CN101791537A - Modified sludge activated carbon used for low-concentration flue gas desulfurization and denitration and preparation method thereof - Google Patents
Modified sludge activated carbon used for low-concentration flue gas desulfurization and denitration and preparation method thereof Download PDFInfo
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Abstract
The invention discloses modified sludge activated carbon used for low-concentration flue gas desulfurization and denitration, which comprises the following ingredients in percentage by weight: 0.41 to 6.46 percent of chitosan and 93.54 to 99.59 percent of sludge. A preparation method comprises the following preparation steps: 1, preparing a chitosan solution; 2, preparing sludge activated carbon; and 3, preparing chitosan modified sludge activated carbon. The invention uses the chitosan for the sludge activated carbon for the first time, so the modified ingredients reach the green environment protection standard on the premise that the invention effectively ensures that the desulfurization and denitration performance of the sludge activated carbon is not lower than the existing level.
Description
Technical field
The invention relates to the active carbon of flue gas desulfurization, denitration, relate in particular to the modified sewage sludge absorbent charcoal of desulfurizing low concentration fume, denitration.
Background technology
Along with the raising of international community to discharge of wastewater and protection of resources requirement, new sewage treatment plant constantly sets up.Also produced a large amount of mud when disposing of sewage, its quantity accounts for about 0.3%～0.5% (are 97% calculating with moisture content) of handling the water yield, these mud instabilities, easy corrupt, foul smelling.A large amount of mud that the municipal sewage plant produces, through precipitation, concentrate, conventional Treatment of Sludge and disposing techniques such as digestion, dehydration and final disposal, need a large amount of capital expenditures and higher operating cost, its operating cost accounts for about 40%～65% of sewage treatment plant's overall running cost.Statistics in 2004 shows, China has built up and the sewage treatment plant that puts into effect surpasses 700, and about 4,500 ten thousand tons of day sewage treatment capacity is discharged about 1,300,000 tons of sludge quantity (dry weight) now, and annual still about 10% amplification increase.Along with improving gradually of sewage treatment plant's operational efficiency and progressively building up of new sewage treatment plant, China's municipal sludge annual discharging sludge quantity (dry weight) finally estimation will be brought up to 8,400,000 tons, account for 3.2% of China's total solid waste discharge amount.Particularly for this big city, Tianjin, how disposing sludge is the pressing problem that the whole world is faced.
Because volatile solid and protein account for 60 ~ 80% and 22 ~ 41% of total dried solid masses respectively in the undigested mud of sewage treatment plant, so organic carbon content height in the undigested mud.In recent years, mud is prepared the active carbon aspect and carried out some experimental studies.At present prepared active sludge carbon aperture is bigger, is generally macropore or mesopore, and specific area is less, is fit to the big molecule of absorption, so use it for the more of decolouring adsorption experiment.Yu Lanlan, Zhong Qin are used for flue gas desulfurization with prepared active sludge carbon, studied the influence of adsorption conditionses such as sulfur dioxide in flue gas concentration, flow velocity and temperature to desulfurization degree, but its desulfuration efficiency are far below merchandise active carbon.
The combined desulfurization and denitration technology is the developing direction of smoke gas treatment in recent years, and wherein catalyst method utilizes CuO, Al
2O
3, catalyst removal sulfur dioxide and nitrogen oxide such as active carbon.Especially the active carbon desulfurization denitration technology has only minority developed country to use at present in the world, does not still have heavy industrialization to use in China.A lot of about the theoretical research of active carbon desulfurization denitration in recent years.And that mud prepares the research of desulphurized aetivated carbon is also at the experimental stage, the adsorption desulfurize poor-performing.The inventor also once disclosed a kind of preparation method who is used for flue gas desulfurization and denitrification gamma type di-aluminium trioxide film and vanadic anhydride modified sewage sludge absorbent charcoal in Chinese 200910068313.X2479.8 patent application, but only considered the performance of its desulfurization, denitration, failed to take into account the standard that modified component should reach environmental protection.
Studies show that shitosan (Chitosan; CS) be a kind of natural alkaline polysaccharide that the abundant chitin in origin source obtains through deacetylated processing; many active hydroxyls and amino and some N-acetylamino isopolarity groups are distributing on its strand; shitosan also has characteristics such as nontoxic, biodegradable in addition, is a kind of very good adsorbent.Scholars more both domestic and external are just studying the processing of using it for dyestuff, heavy metal-containing waste water.。Many active hydroxyls and amino and some N-acetylamino isopolarity groups owing to distributing on the molecular chain of chitosan, can with sulfur dioxide and reaction of nitrogen oxides, suitable modified component as the desulphurization denitration active carbon.Have not yet to see the report of using it for desulphurization denitration.Therefore, chitin modified active sludge carbon can improve desulfurization, denitration performance simultaneously, and to application that promotes active sludge carbon and the environmental protectionization that promotes scavenging material, the kind of enriching dry method while desulphurization denitration scavenging material is very necessary.
