CN102423711A - Catalyst for removing SO2 from flue gas through dry process, its preparation method and application - Google Patents
Catalyst for removing SO2 from flue gas through dry process, its preparation method and application Download PDFInfo
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- CN102423711A CN102423711A CN2011103075203A CN201110307520A CN102423711A CN 102423711 A CN102423711 A CN 102423711A CN 2011103075203 A CN2011103075203 A CN 2011103075203A CN 201110307520 A CN201110307520 A CN 201110307520A CN 102423711 A CN102423711 A CN 102423711A
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- catalyst
- flue gas
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Abstract
The invention relates to a catalyst for removing SO2 from flue gas through a dry process. The catalyst comprises the following components by mass: 1%-8% of VOSO4, and 92%-99% of an activated carbon based material, which, as a carrier, has a specific surface area of 400-1000m<2>/g. A VOSO4 solution is immersed on the activated carbon based material in an isopyknic way for preparing the catalyst. The catalyst of the invention has the advantages of low preparation cost and high desulphurization activity.
Description
Affiliated field
The invention belongs to SO in the dry removal flue gas
2Catalyst and preparation method and application.
Background technology
SO
2Be to pollute the heaviest sour gas in the coal-fired product of China; Industry is at present gone up the conventional mode that removes and still is the wet method calcium-based desulfurization, and this method water consumption in running is big, produce secondary pollution, make dry desulfurization become development trend with drawbacks such as existing denitration technology do not match.Fact proved, activated carbon directly is used for flue gas desulfurization, near ambient temperature and low-speed (＜1000h
-1) under, having the higher activity [Fuel, 1997,76 (6): 549-553] that removes, the MET-Mitsui-BF method [Fuel Processing Technology, 2000,65-66,395-405] of Japan's exploitation directly is used for flue gas with activated coke and removes SO
2, realized industrialization at present.This method is at 100-200 ℃, reaction velocity 400h
-1In the time, have good desulphurizing activatedly, but total Sulfur capacity is lower, and makes that the consumption of activated coke is big because its reaction velocity is low, and equipment operating cost is higher.Ma etc. [Applied Catalysis B:Environmental, 2003,45 (4): 301-309] find Fe (NO
3)
3Solution impregnation is processed Fe through high-temperature calcination after AC goes up
2O
3/ AC catalyst makes the desulphurizing activated of AC increase under 200 ℃, a kind of while sulphur denitrating catalyst and the application process (patent No.s: the 03145680.4) V of exploitation such as its [Fuel Processing Technology, 2008,89 (3), 242-248] and Wang Yanli
2O
5/ AC catalyst has significantly improved AC to SO
2Adsorption capacity, it is active to have a good desulphurization denitration at 150-200 ℃, has broad application prospects.But because Fe
2O
3/ AC and V
2O
5/ AC Preparation of catalysts will be passed through long high-temperature calcination and oxidizing process, makes preparation cost higher, and causes the change of physical propertys such as absorbent charcoal based material specific surface, pore structure easily, and then influences that it is desulphurizing activated.Therefore, seek a kind of low preparation cost, dry method, efficiently remove flue gas SO
2Catalyst have very strong practical value.
Summary of the invention
The object of the present invention is to provide low, the desulphurizing activated high dry desulfurization catalyst of a kind of preparation cost and preparation method and application.
Catalyst of the present invention is with VOSO
4Solution is dipping solution, and carrier is absorbent charcoal based material, carrier B ET specific area 400-1000m
2/ g.Each constituent mass percentage is VOSO
4: 1%-8%, absorbent charcoal based material: 92%-99%.
Aforesaid absorbent charcoal based material is active carbon, activated coke or activated carbon fiber.
Preparation of catalysts method of the present invention is with VOSO
4The solution incipient impregnation is on absorbent charcoal based material, and room temperature leaves standstill 1-3h, and 100-150 ℃ of air drying 3-8h promptly gets required catalyst.
The operating condition of catalyst low-temp desulfurization of the present invention: fixed bed or moving-burden bed reactor, temperature 40-160 ℃, normal pressure, reaction velocity 400-4000h
-1
Compare with the desulphurization catalyst of absorbent charcoal based material carrying metal oxide, the present invention has following advantage:
1. single solution impregnation, the solution preparation is simple.
2. only need low temperature drying promptly to get catalyst, need not calcining and oxidizing process for a long time, both simplified technology, significantly reduced preparation cost, avoided destruction again absorbent charcoal based material physical property.
With active carbon direct desulfurization compared with techniques, the present invention has following advantage:
1. cryogenic absorption SO
2Ability stronger.
2. the air speed of using is wider, at 400-4000h
-1Scope in desulphurizing activated higher, help to reduce catalyst consumption, reduce operating cost.
3. can be applicable to moving bed or fixed bed reactors.
In a word, compared with prior art, the present invention had both significantly improved the cryogenic absorption SO of active carbon own
2Ability, avoided metal oxide catalyst complicated process of preparation, problem that preparation cost is high again, have good application prospects.
