CN1232347C - Honeycomb ceramic catalyst for simultaneously desulfurizing and denitrifying fume and its preparation and use - Google Patents
Honeycomb ceramic catalyst for simultaneously desulfurizing and denitrifying fume and its preparation and use Download PDFInfo
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- CN1232347C CN1232347C CN 03122802 CN03122802A CN1232347C CN 1232347 C CN1232347 C CN 1232347C CN 03122802 CN03122802 CN 03122802 CN 03122802 A CN03122802 A CN 03122802A CN 1232347 C CN1232347 C CN 1232347C
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- flue gas
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Abstract
The present invention relates to honeycomb ceramic catalyst for simultaneously desulphurizing and denitrifying flue gas. The present invention uses cordierite honeycomb ceramic after the surface treatment as a carrier, an activated alumina film and load active components of CuO and Na2O are coated on the cordierite honeycomb ceramic, and a dipping method is used for preparing the honeycomb ceramic catalyst. The present invention has about 88% of denitration rate on the atmospheric pressure flue gas, when the desulfurization rate is higher than 80%, the amount of SO2 adsorbed by each gram of the catalyst is about 62 mg, the bed layer resistance is small, and the present invention is suitable for the industrial application.
Description
Technical field:
The invention belongs to and remove flue gas SO simultaneously
2And NO
xA kind of honeycombed catalyst and preparation and application.
Background technology:
Since the eighties, along with China's rapid economic development, the coal consumption amount increases day by day, coal-fired SO
2Constantly increase with the NOx discharge capacity, become the primary pollution source of atmospheric environment.According to coal conversion, 1998,21 (4): 7-11 report, SO
2A large amount of dischargings with NOx cause environmental destruction, and the acid rain phenomenon is serious.Because the acid rain sedimentation is caused agricultural, forestry and material damage economic loss every year is up to more than 200 hundred million yuan.According to China's strategy of sustainable development and China's Agenda 21, must be in the long run, be based on national conditions, exploitation adapts to the flue gases purification of different scales.
Flue gases purification is divided into independent desulphurization denitration and while desulphurization denitration, because the desulphurization denitration technology is saved manpower, financial resources and material resources simultaneously, enjoys the researcher to pay attention to.At present, being used for simultaneously, the technology of desulphurization denitration mainly contains Fuel and Energy Abstracts, 1997,38 (3): 189, the electronic beam method of 97/02388 report, Fuel and Energy Abstracts, 1998,39 (3): 216,98/02396 and Fuel, 1997,76 (6): the activated carbon method of 549-560 report, Ind.Eng.Chem.Res.2000, the CuO/ γ-Al of 39:3868-3874 report
2O
3Method.Although electronic beam method has been realized industrialization, because operating cost is high-leveled and difficult with large-scale promotion at home, and existing catalyst (comprises active carbon and CuO/ γ-Al
2O
3) because its graininess shape causes bed resistance big, be difficult to overcome dust and stop up, only rest on theoretical research and laboratory or pilot scale stage, so far none routine industrialization.Given this, a kind of bed resistance of necessary exploitation little, can overcome exhaust gas dust influence, desulphurization denitration catalyst when being suitable for industrial applications.
Honeycombed catalyst have pressure drop little, overcome advantage such as dust obstruction, be widely used in denitrating flue gas, but all do not had honeycombed catalyst to be used for the report of desulphurization denitration simultaneously so far both at home and abroad.
Summary of the invention:
It is little to the purpose of this invention is to provide a kind of bed resistance, is suitable for cellular while desulphurization denitration catalyst and the preparation and the application of industrial applications.
Catalyst of the present invention is first carrier with the surface-treated cordierite honeycomb ceramic, and the activated alumina film is second carrier, load active component CuO and Na
2O, the consisting of of catalyst:
Pottery 70-81wt.%,
Activated alumina 19-30wt.%,
Carrier loaded 8.5-12.5 gram CuO of per 100 grams and 4.0-5.4 gram Na
2O
Preparation of catalysts method of the present invention comprises the steps:
(1) with aluminum nitrate: distilled water=0.6～0.8: 1 mass ratio, aluminum nitrate is added in the distilled water, all the dissolving back adds urea, wherein urea: the mass ratio of distilled water is 0.3～0.5: 1, and the gained glue is a coating liquid;
(2) the surface-treated cordierite honeycomb ceramic is soaked in the above-mentioned glue, takes out behind placement 6～8h, in 50～110 ℃ of down dry 8～12h, then in 400～500 ℃ of calcining 6～12h, the ceramic monolith of promptly once being filmed;
(3) can to obtain ceramic content be 70-81wt.% to repeating step (2), and activated alumina content is the 19-30wt.% ceramic monolith of filming;
(4) be that adsorbate is made blank assay to the adsorbance of the ceramic monolith of filming with water, the volume adsorption that obtains 100 gram carriers is the X milliliter;
(5) by carrier loaded 8.5-12.5 gram CuO of per 100 grams and 4.0-5.4 gram Na
2O, preparation CuO content are 8.5-12.5 gram CuO/Xml, Na
2O content is 4.0-5.4 gram Na
2Cu (the NO of O/Xml
3)
2And NaNO
3Mixed liquor is coated with membrane carrier with mixed liquid dipping, takes out behind placement 6～10h, in 50～110 ℃ of down dry 8～12h, in 400～500 ℃ of calcining 6～10h, promptly gets catalyst then.