Summary of the invention
The objective of the invention is only to have considered its desulfurization, denitration performance at the gamma type di-aluminium trioxide film and the vanadic anhydride modified sewage sludge absorbent charcoal of prior art, fail to take into account the deficiency that its modified component fails to reach environmental protection, the present invention adopts chitin modified active sludge carbon first, adopt green material as modified component, its flue gas desulfurization, denitration performance are not less than the level of prior art.
The present invention is achieved by following technical proposals.
The modified sewage sludge absorbent charcoal that is used for desulfurizing low concentration fume, denitration, its raw material components and weight percent content thereof are shitosan 0.41～6.46wt%, mud 93.54～99.59wt%.
The deacetylation of described shitosan is 99%, and described mud is sludge of sewage treatment plants.
Be used for the preparation method of the modified sewage sludge absorbent charcoal of desulfurizing low concentration fume, denitration, preparation process is as follows:
1. prepare chitosan solution
0.10～0.20g shitosan is dissolved in the acetic acid solution (1vol%) of 5～15mL, adds the distilled water of 3～10mL again, ultrasonic dispersion 3～12h makes the shitosan homogeneous solution of 0.5～2.5wt%;
2. prepare active sludge carbon
Dewatered sludge is put into retort, 200～800 ℃ of following charings, adopt the nitrogen secluding air, nitrogen flow is 10～100L/h, and the rate of heat addition is controlled at 5～35 ℃/min, and charing 0.5～4h makes carbonized material; The carbonized material that makes is activated down at 200～1000 ℃, adopting flow is the water vapour of 10～100L/h again, and the rate of heat addition is controlled at 5～35 ℃/min, and activation 0.5～4h makes active sludge carbon;
3. prepare flue gas desulfurization, denitration with chitin modified active sludge carbon
2～10g active sludge carbon is immersed above-mentioned steps 1. in the solution, stir 1～5h after, take out, through suction filtration, drying is cleaned to neutral with the 0.01mol/L sodium hydroxide solution, drying at room temperature makes flue gas desulfurization, denitration with chitin modified active sludge carbon.
Described step preferred version 1. is dissolved in the acetic acid solution (1vol%) of 10mL for shitosan 0.15g, and the distilled water of adding is 5mL, and ultrasonic dispersion 6h makes the homogeneous solution of 2.0wt%.
Described step preferred version 2. is that carbonization temperature is 400 ℃, carbonization time 1h, and activation temperature is 500 ℃, soak time 1h.
Described step preferred version 3. stirs 3h for the 5g active sludge carbon immerses in the solution.
The invention has the beneficial effects as follows, first shitosan is used for the preparation of modified sewage sludge absorbent charcoal, under the desulfurization that effectively guarantees active sludge carbon, prerequisite that denitration performance is not less than existing level, make modified component reach the standard of environmental protection.Chitin modified active sludge carbon of the present invention is mainly used in low-concentration flue gas is carried out desulfurization and denitration simultaneously.
Description of drawings
Fig. 1 is the ESEM shape appearance figure of the active sludge carbon of prior art;
Fig. 2 is the ESEM shape appearance figure of the embodiment of the invention 2 modified sewage sludge absorbent charcoals.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
The deacetylation of the used shitosan of raw material of the present invention is 99%, and mud is from sewage treatment plant.
Embodiment 1
1. prepare chitosan solution
The 0.20g shitosan is dissolved in the acetic acid solution (1vol%) of 15mL, adds the distilled water of 10mL again, ultrasonic again dispersion 3h makes the homogeneous solution of 2.5wt%;
2. prepare active sludge carbon
Dewatered sludge is put into retort, 200 ℃ of following charings, adopt the nitrogen secluding air, nitrogen flow is 50L/h, and the rate of heat addition is controlled at 5 ℃/min, and charing 4h makes carbonized material.The carbonized material that makes is activated down at 1000 ℃, adopting flow is the water vapour of 100L/h again, and the rate of heat addition is controlled at 15 ℃/min, and activation 0.5h makes active sludge carbon.
3. prepare flue gas and desulfurizing and denitrifying with chitin modified active sludge carbon
The 10g active sludge carbon is immersed above-mentioned steps 1. in the solution, stir 1h after, take out again, through suction filtration, drying is cleaned to neutral with the 0.01mol/L sodium hydroxide solution, drying at room temperature makes flue gas and desulfurizing and denitrifying with chitin modified active sludge carbon.
The desulphurization denitration experiment of embodiment 1
The present invention is with 600ppmNO/Ar, 600ppmNH
3/ Ar, 1450ppm SO
3/ Ar and 3.2%O
2+ 3.5%H
2The O/Ar mist mixes the back as pending source of the gas.Adopt Britain to produce comprehensive flue gas analyzer (KANE940) and detect sulfur dioxide and the nitric oxide production concentration in the atmosphere of reaction front and back under the different condition.
