CN115041195A - 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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- CN115041195A CN115041195A CN202210890375.4A CN202210890375A CN115041195A CN 115041195 A CN115041195 A CN 115041195A CN 202210890375 A CN202210890375 A CN 202210890375A CN 115041195 A CN115041195 A CN 115041195A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003546 flue gas Substances 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 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 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 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 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 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
- 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 8
- 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 8
- 238000000227 grinding Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 229940093476 ethylene glycol Drugs 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 28
- 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
- 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
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 13
- 235000010269 sulphur dioxide Nutrition 0.000 description 13
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 229910052815 sulfur oxide Inorganic materials 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 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
- 230000001476 alcoholic effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-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
- 238000004364 calculation method Methods 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000005034 decoration 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
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000006228 supernatant Substances 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
- 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
- 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
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement 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
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012086 standard solution Substances 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
- 238000002604 ultrasonography Methods 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. The invention respectively prepares FeS 2 And CoS 2 Then CoS is added 2 Defect processing is carried out to obtain CoS 2‑x By reacting FeS 2 And CoS 2 Or CoS 2‑x And carrying out ball milling to obtain the composite catalyst. After the defect cobalt disulfide and the ferrous disulfide are combined, the surface defect is introduced, so that FeS 2 Fe in (1) 2+ Can form double active sites with sulfur vacancy, and promote H 2 O 2 Generate a large amount of OH with strong oxidizing property, oxidize the pollutant SO 2 Obtaining the sulfuric acid with economic benefit. The composite catalyst of the invention can reach a removal rate of 1 to sulfur dioxide in the flue gas after treating the flue gas for 8min00 percent, has higher catalytic efficiency, simple preparation process and is suitable for industrial large-scale 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 demand for energy has been increasing in recent years, and the total energy consumption has been increasing year by year. However, a large amount of soot, such as Sulfur Oxides (SO), is generated during energy consumption x ) It can cause severe problems such as haze, acid rain, photochemical pollution and ozone layer destruction, and has severe influence on the environment. To this end, researchers have developed a variety of techniques to reduce the large emissions of coal-fired pollutants.
Most of the existing flue gas treatment technologies have the problems of large occupied area, complex equipment, high investment and operation cost and the like, and the treatment of the flue gas and the waste gas of the power plant is a difficult point for pollutant treatment for a long time. At present, various desulfurization technologies are available on the market, and ammonia flue gas desulfurization refers to the absorption of SO in flue gas by ammonia water or liquid ammonia 2 Generated (NH) 4 ) 2 SO 3 Is oxidized into (NH) by air 4 ) 2 SO 4 After treatment, a solid (NH) is obtained 4 ) 2 SO 4 The product is simultaneously added with ammonia water to adjust the pH value of the absorption liquid so as 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 easily decomposed by heating to generate NH 3 And SO 2 Resulting in ammonia slip and evaporation. However, ammonia water used as an absorbent for ammonia flue gas desulfurization is not easily available, the required cost is high, and the crystallization process has the problems of low crystallization rate, unstable nucleation, poor crystal quality and the like, so that the separation effect is poor, the operation is unstable, and the economic benefit of enterprises is seriously influenced.
Therefore, how to provide the catalyst for high-efficiency flue gas desulfurization has important significance for treating the atmospheric pollutants.
Disclosure of Invention
The invention aims to provide a composite catalyst for flue gas treatment and 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 the preparation of (1): grinding ferrous sulfate, sodium thiosulfate pentahydrate and sulfur powder, and reacting with water to obtain FeS 2 ；
(2)CoS 2 The preparation of (1): mixing cobalt chloride hexahydrate, sodium sulfide nonahydrate and ethylene glycol, and reacting to obtain CoS 2 ；
CoS 2-x The preparation of (1): adding CoS 2 Mixing with water, sequentially performing ultrasonic treatment and centrifugation, washing the product with an alcohol solution, and drying to obtain CoS 2-x ；
(3)FeS 2 @CoS 2 Or FeS 2 @CoS 2-x The preparation of (1): FeS obtained in the 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: 1-4: 0.1 to 1; the mass-volume ratio of the ferrous sulfate to the water is 2-4 g: 50-100 mL.