The aforesaid volume that is coated with the used mixed liquor of membrane carrier with mixed liquid dipping is for more than or equal to the X milliliter.
The method that the prepared catalyst of the present invention is applied to carry out simultaneously desulphurization denitration comprises the steps:
(1) with NH
3Be reducing agent, press NH
3: NO
xMol ratio is 1-1.2: 1 ratio is with NH
3In the input flue gas;
(2) catalyst is placed fixed bed reactors, contain NH
3Flue gas enter fixed bed reactors, at atmospheric operation, operating temperature is 400 ℃, the operation air speed is 1700～3000h
-1Condition under carry out desulphurization denitration simultaneously.
The present invention has following advantage:
1. desulphurization denitration catalyst when being preparing carriers with the cordierite honeycomb ceramic, bed resistance is little, is applicable to industrial applications.
2. this catalyst can overcome the clogging that dust causes.
3. this catalyst has higher denitration activity and well desulphurizing activated.
The specific embodiment:
Embodiment 1
Take by weighing 152gAl (NO
3)
39H
2O is dissolved in the 200ml distilled water, and heating all adds the 80g urea in the dissolving back, promptly gets coating liquid.With taking out behind the above-mentioned coating liquid immersion surface treatment pottery 8h, in 50 ℃ of dry 8h, 110 ℃ of dry 12h, 500 ℃ of calcining 6h.Repeat to film obtain that ceramic content is 81% for 5 times, activated alumina content is 19% the membrane carrier that is coated with.With water is that adsorbent is made blank assay to the adsorbance of the ceramic monolith of filming, and finds that the adsorbable water yield of 100 gram carriers is 36 milliliters.Preparation CuO content is 0.236gCuO/ml, Na
2O content is 0.11gNa
2Cu (the NO of O/ml
3)
2And NaNO
3Mixed liquor, dipping is coated with membrane carrier, takes out behind the placement 6h, in 50 ℃ of dry 8h, 110 ℃ of dry 12h, 500 ℃ of calcining 6h obtain carrier loaded 8.5 gram CuO of per 100 grams and 4.0 gram Na
2The catalyst of O.The catalyst of getting Φ 21 * 30mm places reaction tube (Φ 21mm), and the control reaction temperature is at 400 ℃, and air speed is 2300h
-1, flue gas consists of 1500ppm SO
2, 400ppmNO, 5.4%O
2, 2.5%H
2O, balance Ar is with 400ppm NH
3Make reducing agent, stable state NO removal efficiency is 92% under this operating condition, SO
2Conversion ratio is 6.0% greater than 80% Sulfur capacity.
Embodiment 2
Method for preparing catalyst is with embodiment 1.The catalyst of getting Φ 21 * 30mm places reaction tube (Φ 21mm), and the control reaction temperature is at 400 ℃, and air speed is 1800h
-1, flue gas consists of 1800ppmSO
2, 500ppm NO, 5.4%O
2, 2.5%H
2O, balance Ar is with 600ppm NH
3Make reducing agent, stable state NO removal efficiency is 92% under this operating condition, SO
2Conversion ratio is 6.2% greater than 80% Sulfur capacity.
Embodiment 3
Method for preparing catalyst is with embodiment 1.The catalyst of getting Φ 21 * 30mm places reaction tube (Φ 21mm), and the control reaction temperature is at 400 ℃, and air speed is 1500h
-1, flue gas consists of 2200ppmSO
2, 550ppm NO, 5.4%O
2, 2.5%H
2O, balance Ar is with 550ppm NH
3Make reducing agent, stable state NO conversion ratio is 90% under this operating condition, SO
2It is 6.6% that conversion ratio reaches 80% Sulfur capacity.
