CN102407102A - V205/AC desulfurization catalyst, preparation method and application - Google Patents
V205/AC desulfurization catalyst, preparation method and application Download PDFInfo
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- CN102407102A CN102407102A CN2011103072563A CN201110307256A CN102407102A CN 102407102 A CN102407102 A CN 102407102A CN 2011103072563 A CN2011103072563 A CN 2011103072563A CN 201110307256 A CN201110307256 A CN 201110307256A CN 102407102 A CN102407102 A CN 102407102A
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Abstract
Mass percentage of each component of V205/AC desulfurization catalyst is as follows: V205 0.5-10% and activated carbon-based material 90-99.5%. Specific surface area of carrier is 400-1000m2/g and granularity is 30-60 screen meshes. The preparation method comprises: isovolumetric dipping VOSO4 solution on the activated carbon-based material, depositing at room temperature for 1-3 hours, drying in air at 50-80 degrees centigrade for 2-5 hours, and hot processing under inert atmosphere at 300-500 degrees centigrade for 1-3 hours to obtain the catalyst. The invention has low preparation cost and high desulfurization rate.
Description
Affiliated field
The invention belongs to SO in the dry removal flue gas
2Catalyst and preparation method and application.
Background technology
Coal is as the topmost primary energy of China, burning utilize produce in the process such as SO
2, NO
x, pollutant such as heavy metal Hg, major polluting atmosphere environment.SO wherein
2Ratio at the pollution that caused by coal burning thing is maximum, is the main component of China's acid rain.The existing industrial treatment mode of China mainly is a wet method calcium-based desulfurization technology; But this technology exist water consumption big, be prone to cause secondary pollution, with shortcoming such as be about to require the denitration technology of carrying out and do not match, and dry desulfurizing process more and more receives people's attention owing to can solve the above-mentioned shortcoming in the wet desulphurization.In this regard, the MET-Mitsui-BF method [Fuel Processing Technology, 2000,65-66,395-405] of Japan exploitation directly is used for flue gas with activated coke and removes SO
2, at 100-200 ℃, reaction velocity 400h
-1In the time, have good desulphurizing activatedly, and this method has realized industrialization at present.But because activated coke (Activated Coke, AC) absorption SO own
2Its Sulfur capacity and the reaction velocity of making limited in one's ability lower, thereby make that the consumption of activated coke is big, equipment operating cost is higher.A kind of while desulphurization denitration catalyst and the application process (patent No.s: the 03145680.4) V of exploitation such as Ma etc. [Fuel Processing Technology, 2008,89 (3), 242-248] and Wang Yanli
2O
5/ AC catalyst is verified can to solve active carbon absorption SO itself
2The defective that ability is lower has good desulphurization denitration activity.Its Preparation of catalysts is with NH
4VO
3With oxalic acid form 60 ℃ the time by a certain percentage mixed solution be maceration extract, through 50 ℃ of dry 12h in the air, 120 ℃ of dry 5h, 500 ℃ of argon gas or nitrogen atmosphere down in calcining 5-8h and the 250 ℃ of air oxidation 5h and V
2O
5/ AC catalyst, the absorption Sulfur capacity obviously increases, but the preparation process is complicated, especially for making NH
4VO
3The rising that the long-time high-temperature calcination of fully decomposing and carrying out and oxidation directly cause the Preparation of Catalyst cost, and the process of oxidation in 250 ℃ of following air causes carbon to ablate easily, thus the pore structure of change catalyst is unfavorable for SO
2Absorption.
Summary of the invention
The object of the present invention is to provide a kind of preparation cost low, the dry desulfurization V that desulfurization performance is high
2O
5/ AC catalyst and preparation method and application.
Catalyst of the present invention is with V
2O
5Be active component, absorbent charcoal based material (active carbon, activated coke, activated carbon fiber) is a carrier, carrier B ET specific area 400-1000m
2/ g, granularity is the 30-60 order, the mass percent of each component is: V
2O
5: 0.5%-10%, absorbent charcoal based material: 90%-99.5%.