Preferably, in the above 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 above preparation method of the composite catalyst for flue gas treatment, in the step (2), the mass-to-volume ratio of cobalt chloride hexahydrate, sodium sulfide nonahydrate and ethylene glycol is 1-3 g: 5-10 g: 50 mL.
Preferably, in the preparation method of the composite catalyst for flue gas treatment, the reaction temperature in the step (2) is 160-200 ℃; the reaction time is 20-30 h.
Preferably, in the preparation method of the 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 the step (3) 2 And CoS 2 The mass ratio of (A) to (B) is 2-4: 1; FeS 2 And CoS 2-x The mass ratio of (A) to (B) is 3-7: 1.
preferably, in the above preparation method of the composite catalyst for flue gas treatment, the rotation speed of the ball mill in the step (3) is 300-500 rpm; the ball milling time is 1-4 h.
The invention also provides the composite catalyst for treating the flue gas, which is prepared by the preparation method.
The invention also provides application of the composite catalyst for flue gas treatment in catalytic flue gas desulfurization.
In the invention, after the defect cobalt disulfide and ferrous disulfide are combined, surface defects are introduced, so that FeS is obtained 2 Fe in (1) 2+ Can form double active sites with sulfur vacancy, and promote H 2 O 2 Generate a large amount of OH with strong oxidizing property, oxidize the pollutant SO 2 The sulfuric acid with economic benefit is obtained. SO is caused by the existence of sulfur vacancy in the reaction process 2 S which can react with OH at almost zero distance and is released 2- O is formed when it is present together with free oxygen present in the system 2- ，Fe 3+ Is further reduced to Fe 2+ So as to achieve the self-repairing purpose. On the basis of the above, CoS 2 At H 2 O 2 Sulfur defects, H, can form in solution 2 O 2 CoS in solution 2-x Also has sulfur vacancy, so that the exposed cobalt ion can be used as a channel for transferring electrons through a Co-Fe bond to promote Fe existing on the surface of the catalyst 3+ To Fe 2+ And converting to form a recyclable reaction.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the composite catalyst of the invention can reach 100 percent of removal rate of sulfur dioxide in the flue gas after treating the flue gas for 8min, has higher catalytic efficiency and simple preparation process, and is suitable for industrial large-scale 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 the preparation of (1): grinding ferrous sulfate, sodium thiosulfate pentahydrate and sulfur powder, mixing with water, and reacting to obtain FeS 2 ；
(2)CoS 2 The preparation of (1): mixing cobalt chloride hexahydrate, sodium sulfide nonahydrate and ethylene glycol, and reacting to obtain CoS 2 ；
CoS 2-x The preparation of (1): adding CoS 2 Mixing with water, sequentially performing ultrasonic treatment and centrifugation, washing the product with an alcohol solution, and drying to obtain CoS 2-x ；
(3)FeS 2 @CoS 2 Or FeS 2 @CoS 2-x The preparation of (1): FeS obtained in the 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 step (1) and the step (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: 1-4: 0.1 to 1, and more preferably 2.2 to 3.9: 1.3-3.7: 0.3 to 0.9, more preferably 3.2: 2.6: 0.5; the mass-volume ratio of the ferrous sulfate to the water is preferably 2-4 g: 50 to 100mL, more preferably 2.6 to 3.7 g: 62 to 93mL, more preferably 2.9 g: 76 mL.
In the invention, the reaction temperature in the step (1) is preferably 200-230 ℃, more preferably 207-223 ℃, and more preferably 216 ℃; the reaction time is preferably 20 to 30 hours, more preferably 22 to 29 hours, and even more preferably 25 hours.
In the invention, after the reaction in the step (1) is finished, the product is washed and dried; washing is preferably carried out for 6-10 times, more preferably 7-9 times, and even more preferably 8 times by sequentially washing with water, carbon tetrachloride and absolute ethyl alcohol independently; the drying is preferably vacuum drying; the drying temperature is preferably 60-65 ℃, more preferably 61-64 ℃, and more preferably 62 ℃; the drying time is preferably 6-10 h, more preferably 7-9 h, and even more preferably 8 h; the degree of vacuum for drying is preferably-0.1 MPa.
