ℃; the reaction time is 20-30 h.
Preferably, in the above preparation method of a composite catalyst for flue gas treatment, the time of ultrasound in the step (2) is 2-3 hours; the power of the ultrasonic wave is 200-400W.
Preferably, in the above method for preparing a composite catalyst for flue gas treatment, the FeS in step (3) 2 And CoS 2 The mass ratio of (2-4): 1, a step of; feS (FeS) 2 And CoS 2-x The mass ratio of (3-7): 1.
preferably, in the above preparation method of the composite catalyst for flue gas treatment, the rotational speed of ball milling in the step (3) is 300-500 rpm; the ball milling time is 1-4 h.
The invention also provides a composite catalyst for flue gas treatment prepared by the preparation method.
The invention also provides application of the composite catalyst for flue gas treatment in catalyzing flue gas desulfurization.
In the invention, after the defect cobalt disulfide is combined with ferrous disulfide, surface defects are introduced, so that FeS 2 Fe of (3) 2+ Double active sites with sulfur vacancies can promote H 2 O 2 Generates a large amount of OH with strong oxidability, oxidizes pollutant SO 2 The sulfuric acid with economic benefit is obtained. The existence of sulfur vacancies during the reaction causes SO 2 S capable of reacting with OH at almost zero distance and falling off 2- O is formed when the free oxygen exists in the system 2- ，Fe 3+ Further reduced to Fe 2+ So as to achieve the purpose of self-repairing. Based on this, coS 2 At H 2 O 2 Sulfur defects can form in the solution, H 2 O 2 CoS in solution 2-x Also has sulfur vacancy, so that the exposed cobalt ions can be used as a channel for transferring electrons through Co-Fe bonds to promote Fe existing on the surface of the catalyst 3+ To Fe 2+ The conversion forms a recyclable reaction.
Compared with the prior art, the invention has the following beneficial effects:
the removal rate of sulfur dioxide in the flue gas after the composite catalyst is used for treating the flue gas for 8min can reach 100%, the composite catalyst has higher catalytic efficiency, and the preparation process is simple and is suitable for industrial mass production.
Detailed Description
The invention provides a preparation method of a composite catalyst for flue gas treatment, which comprises the following steps:
(1)FeS 2 is prepared from the following steps: grinding ferrous sulfate, sodium thiosulfate pentahydrate and sulfur powder, mixing with water, and reacting to obtain FeS 2 ；
(2)CoS 2 Is prepared from the following steps: mixing cobalt chloride hexahydrate, sodium sulfide nonahydrate and ethylene glycol, and reacting to obtain CoS 2 ；
CoS 2-x Is prepared from the following steps: will CoS 2 Mixing with water, sequentially performing ultrasonic treatment, centrifuging, washing the product with alcohol solution, and drying to obtain CoS 2-x ；
(3)FeS 2 @CoS 2 Or FeS 2 @CoS 2-x Is prepared from the following steps: feS of step (1) 2 And CoS of step (2) 2 Or CoS 2-x Ball milling is carried out to obtain FeS 2 @CoS 2 Or FeS 2 @CoS 2-x A composite catalyst;
wherein x is more than 0 and less than 2;
the steps (1) and (2) are not limited in order.
In the invention, the mass ratio of the ferrous sulfate, the sodium thiosulfate pentahydrate and the sulfur powder in the step (1) is preferably 2-4: 1 to 4:0.1 to 1, more preferably 2.2 to 3.9:1.3 to 3.7:0.3 to 0.9, more preferably 3.2:2.6:0.5; the mass volume ratio of ferrous sulfate to water is preferably 2-4 g:50 to 100mL, more preferably 2.6 to 3.7g:62 to 93mL, more preferably 2.9g:76mL.
In the present invention, the temperature of the reaction in step (1) is preferably 200 to 230 ℃, more preferably 207 to 223 ℃, still more preferably 216 ℃; the reaction time is preferably 20 to 30 hours, more preferably 22 to 29 hours, and still more preferably 25 hours.
In the invention, the reaction in the step (1) is finished and then the product is washed and dried; the washing is preferably carried out by independently washing with water, carbon tetrachloride and absolute ethyl alcohol for 6 to 10 times, more preferably 7 to 9 times, and even more preferably 8 times; drying is preferably vacuum drying; the drying temperature is preferably 60 to 65 ℃, more preferably 61 to 64 ℃, and even more preferably 62 ℃; the drying time is preferably 6 to 10 hours, more preferably 7 to 9 hours, and still more preferably 8 hours; the vacuum degree of drying is preferably-0.1 MPa.