The preparation of carbon base catalyst of the present invention is the composition by catalyst, with VOSO
1The solution incipient impregnation is on absorbent charcoal based material, and room temperature leaves standstill 1-3h, 50-80 ℃ of air drying 2-5h, and 300-500 ℃ of heat treatment 1-3h promptly gets required catalyst under the inert atmosphere.
The operating condition of catalyst low-temp desulfurization of the present invention: fixed bed or moving-burden bed reactor, temperature 40-200 ℃, normal pressure, reaction gas speed 400-8000h
-1
With traditional V
2O
5/ AC Preparation of catalysts technology is compared, and biggest advantage of the present invention is significantly to have simplified technological process, has reduced V
2O
5/ AC Preparation of catalysts cost:
1. adopt single solution impregnation, the dipping solution preparation is simple.
2. a step drying need not dry run more than 100 ℃.
3. not only reduce the calcining heat in the inert atmosphere, and shortened calcination time.
4. avoided oxidizing process in 250 ℃ of air, both further reduced preparation cost, avoided the destruction of oxidizing process again, helped improving the desulphurizing activated of catalyst absorbent charcoal based material physical property.
5. the V for preparing
2O
5/ AC is desulphurizing activated higher, absorption SO
2Ability stronger.
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, 50 ℃ of dry 5h, 100ml/minN
2In 500 ℃ of heat treatment 1h, promptly get mass percent and be 2% V under the atmosphere
2O
5/ 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 3600min, it is 17.80% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment two:
With 12ml concentration is 0.0620mol/L VOSO
4(specific area is 716m to solution impregnation at 30-60 purpose 12g active carbon
2/ g) on, room temperature leaves standstill 2h, 80 ℃ of dry 3h, 100ml/minN
2In 300 ℃ of heat treatment 1h, promptly get mass percent and be 0.5% V under the atmosphere
2O
5/ 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 1000h
-1, SO
2Time of break-through be 540min, it is 7.79% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment three:
With 3ml concentration is the VOSO of 1.0868mol/L
4(specific area is 553m to solution impregnation at 30-60 purpose 3g active carbon
2/ g) on, room temperature leaves standstill 3h, 80 ℃ of dry 2h, 100ml/min N
2In 500 ℃ of heat treatment 2h, promptly get mass percent and be 9% V under the atmosphere
2O
5/ 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 4000h
-1, SO
2Time of break-through be 90min, it is 4.65% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment four:
With 6ml concentration is the VOSO of 0.5784mol/L
4(specific area is 841m to solution impregnation at 30-60 purpose 6g active carbon
2/ g) on, room temperature leaves standstill 1h, 60 ℃ of dry 4h, 100ml/minN
2In 500 ℃ of heat treatment 2h, promptly get mass percent and be 5% V under the atmosphere
2O
5/ 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 2000h
-1, SO
2Time of break-through be 330min, it is 8.50% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment five:
With 3ml concentration is the VOSO of 0.3399mol/L
4(specific area is 782m to solution impregnation at 30-60 purpose 3g active carbon
2/ g) on, room temperature leaves standstill 2h, 70 ℃ of dry 3h, 100ml/minN
2In 400 ℃ of heat treatment 3h, promptly get mass percent and be 3% V under the atmosphere
2O
5/ 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 4000h
-1, SO
2Time of break-through be 150min, it is 7.96% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment six:
With 1.5ml concentration is the VOSO of 0.8271mol/L
4(specific area is 603m to solution impregnation at 30-60 purpose 1.5g active carbon
2/ g) on, room temperature leaves standstill 3h, 70 ℃ of dry 3h, 100ml/min N
2In 500 ℃ of heat treatment 1h, promptly get mass percent and be 7% V under the atmosphere
2O
5/ AC catalyst.This catalyst is packed in the fixed bed reactors, and reaction temperature is controlled at 200 ℃, 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 8000h