In the invention, in the step (2), the mass-to-volume ratio of the cobalt chloride hexahydrate, the sodium sulfide nonahydrate and the ethylene glycol is preferably 1-3 g: 5-10 g: 50mL, more preferably 1.2 to 2.8 g: 6-9 g: 50mL, more preferably 2.3 g: 8 g: 50 mL.
In the invention, the reaction temperature in the step (2) is preferably 160-200 ℃, more preferably 174-193 ℃, and more preferably 182 ℃; the reaction time is preferably 20 to 30 hours, more preferably 21 to 28 hours, and even more preferably 24 hours.
In the invention, after the reaction in the step (2) is finished, the product is washed and dried; the washing is preferably carried out for 2-5 times, and more preferably 3 times by sequentially and independently washing with water and absolute ethyl alcohol; the drying is vacuum drying; the drying temperature is preferably 70-90 ℃, more preferably 73-86 ℃, and more preferably 78 ℃; the drying time is preferably 6-10 h, more preferably 7-9 h, and even more preferably 8 h; the degree of vacuum for drying is preferably-0.1 MPa.
In the invention, the time of ultrasonic treatment in the step (2) is preferably 2-3 h, more preferably 2.2-2.8 h, and more preferably 2.5 h; the power of the ultrasonic wave is preferably 200-400W, more preferably 230-360W, and even more preferably 300W.
In the invention, the rotation speed of centrifugation in the step (2) is preferably 10000-13000 rpm, more preferably 11000-12000 rpm, and more preferably 11500 rpm; the time for centrifugation is preferably 5 to 10min, more preferably 6 to 9min, and still more preferably 7 min.
In the present invention, the alcohol solution in step (2) is preferably absolute ethanol.
In the present invention, the number of times of alcoholic solution washing in step (2) is preferably 1 to 5 times, and more preferably 3 times.
In the present invention, the drying after the alcohol solution washing in step (2) is preferably vacuum drying; the drying temperature is preferably 70-90 ℃, more preferably 73-89 ℃, and more preferably 80 ℃; the drying time is preferably 6-10 h, more preferably 7-9 h, and even more preferably 8 h; the degree of vacuum for drying is preferably-0.1 MPa.
In the present invention, FeS in step (3) 2 And CoS 2 The mass ratio of (A) to (B) is preferably 2-4: 1, more preferably 2.3 to 3.6: 1, more preferably 2.9: 1; FeS 2 And CoS 2-x The mass ratio of (A) to (B) is preferably 3-7: 1, more preferably 4 to 6: 1, more preferably 5: 1.
in the invention, the rotation speed of the ball milling in the step (3) is preferably 300-500 rpm, more preferably 330-480 rpm, and more preferably 370 rpm; the time for ball milling is preferably 1 to 4 hours, more preferably 1.5 to 3 hours, and even more preferably 2 hours.
The invention also provides the composite catalyst for treating the flue gas, which is prepared by the preparation method.
The invention also provides application of the composite catalyst for flue gas treatment in catalytic flue gas desulfurization.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1)FeS 2 The preparation of (1): 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 for 30min at room temperature, transferring to a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for 24h at 200 ℃, washing the product for 8 times with water, carbon tetrachloride and absolute ethyl alcohol in sequence after the reaction is finished, and drying in vacuum at 60 ℃ and-0.1 MPa for 6h to obtain FeS 2 ；
(2)CoS 2 The preparation of (1): mixing 2.4g of cobalt chloride hexahydrate, 5.3g of sodium sulfide nonahydrate and 50mL of ethylene glycol, transferring the mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting at 180 ℃ for 24 hours, and reactingAfter the reaction is finished, the product is sequentially washed by water and absolute ethyl alcohol for 3 times respectively, and is dried for 7 hours in vacuum at 80 ℃ and under the pressure of-0.1 MPa to obtain CoS 2 ；
(3)FeS 2 @CoS 2 The preparation of (1): FeS obtained in the step (1) 2 And CoS of step (2) 2 According to the mass ratio of 3: 1 ball milling for 2h at the rotating speed of 400rpm to obtain FeS 2 @CoS 2 And (3) compounding a catalyst.