The specific embodiment
Embodiment one:
With 30ml concentration is 0.2243mol/L VOSO
4(specific area is 915m to solution impregnation at 30-60 purpose 30g active carbon
2/ g) on, room temperature leaves standstill 3h, 110 ℃ of dry 5h promptly get mass percent and are 3.5% VOSO
4/ AC catalyst.This catalyst is packed in the fixed bed reactors, and reaction temperature is controlled at 120 ℃, feeds simulated flue gas SO under the normal pressure
21500ppm, O
24.5%, steam 2.5%, balance gas N
2, reaction velocity is controlled at 400h
-1, SO
2Time of break-through be 2930min, it is 14.62% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment two:
With 15ml concentration is 0.0620mol/L VOSO
4(specific area is 802m to solution impregnation at 30-60 purpose 15g active carbon
2/ g) on, room temperature leaves standstill 1h, 100 ℃ of dry 8h promptly get mass percent and are 1% VOSO
4/ AC catalyst.This catalyst is packed in the fixed bed reactors, and reaction temperature is controlled at 80 ℃, feeds simulated flue gas SO under the normal pressure
21500ppm, O
24.5%, steam 2.5%, balance gas N
2, reaction velocity is controlled at 800h
-1, SO
2Time of break-through be 795min, it is 9.51% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment three:
With 6ml concentration is 0.3433mol/LVOSO
4(specific area is 650m to solution impregnation at 30-60 purpose 6g active carbon
2/ g) on, room temperature leaves standstill 2h, 150 ℃ of dry 3h promptly get mass percent and are 5.3% VOSO
4/ AC catalyst.This catalyst is packed in the fixed bed reactors, and reaction temperature is controlled at 40 ℃, feeds simulated flue gas SO under the normal pressure
21500ppm, O
24.5%, steam 2.5%, balance gas N
2, reaction velocity is controlled at 2000h
-1, SO
2Time of break-through be 180min, it is 6.90% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment four:
With 3ml concentration is 0.1252mol/L VOSO
4(specific area is 400m to solution impregnation at 30-60 purpose 3g active carbon
2/ g) on, room temperature leaves standstill 3h, 120 ℃ of dry 8h promptly get mass percent and are 2% VOSO
4/ AC catalyst.This catalyst is packed in the fixed bed reactors, and reaction temperature is controlled at 60 ℃, feeds simulated flue gas SO under the normal pressure
21500ppm, O
24.5%, steam 2.5%, balance gas N
2, reaction velocity is controlled at 4000h
-1, SO
2Time of break-through be 45min, it is 2.80% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment five:
With 8ml concentration is 0.5368mol/L VOSO
4(specific area is 562m to solution impregnation at 30-60 purpose 8g active carbon
2/ g) on, room temperature leaves standstill 2h, 130 ℃ of dry 5h promptly get mass percent and are 8% VOSO
4/ AC catalyst.This catalyst is packed in the fixed bed reactors, and reaction temperature is controlled at 100 ℃, feeds simulated flue gas SO under the normal pressure
21500ppm, O
24.5%, steam 2.5%, balance gas N
2, reaction velocity is controlled at 1500h
-1, SO
2Time of break-through be 240min, it is 4.76% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment six
With 4ml concentration is 0.4646mol/L VOSO
4(specific area is 423m to solution impregnation at 30-60 purpose 4g active carbon
2/ g) on, room temperature leaves standstill 1h, 140 ℃ of dry 6h promptly get mass percent and are 7% VOSO
4/ AC catalyst.This catalyst is packed in the fixed bed reactors, and reaction temperature is controlled at 160 ℃, feeds simulated flue gas SO under the normal pressure
21500ppm, O
24.5%, steam 2.5%, balance gas N
2, reaction velocity is controlled at 3300h
-1, SO
2Time of break-through be 60min, it is 3.31% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Claims (4)
1. one kind is used for dry removal flue gas SO
2Catalyst, it is characterized in that each constituent mass percentage of catalyst is VOSO
4: 1%-8%, absorbent charcoal based material: 92%-99%, carrier specific area 400-1000m
2/ g.
2. a kind of dry removal flue gas SO that is used for as claimed in claim 1
2Catalyst, it is characterized in that described absorbent charcoal based material is active carbon, activated coke or activated carbon fiber.
3. according to claim 1 or claim 2 a kind of dry removal flue gas SO that is used for
2The Preparation of catalysts method, it is characterized in that the Preparation of catalysts method is with VOSO
4The solution incipient impregnation is on absorbent charcoal based material, and room temperature leaves standstill 1-3h, and 100-150 ℃ of air drying 3-8h promptly gets required catalyst.
4. according to claim 1 or claim 2 a kind of dry removal flue gas SO that is used for
2Application of Catalyst, it is characterized in that comprising following operating condition: be applied to fixed bed or moving-burden bed reactor, temperature 40-160 ℃, normal pressure, reaction velocity 400-4000h
-1
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|---|---|---|---|
| CN2011103075203A CN102423711A (en) | 2011-10-08 | 2011-10-08 | Catalyst for removing SO2 from flue gas through dry process, its preparation method and application |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102847432A (en) * | 2012-09-24 | 2013-01-02 | 河北科技大学 | Method for adsorption-catalytic oxidation of sulfur dioxide by using metal modified antibiotic bacterium residue activated carbon |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648107A (en) * | 2009-09-11 | 2010-02-17 | 山东迅达化工集团有限公司 | Catalytic oxidation adsorption desulfurizer and preparation method thereof |
-
2011
- 2011-10-08 CN CN2011103075203A patent/CN102423711A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648107A (en) * | 2009-09-11 | 2010-02-17 | 山东迅达化工集团有限公司 | Catalytic oxidation adsorption desulfurizer and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102847432A (en) * | 2012-09-24 | 2013-01-02 | 河北科技大学 | Method for adsorption-catalytic oxidation of sulfur dioxide by using metal modified antibiotic bacterium residue activated carbon |
| CN102847432B (en) * | 2012-09-24 | 2015-04-22 | 河北科技大学 | Method for adsorption-catalytic oxidation of sulfur dioxide by using metal modified antibiotic bacterium residue activated carbon |
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Application publication date: 20120425 |