In the invention, the mass volume ratio of cobalt chloride hexahydrate, sodium sulfide nonahydrate and ethylene glycol in the step (2) is preferably 1-3 g: 5-10 g:50mL, more preferably 1.2 to 2.8g: 6-9 g:50mL, more preferably 2.3g:8g:50mL.
In the present invention, the temperature of the reaction in step (2) is preferably 160 to 200 ℃, more preferably 174 to 193 ℃, still more preferably 182 ℃; the reaction time is preferably 20 to 30 hours, more preferably 21 to 28 hours, and still more preferably 24 hours.
In the invention, the reaction in the step (2) is finished and then the product is washed and dried; the washing is preferably carried out for 2 to 5 times, more preferably 3 times by using water and absolute ethyl alcohol in sequence; drying is vacuum drying; the drying temperature is preferably 70 to 90 ℃, more preferably 73 to 86 ℃, and even more preferably 78 ℃; the drying time is preferably 6 to 10 hours, more preferably 7 to 9 hours, and still more preferably 8 hours; the vacuum degree of drying is preferably-0.1 MPa.
In the present invention, the time of the ultrasound in the step (2) is preferably 2 to 3 hours, more preferably 2.2 to 2.8 hours, still more preferably 2.5 hours; the power of the ultrasonic wave is preferably 200 to 400W, more preferably 230 to 360W, and still more preferably 300W.
In the present invention, the rotational speed of centrifugation in step (2) is preferably 10000 to 13000rpm, more preferably 11000 to 12000rpm, still more preferably 11500rpm; the time for centrifugation is preferably 5 to 10 minutes, more preferably 6 to 9 minutes, and still more preferably 7 minutes.
In the present invention, the alcohol solution in step (2) is preferably absolute ethanol.
In the present invention, the number of times of washing with the alcohol solution in the step (2) is preferably 1 to 5 times, more preferably 3 times.
In the present invention, the drying after the washing with the alcohol solution in the step (2) is preferably vacuum drying; the drying temperature is preferably 70 to 90 ℃, more preferably 73 to 89 ℃, and even more preferably 80 ℃; the drying time is preferably 6 to 10 hours, more preferably 7 to 9 hours, and still more preferably 8 hours; the vacuum degree of drying is preferably-0.1 MPa.
In the present invention, feS in step (3) 2 And CoS 2 The mass ratio of (2) to (4) is preferably: 1, more preferably 2.3 to 3.6:1, more preferably 2.9:1, a step of; feS (FeS) 2 And CoS 2-x The mass ratio of (3) to (7) is preferable: 1, more preferably 4 to 6:1, more preferably 5:1.
in the present invention, the rotation speed of the ball milling in the step (3) is preferably 300 to 500rpm, more preferably 330 to 480rpm, still more preferably 370rpm; the time for the ball milling is preferably 1 to 4 hours, more preferably 1.5 to 3 hours, and still more preferably 2 hours.
The invention also provides a composite catalyst for flue gas treatment prepared by the preparation method.
The invention also provides an application of the composite catalyst for flue gas treatment in catalyzing flue gas desulfurization.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments 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.
Example 1
(1)FeS 2 Is prepared from the following steps: grinding 3.1g of ferrous sulfate, 3.2g of sodium thiosulfate pentahydrate and 0.64g of sulfur powder for 30min, mixing with 60mL of water, magnetically stirring at room temperature for 30min, transferring to a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting at 200 ℃ for 24h, washing the product with water, carbon tetrachloride and absolute ethyl alcohol respectively for 8 times after the reaction, and vacuum drying at 60 ℃ and minus 0.1MPa for 6h to obtain FeS 2 ；
(2)CoS 2 Is prepared from the following steps: mixing 2.4g of cobalt chloride hexahydrate, 5.3g of sodium sulfide nonahydrate and 50mL of ethylene glycol, transferring into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 180 ℃, washing the product with water and absolute ethyl alcohol respectively for 3 times after the reaction is finished, and vacuum drying for 7 hours at 80 ℃ and minus 0.1MPa to obtain CoS 2 ；
(3)FeS 2 @CoS 2 Is prepared from the following steps: feS of step (1) 2 And CoS of step (2) 2 According to the mass ratio of 3:1 ball milling for 2 hours at 400rpm to obtain FeS 2 @CoS 2 A composite catalyst.