Example 2
(1)FeS 2 The preparation of (1): 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 for 30min at room temperature, transferring to a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for 26h at 210 ℃, sequentially washing products for 6 times with water, carbon tetrachloride and absolute ethyl alcohol respectively after the reaction is finished, and vacuum drying for 10h at 60 ℃ and-0.1 MPa to obtain FeS 2 ；
(2)CoS 2 The preparation of (1): mixing 1.9g of cobalt chloride hexahydrate, 7.4g of sodium sulfide nonahydrate and 50mL of ethylene glycol, then transferring the mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for 20 hours at 190 ℃, sequentially washing the product for 4 times with water and absolute ethyl alcohol respectively after the reaction is finished, and drying for 8 hours in vacuum at 90 ℃ and-0.1 MPa to obtain CoS 2 ；
(3)FeS 2 @CoS 2 The preparation of (1): FeS obtained in the step (1) 2 And CoS of step (2) 2 According to the mass ratio of 3.5: 1 ball milling for 2.5h at the rotating speed of 300rpm to obtain FeS 2 @CoS 2 And (3) compounding a catalyst.
Example 3
(1)FeS 2 The preparation of (1): 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 for 30min at room temperature, transferring to a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for 28h at 220 ℃, sequentially washing the product for 7 times with water, carbon tetrachloride and absolute ethyl alcohol after the reaction is finished, and drying in vacuum at 60 ℃ and-0.1 MPa for 8h to obtain FeS 2 ；
(2)CoS 2-x (0 < x < 2): CoS obtained in example 1 2 Ultrasonically dispersing with 60mL of water for 3h, and thenCentrifuging at 13000rpm for 10min, removing supernatant, washing the product with alcoholic solution 3 times, vacuum drying at 80 deg.C under-0.1 MPa for 7h to obtain CoS 2-x ；
(3)FeS 2 @CoS 2-x (0 < x < 2): FeS obtained in the step (1) 2 And CoS of step (2) 2-x According to the mass ratio of 5: 1 ball milling for 3h at the rotating speed of 500rpm to obtain FeS 2 @CoS 2-x And (3) compounding a catalyst.
Example 4
(1)FeS 2 See example 3 for preparation of;
(2)CoS 2-x (0 < x < 2): CoS obtained in example 1 2 Ultrasonically dispersing with 60mL of water for 2.5h, centrifuging at 10000rpm for 7min, removing supernatant, washing the product with alcoholic solution for 2 times, and vacuum drying at 70 deg.C under-0.1 MPa for 10h to obtain CoS 2-x ；
(3)FeS 2 @CoS 2-x (0 < x < 2): FeS obtained in the step (1) 2 And CoS of step (2) 2-x According to the mass ratio of 6: 1 ball milling for 3h at the rotating speed of 300rpm to obtain FeS 2 @CoS 2-x And (3) compounding a catalyst.
The performance test method comprises the following steps:
(1) selecting a coal-fired boiler in a boiler workshop of a large coal-fired thermal power plant, spraying 30% of hydrogen peroxide at the rate of 50mL/min under the flow of 1L/min, and simultaneously enabling the gas to pass through a reactor filled with 125mg of the composite catalyst of the embodiment 1-4 respectively; collecting air samples at the inlet and outlet of the processor at different times with porous glass plate absorption tubes filled with 10.0mL of formaldehyde buffer solution;
(2) preparing 0.0, 0.40, 0.80, 1.20 and 1.60mg/mL sulfur dioxide standard solution series, adding 1.0mL of 3g/L sulfamic acid solution into each standard tube, shaking up, and standing for 10 min; adding 1.0mL of 1mol/L sodium hydroxide solution, then quickly pouring the solution in the standard tube into a colorimetric test tube with a plug containing 3mL of pararosaniline hydrochloride solution, uniformly mixing, and reacting for 15min in a water bath at 20 ℃; under the condition of wavelength of 575nm, taking water as reference to measure absorbance, 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 the pararosaniline hydrochloride, sucking 20mL of the solution in a volumetric flask with 250mL, adding 200mL of phosphoric acid solution, and diluting the solution with water to scale;
(3) washing the air inlet pipe for 3 times by using absorption liquid, taking 4.0mL of pararosaniline hydrochloride solution into a colorimetric test tube with a plug, adding 6mL of absorption liquid, and uniformly mixing; and (3) measuring the absorbance mean value of the sample in the step (1) by using the operation conditions of the measurement standard series, and obtaining the sulfur dioxide concentration (mg/mL) from the standard curve after subtracting the absorbance value of the blank from the absorbance mean value of the sample.