Embodiment 4
Take by weighing 160gAl (NO
3)
39H
2O is dissolved in the 200ml distilled water, and heating all adds the 100g urea in the dissolving back, promptly gets coating liquid.With taking out behind the above-mentioned coating liquid immersion surface treatment pottery 6h, in 50 ℃ of dry 10h, 110 ℃ of dry 12h are then in 400 ℃ of calcining 12h.Repeat to film obtain that ceramic content is 75% for 7 times, activated alumina content is 25% the membrane carrier that is coated with.With water is that adsorbent is made blank assay to the adsorbance of the ceramic monolith of filming, and finds that the adsorbable water yield of 100 gram carriers is 40 milliliters.Preparation CuO content is 0.265gCuO/ml, Na
2O content is 0.14gNa
2Cu (the NO of O/ml
3)
2And NaNO
3Mixed liquor, dipping is coated with membrane carrier, takes out behind the placement 8h, in 50 ℃ of dry 8h, 110 ℃ of dry 12h, 450 ℃ of calcining 8h make carrier loaded 10.6 gram CuO of per 100 grams and 5.4 gram Na
2The catalyst of O.The catalyst of getting Φ 21 * 30mm places reaction tube (Φ 21mm), and the control reaction temperature is at 400 ℃, and air speed is 2300h
-1, flue gas consists of 1800ppmSO
2, 450ppm NO, 5.4%O
2, 2.5%H
2O, balance Ar is with 500ppm NH
3Make reducing agent, stable state NO removal efficiency is 85% under this operating condition, SO
2It is 6.8% that conversion ratio reaches 80% Sulfur capacity.
Embodiment 5
Carrier coating method and blank assay are with embodiment 4.Preparation CuO content is 0.313gCuO/ml, Na
2O content is 0.14gNa
2Cu (the NO of O/ml
3)
2And NaNO
3Mixed liquor, dipping is coated with membrane carrier, takes out behind the placement 10h, in 50 ℃ of dry 10h, 110 ℃ of dry 12h, 400 ℃ of calcining 10h obtain carrier loaded 12.5 gram CuO of per 100 grams and 5.4 gram Na
2The catalyst of O.The catalyst of getting Φ 21 * 30mm places reaction tube (Φ 21mm), and the control reaction temperature is at 400 ℃, and air speed is 3000h
-1, flue gas consists of 1500ppm SO
2, 600ppm NO, 5.4%O
2, 2.5%H
2O, Ar is a balance gas, with 600ppmNH
3Be reducing agent, the NO removal efficiency is 85% under this operating condition, SO
2It is 6.5% that conversion ratio reaches 80% Sulfur capacity.
Embodiment 6
Take by weighing 155gAl (NO
3)
39H
2O is dissolved in the 200ml distilled water, and heating all adds the 100g urea in the dissolving back, promptly gets coating liquid., with taking out behind the above-mentioned coating liquid immersion surface treatment pottery 6h, in 50 ℃ of dry 10h, 110 ℃ of dry 12h are then in 400 ℃ of calcining 12h.Repeat to film obtain that ceramic content is 70% for 9 times, activated alumina content is 30% the membrane carrier that is coated with.With water is that adsorbent is made blank assay to the adsorbance of the ceramic monolith of filming, and finds that the adsorbable water yield of 100 gram carriers is 43 milliliters.Preparation CuO content is 0.247gCuO/ml, Na
2O content is 0.1gNa
2Cu (the NO of O/ml
3)
2And NaNO
3Mixed liquor, dipping is coated with membrane carrier, takes out behind the placement 6h, in 50 ℃ of dry 8h, 110 ℃ of dry 12h, 500 ℃ of calcining 6h obtain carrier loaded 10.6 gram CuO of per 100 grams and 4.6 gram Na
2The catalyst of O.The catalyst of getting Φ 21 * 30mm places reaction tube (Φ 21mm), and the control reaction temperature is at 400 ℃, and air speed is 2500h
-1, flue gas consists of 1900ppm SO
2, 500ppm NO, 5.4%O
2, 2.5%H
2O, balance Ar is with 550ppm NH
3Make reducing agent, stable state NO removal efficiency is 88% under this operating condition, SO
2Conversion ratio is 6.3% greater than 80% Sulfur capacity.