Example 2
(1)FeS 2 Is prepared from the following steps: grinding 4g of ferrous sulfate, 4g of sodium thiosulfate pentahydrate and 0.8g of sulfur powder for 30min, mixing with 100mL of water, magnetically stirring at room temperature for 30min, transferring into a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting at 210 ℃ for 26h, washing the product with water, carbon tetrachloride and absolute ethyl alcohol for 6 times in sequence after the reaction is finished, and standing at 60 ℃ and minus 0.1MPaAir drying for 10h to obtain FeS 2 ；
(2)CoS 2 Is prepared from the following steps: mixing 1.9g of cobalt chloride hexahydrate, 7.4g of sodium sulfide nonahydrate and 50mL of ethylene glycol, transferring into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 20 hours at 190 ℃, washing the product with water and absolute ethyl alcohol respectively for 4 times in sequence after the reaction is finished, and vacuum drying for 8 hours at 90 ℃ and minus 0.1MPa to obtain CoS 2 ；
(3)FeS 2 @CoS 2 Is prepared from the following steps: feS of step (1) 2 And CoS of step (2) 2 According to the mass ratio of 3.5: ball milling is carried out for 2.5 hours at the rotating speed of 300rpm to obtain FeS 2 @CoS 2 A composite catalyst.
Example 3
(1)FeS 2 Is prepared from the following steps: grinding 2.8g of ferrous sulfate, 3.6g of sodium thiosulfate pentahydrate and 0.9g of sulfur powder for 30min, mixing with 70mL of water, magnetically stirring at room temperature for 30min, transferring to a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting at 220 ℃ for 28h, washing the product with water, carbon tetrachloride and absolute ethyl alcohol respectively for 7 times after the reaction, and vacuum drying at 60 ℃ and minus 0.1MPa for 8h to obtain FeS 2 ；
(2)CoS 2-x (0 < x < 2): coS prepared in example 1 2 Ultrasonic dispersing with 60mL water for 3 hr, centrifuging at 13000rpm for 10min, removing supernatant, washing the product with alcohol solution for 3 times, and vacuum drying at 80 deg.C and-0.1 MPa for 7 hr to obtain CoS 2-x ；
(3)FeS 2 @CoS 2-x (0 < x < 2): feS of step (1) 2 And CoS of step (2) 2-x According to the mass ratio of 5:1 ball milling for 3 hours at 500rpm to obtain FeS 2 @CoS 2-x A composite catalyst.
Example 4
(1)FeS 2 See example 3 for the preparation of (c);
(2)CoS 2-x (0 < x < 2): coS prepared in example 1 2 Ultrasonic dispersing with 60mL water for 2.5h, centrifuging at 10000rpm for 7min, removing supernatant, washing the product with alcohol solution for 2 times, and vacuum drying at 70 deg.C and-0.1 MPa10h, obtain CoS 2-x ；
(3)FeS 2 @CoS 2-x (0 < x < 2): feS of step (1) 2 And CoS of step (2) 2-x According to the mass ratio of 6:1 ball milling for 3 hours at the rotating speed of 300rpm to obtain FeS 2 @CoS 2-x A composite catalyst.
The performance test method comprises the following steps:
(1) Selecting a coal-fired boiler of a boiler plant of a large coal-fired thermal power plant, spraying 30% hydrogen peroxide at a flow rate of 50mL/min under a flow rate of 1L/min, and simultaneously enabling the gas to pass through a reactor filled with 125mg of the composite catalyst of examples 1-4 respectively; respectively collecting air samples at the inlet and the outlet of a processor at different times by using a porous glass plate absorption tube filled with 10.0mL of formaldehyde buffer solution;
(2) Preparing sulfur dioxide standard liquid series of 0.0, 0.40, 0.80, 1.20 and 1.60mg/mL, respectively adding sulfamic acid solution of 1.0mL and 3g/L into each standard tube, shaking uniformly, and standing for 10min; 1.0mL of 1mol/L sodium hydroxide solution is added, then the solution in a standard tube is rapidly poured into a colorimetric test tube with a plug filled with 3mL of pararosaniline hydrochloride solution, and the mixture is uniformly mixed and reacted in a water bath at 20 ℃ for 15min; measuring absorbance by taking water as a reference under the condition of 575nm wavelength, measuring each concentration for 3 times, and drawing a standard curve according to the measured absorbance average value to the corresponding sulfur dioxide concentration (mg/mL); the preparation method of the pararosaniline hydrochloride solution comprises the following steps: accurately weighing 0.2g of pararosaniline hydrochloride, dissolving in 100mL of 1mol/L hydrochloric acid, sucking 20mL of the solution into a 250mL volumetric flask, adding 200mL of phosphoric acid solution, and diluting with water to a scale;
(3) Washing an air inlet pipe for 3 times by using an absorption liquid, taking 4.0mL of pararosaniline hydrochloride solution into a colorimetric test tube with a plug, adding 6mL of the absorption liquid, and uniformly mixing; determining the average value of absorbance of the sample in the step (1) by using the operation conditions of a determination standard series, and obtaining the concentration (mg/mL) of sulfur dioxide from a standard curve after subtracting the absorbance value of the blank from the average value of absorbance of the sample.