-1, SO
2Time of break-through be 45min, it is 5.60% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment seven:
With 3ml concentration is the VOSO of 0.2242mol/L
4(specific area is 657m to solution impregnation at 30-60 purpose 3g active carbon
2/ g) on, room temperature leaves standstill 2h, 50 ℃ of dry 5h, 100ml/min N
2In 500 ℃ of heat treatment 2h, promptly get mass percent and be 2% V under the atmosphere
2O
5/ 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 4000h
-1, SO
2Time of break-through be 90min, it is 5.65% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Embodiment eight:
With 3ml concentration is the VOSO of 0.2242mol/L
4(specific area is 410m to solution impregnation at 30-60 purpose 3g active carbon
2/ g) on, room temperature leaves standstill 2h, 50 ℃ of dry 5h, 100ml/min N
2In 500 ℃ of heat treatment 2h, oxidation 3h in 250 ℃ of air promptly gets mass percent and is 2% V under the atmosphere
2O
5/ 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 4000h
-1, SO
2Time of break-through be 60min, it is 4.23% that desulfurization degree drops to 90% o'clock Sulfur capacity.
Claims (4)
1. V
2O
5/ AC desulphurization catalyst is characterized in that the mass percent of each component of catalyst is: V
2O
5: 0.5%-10%, absorbent charcoal based material: 90%-99.5%, the specific area 400-1000m of carrier
2/ g, granularity is the 30-60 order.
2. a kind of V as claimed in claim 1
2O
5/ AC desulphurization catalyst is characterized in that described carrier is active carbon, activated coke or activated carbon fiber.
3. according to claim 1 or claim 2 a kind of V
2O
5The preparation method of/AC desulphurization catalyst is characterized in that it being the composition by catalyst, with VOSO
4The solution incipient impregnation is on absorbent charcoal based material, and room temperature leaves standstill 1-3h, 50-80 ℃ of air drying 2-5h, and 300-500 ℃ of heat treatment 1-3h promptly gets required catalyst under the inert atmosphere.
4. according to claim 1 or claim 2 a kind of V
2O
5The application of/AC desulphurization catalyst is characterized in that operating condition is to be applied to fixed bed or moving-burden bed reactor, temperature 40-200 ℃, and normal pressure, reaction gas speed 400-8000h
-1
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Cited By (4)
| 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 |
| CN103433034A (en) * | 2013-09-13 | 2013-12-11 | 国电环境保护研究院 | Low-temperature SCR (Selective Catalytic Reduction) catalyst based on active coke loaded manganese-cerium composite oxide and preparation method of low-temperature SCR catalyst |
| CN106925284A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of preparation method of high efficiency, low cost desulfurization catalyst of flue gas |
| CN109158115A (en) * | 2018-08-21 | 2019-01-08 | 山东京博众诚清洁能源有限公司 | A kind of catalyst and preparation method thereof, sulphuric acid plant and acid preparation method |
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 CN2011103072563A patent/CN102407102A/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 (6)
| 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 |
| CN103433034A (en) * | 2013-09-13 | 2013-12-11 | 国电环境保护研究院 | Low-temperature SCR (Selective Catalytic Reduction) catalyst based on active coke loaded manganese-cerium composite oxide and preparation method of low-temperature SCR catalyst |
| CN106925284A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of preparation method of high efficiency, low cost desulfurization catalyst of flue gas |
| CN109158115A (en) * | 2018-08-21 | 2019-01-08 | 山东京博众诚清洁能源有限公司 | A kind of catalyst and preparation method thereof, sulphuric acid plant and acid preparation method |
| CN109158115B (en) * | 2018-08-21 | 2021-06-15 | 山东京博众诚清洁能源有限公司 | Catalyst and preparation method thereof, acid making device and acid making method |
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Application publication date: 20120411 |