Wherein, the sulfur dioxide treatment amount is calculated at different time, and is expressed by C, and the calculation formula is C ═ C 0 -C 1 In which C is 0 Is the initial concentration of sulfur dioxide, i.e. the concentration of sulfur dioxide at the inlet of the treater, C 1 The concentration of sulphur dioxide in the exhaust gas, i.e. the outlet concentration, is the corresponding treatment time. The removal rate is the ratio of the removal amount of sulfur dioxide to the initial concentration, and the calculation mode is C/C 0 (%). The results of the sulfur dioxide removal rate at various times are shown in table 1.
TABLE 1 Sulfur dioxide removal Rate results
As can be seen from Table 1, the composite catalyst of the invention has high catalytic efficiency when used in flue gas desulfurization treatment, can achieve a removal rate of over 90% when treated for 30s, can completely remove sulfur dioxide in flue gas after 8min treatment, realizes purification and desulfurization of flue gas, and reduces treatment cost because the treated sulfur dioxide is absorbed by water to obtain sulfuric acid with economic benefits.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the composite catalyst for flue gas treatment is characterized by comprising the following steps of:
(1)FeS 2 the preparation of (1): grinding ferrous sulfate, sodium thiosulfate pentahydrate and sulfur powder, and reacting with water to obtain FeS 2 ；
(2)CoS 2 The preparation of (1): mixing cobalt chloride hexahydrate, sodium sulfide nonahydrate and ethylene glycol, and reacting to obtain CoS 2 ；
CoS 2-x The preparation of (1): adding CoS 2 Mixing with water, sequentially performing ultrasonic treatment and centrifugation, washing the product with an alcohol solution, and drying to obtain CoS 2-x ；
(3)FeS 2 @CoS 2 Or FeS 2 @CoS 2-x The preparation of (1): FeS obtained in the 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.
2. The preparation method of the composite catalyst for flue gas treatment according to claim 1, wherein the mass ratio of the ferrous sulfate, the sodium thiosulfate pentahydrate and the sulfur powder in the step (1) is 2-4: 1-4: 0.1 to 1; the mass-volume ratio of the ferrous sulfate to the water is 2-4 g: 50-100 mL.
3. The preparation method of the composite catalyst for flue gas treatment according to claim 1 or 2, wherein the reaction temperature in the step (1) is 200-230 ℃; the reaction time is 20-30 h.
4. The preparation method of the composite catalyst for flue gas treatment according to claim 3, wherein the mass-to-volume ratio of the cobalt chloride hexahydrate, the sodium sulfide nonahydrate and the ethylene glycol in the step (2) is 1-3 g: 5-10 g: 50 mL.
5. The preparation method of the composite catalyst for flue gas treatment according to claim 1, 2 or 4, wherein the reaction temperature in the step (2) is 160-200 ℃; the reaction time is 20-30 h.
6. The preparation method of the composite catalyst for flue gas treatment according to claim 5, wherein the ultrasonic treatment time in the step (2) is 2-3 h; the power of the ultrasonic wave is 200-400W.
7. The preparation method of the composite catalyst for flue gas treatment according to claim 1, 4 or 6, wherein FeS is used in the step (3) 2 And CoS 2 The mass ratio of (A) to (B) is 2-4: 1; FeS 2 And CoS 2-x The mass ratio of (A) to (B) is 3-7: 1.
8. the preparation method of the composite catalyst for flue gas treatment according to claim 7, wherein the rotation speed of the ball mill in the step (3) is 300-500 rpm; the ball milling time is 1-4 h.
9. A composite catalyst for flue gas treatment prepared by the preparation method of any one of claims 1 to 8.
10. Use of a composite catalyst for flue gas treatment according to claim 9 in catalytic flue gas desulfurization.
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| GB1511865A (en) * | 1974-08-27 | 1978-05-24 | Nippon Oil Co Ltd | Process for oxidising sulphur dioxide |
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| WO2012031330A1 (en) * | 2010-09-10 | 2012-03-15 | The University Of Queensland | Catalyst and method for producing same |
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