Wherein the sulfur dioxide treatment capacity is calculated at different times and is expressed as C, and the calculation formula is C=C 0 -C 1 Wherein C 0 For the initial concentration of sulfur dioxide, i.e. the concentration of sulfur dioxide at the inlet of the processor, C 1 For the concentration of sulphur dioxide in the exhaust gas corresponding to the treatment time, i.e. the concentration at the outlet. The removal rate is the ratio of the removal amount of sulfur dioxide to the initial concentration of sulfur dioxide, and the calculation mode is C/C 0 (%) and the following. The sulfur dioxide removal rate results at various times are shown in table 1.
TABLE 1 Sulfur dioxide removal Rate results
As shown in Table 1, the composite catalyst of the invention is used in flue gas desulfurization treatment, has high catalytic efficiency, can reach a removal rate of more than 90% in 30s, can completely remove sulfur dioxide in flue gas after 8min of treatment, realizes purification and desulfurization of flue gas, and the treated sulfur dioxide is absorbed by water to obtain sulfuric acid with economic benefit, thereby reducing treatment cost.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (2)
1. The application of the composite catalyst for flue gas treatment in catalyzing flue gas desulfurization is characterized in that the preparation method of the composite catalyst for flue gas treatment comprises the following steps:
（1）FeS 2 is prepared from the following steps: grinding ferrous sulfate, sodium thiosulfate pentahydrate and sulfur powder, and reacting with water to obtain FeS 2 ；
（2）CoS 2 Is prepared from the following steps: sulfiding cobalt chloride hexahydrate, nonahydrateMixing sodium and glycol, and reacting to obtain CoS 2 ；
CoS 2-x Is prepared from the following steps: will CoS 2 Mixing with water, sequentially performing ultrasonic treatment, centrifuging, washing the product with alcohol solution, and drying to obtain CoS 2-x ；
（3）FeS 2 @CoS 2 Or FeS 2 @CoS 2-x Is prepared from the following steps: feS of step (1) 2 And CoS of step (2) 2 Or CoS 2-x Ball milling is carried out to obtain FeS 2 @CoS 2 Or FeS 2 @CoS 2-x A composite catalyst;
wherein x is more than 0 and less than 2;
in the step (1), the mass ratio of ferrous sulfate, sodium thiosulfate pentahydrate and sulfur powder is 2-4: 1-4: 0.1-1; the mass volume ratio of ferrous sulfate to water is 2-4 g: 50-100 mL;
the reaction temperature in the step (1) is 200-230 ℃; the reaction time is 20-30 h;
in the step (2), the mass volume ratio of cobalt chloride hexahydrate, sodium sulfide nonahydrate and ethylene glycol is 1-3 g: 5-10 g:50mL;
the temperature of the reaction in the step (2) is 160-200 ℃; the reaction time is 20-30 h;
the ultrasonic time in the step (2) is 2-3 hours; the power of the ultrasonic wave is 200-400W;
FeS in the step (3) 2 And CoS 2 The mass ratio of (2-4): 1, a step of; feS (FeS) 2 And CoS 2-x The mass ratio of (3-7): 1.
2. the use of a composite catalyst for flue gas treatment according to claim 1 for catalyzing flue gas desulfurization, wherein the rotational speed of ball milling in step (3) is 300-500 rpm; the ball milling time is 1-4 hours.
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| CN113289642A (en) * | 2021-06-22 | 2021-08-24 | 广西民族大学 | Self-repairing Fenton catalyst and preparation method and application thereof |
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| WO2012031330A1 (en) * | 2010-09-10 | 2012-03-15 | The University Of Queensland | Catalyst and method for producing same |
| CN111732181A (en) * | 2020-07-06 | 2020-10-02 | 广西民族大学 | Multiphase Fenton reagent and application thereof |
| CN112301361A (en) * | 2020-10-30 | 2021-02-02 | 安徽晟源环保新型材料有限公司宿马分公司 | Hollow CoS2Oxygen evolution catalyst of microsphere modified nitrogen-doped porous carbon and preparation method thereof |
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