Claims (4)
1. a ceramic honeycomb catalyst that is used for flue gas and desulfurizing and denitrifying is characterized in that catalyst is first carrier with the surface-treated cordierite honeycomb ceramic, and the activated alumina film is second carrier, load active component CuO and Na
2O, the consisting of of catalyst:
Pottery 70-81wt.%,
Activated alumina 19-30wt.%,
Carrier loaded 8.5-12.5 gram CuO of per 100 grams and 4.0-5.4 gram Na
2O
2. a kind of preparation method who is used for the ceramic honeycomb catalyst of flue gas and desulfurizing and denitrifying as claimed in claim 1 is characterized in that comprising the steps:
(1) with aluminum nitrate: distilled water=0.6～0.8: 1 mass ratio, aluminum nitrate is added in the distilled water, all the dissolving back adds urea, wherein urea: the mass ratio of distilled water is 0.3～0.5: 1, and the gained glue is a coating liquid;
(2) the surface-treated cordierite honeycomb ceramic is soaked in the above-mentioned glue, takes out behind placement 6～8h, in 50～110 ℃ of down dry 8～12h, then in 400～500 ℃ of calcining 6～12h, the ceramic monolith of promptly once being filmed;
(3) can to obtain ceramic content be 70-81wt.% to repeating step (2), and activated alumina content is the 19-30wt.% ceramic monolith of filming;
(4) be that adsorbate is made blank assay to the adsorbance of the ceramic monolith of filming with water, the volume adsorption that obtains 100 gram carriers is the X milliliter;
(5) by carrier loaded 8.5-12.5 gram CuO of per 100 grams and 4.0-5.4 gram Na
2O, preparation CuO content are 8.5-12.5 gram CuO/Xml, Na
2O content is 4.0-5.4 gram Na
2Cu (the NO of O/Xml
3)
2And NaNO
3Mixed liquor is coated with membrane carrier with mixed liquid dipping, takes out behind placement 6～10h, in 50～110 ℃ of down dry 8～12h, in 400～500 ℃ of calcining 6～10h, promptly gets catalyst then.
3. a kind of preparation method who is used for the ceramic honeycomb catalyst of flue gas and desulfurizing and denitrifying as claimed in claim 2 is characterized in that the described volume that is coated with the used mixed liquor of membrane carrier with mixed liquid dipping is for more than or equal to the X milliliter.
4. a kind of application process that is used for the ceramic honeycomb catalyst of flue gas and desulfurizing and denitrifying as claimed in claim 1 is characterized in that comprising the steps:
(1) with NH
3Be reducing agent, press NH
3: NO
XMol ratio is 1-1.2: 1 ratio is with NH
3In the input flue gas;
(2) catalyst is placed fixed bed reactors, contain NH
3Flue gas enter fixed bed reactors, at atmospheric operation, operating temperature is 400 ℃, the operation air speed is 1700～3000h
-1Condition under carry out desulphurization denitration simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03122802 CN1232347C (en) | 2003-04-14 | 2003-04-14 | Honeycomb ceramic catalyst for simultaneously desulfurizing and denitrifying fume and its preparation and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03122802 CN1232347C (en) | 2003-04-14 | 2003-04-14 | Honeycomb ceramic catalyst for simultaneously desulfurizing and denitrifying fume and its preparation and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1457920A CN1457920A (en) | 2003-11-26 |
| CN1232347C true CN1232347C (en) | 2005-12-21 |
Family
ID=29430306
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|---|---|---|---|
| CN 03122802 Expired - Lifetime CN1232347C (en) | 2003-04-14 | 2003-04-14 | Honeycomb ceramic catalyst for simultaneously desulfurizing and denitrifying fume and its preparation and use |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100471560C (en) * | 2007-05-23 | 2009-03-25 | 中国科学院山西煤炭化学研究所 | Flue gas denitration catalyst for resisting sulfur dioxide poisoning and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716509B (en) * | 2009-11-13 | 2012-05-23 | 北京化工大学 | Granular catalyst used for studying coal-fired flue gas denitration and preparation method thereof |
| CN105126563B (en) * | 2015-08-24 | 2017-11-28 | 秦皇岛玻璃工业研究设计院 | The desulphurization denitration medium and desulphurization denitration apparatus and method of a kind of flue gas of glass melting furnace |
| CN107952438A (en) * | 2017-12-05 | 2018-04-24 | 宁波高新区敦和科技有限公司 | A kind of exhuast gas desulfurization mixed carrier catalyst and preparation method thereof |
| CN107961784A (en) * | 2017-12-12 | 2018-04-27 | 宁波高新区敦和科技有限公司 | A kind of catalyst for flue gas and desulfurizing and denitrifying and preparation method thereof |
| CN108126700A (en) * | 2017-12-30 | 2018-06-08 | 宁波高新区州致科技有限公司 | A kind of exhuast gas desulfurization mixed carrier catalyst and preparation method thereof |
| CN108187656A (en) * | 2017-12-30 | 2018-06-22 | 宁波高新区州致科技有限公司 | It is a kind of for catalyst of flue gas and desulfurizing and denitrifying and preparation method thereof |
| CN112552932A (en) * | 2020-11-13 | 2021-03-26 | 新兴铸管股份有限公司 | Dry quenching furnace circulating waste gas purification system |
-
2003
- 2003-04-14 CN CN 03122802 patent/CN1232347C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100471560C (en) * | 2007-05-23 | 2009-03-25 | 中国科学院山西煤炭化学研究所 | Flue gas denitration catalyst for resisting sulfur dioxide poisoning and preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN1457920A (en) | 2003-11-26 |
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Granted publication date: 20051221 |