According to the variable quantity of sulfur dioxide and nitric oxide concentration, calculate chitin modified active sludge carbon desulfurization degree and denitration rate and be respectively 78.3% and 56.2% respectively.
Embodiment 2
1. prepare chitosan solution
The 0.15g shitosan is dissolved in the acetic acid solution (1vol%) of 10mL, adds the distilled water of 5mL again, ultrasonic again dispersion 6h makes the homogeneous solution of 2.0wt%;
2. prepare active sludge carbon
Dewatered sludge is put into retort, 400 ℃ of following charings, adopt the nitrogen secluding air, nitrogen flow is 100L/h, and the rate of heat addition is controlled at 15 ℃/min, and charing 1h makes carbonized material.The carbonized material that makes is activated down at 500 ℃, adopting flow is the water vapour of 50L/h again, and the rate of heat addition is controlled at 35 ℃/min, and activation 1h makes active sludge carbon.
3. prepare flue gas and desulfurizing and denitrifying with chitin modified active sludge carbon
The 5g active sludge carbon is immersed above-mentioned steps 1. in the solution, stir 3h after, take out again, through suction filtration, drying is cleaned to neutral with the 0.01mol/L sodium hydroxide solution, drying at room temperature makes flue gas and desulfurizing and denitrifying with chitin modified active sludge carbon.
The desulphurization denitration experiment of embodiment 2
The step of desulfurization, denitration experiment is same as embodiment 1, respectively according to the variable quantity of sulfur dioxide and nitric oxide concentration, calculates chitin modified active sludge carbon desulfurization degree and denitration rate and is respectively 85.6% and 73.1%.
Embodiment 3
1. prepare chitosan solution
The 0.10g shitosan is dissolved in the acetic acid solution (1vol%) of 5mL, adds the distilled water of 3mL again, ultrasonic again dispersion 12h makes the homogeneous solution of 0.5wt%;
2. prepare active sludge carbon
Dewatered sludge is put into retort, 800 ℃ of following charings, adopt the nitrogen secluding air, nitrogen flow is 10L/h, and the rate of heat addition is controlled at 35 ℃/min, and charing 0.5h makes carbonized material.The carbonized material that makes is activated down at 200 ℃, adopting flow is the water vapour of 10L/h again, and the rate of heat addition is controlled at 5 ℃/min, and activation 4h makes active sludge carbon.
3. prepare flue gas and desulfurizing and denitrifying with chitin modified active sludge carbon
The 2g active sludge carbon is immersed above-mentioned steps 1. in the solution, stir 5h after, take out again, through suction filtration, drying is cleaned to neutral with the 0.01mol/L sodium hydroxide solution, drying at room temperature makes flue gas and desulfurizing and denitrifying with chitin modified active sludge carbon.
The desulfurization of embodiment 3
The step of desulfurization, denitration experiment is same as embodiment 1, respectively according to the variable quantity of sulfur dioxide and nitric oxide concentration, calculates chitin modified active sludge carbon desulfurization degree and denitration rate and is respectively 80.2 and 65.7%.
Fig. 1 is an active sludge carbon ESEM shape appearance figure.As seen from Figure 1, the surfacing of active sludge carbon formed uniform aperture, but the aperture is bigger.Fig. 2 is chitin modified active sludge carbon ESEM shape appearance figure.As seen from Figure 2, the surface of the active sludge carbon chitosan particle that distributed has reduced the aperture of active sludge carbon, has increased the specific area of active sludge carbon, improves its absorption property.
The present invention is not limited to the foregoing description, and the variation of a lot of details is possible, but therefore this do not run counter to scope and spirit of the present invention.
Claims (6)
1. modified sewage sludge absorbent charcoal that is used for desulfurizing low concentration fume, denitration, its raw material components and weight percent content thereof are shitosan 0.41～6.46wt%, mud 93.54～99.59wt%.
2. according to the modified sewage sludge absorbent charcoal that is used for desulfurizing low concentration fume, denitration of claim 1, it is characterized in that the deacetylation of described shitosan is 99%, described mud is sludge of sewage treatment plants.
3. the preparation method of the modified sewage sludge absorbent charcoal that is used for desulfurizing low concentration fume, denitration of claim 1, preparation process is as follows:
1. prepare chitosan solution
0.10～0.20g shitosan is dissolved in the acetic acid solution (1vol%) of 5～15mL, adds the distilled water of 3～10mL again, ultrasonic dispersion 3～12h makes the shitosan homogeneous solution of 0.5～2.5wt%;
2. prepare active sludge carbon
Dewatered sludge is put into retort, 200～800 ℃ of following charings, adopt the nitrogen secluding air, nitrogen flow is 10～100L/h, and the rate of heat addition is controlled at 5～35 ℃/min, and charing 0.5～4h makes carbonized material; The carbonized material that makes is activated down at 200～1000 ℃, adopting flow is the water vapour of 10～100L/h again, and the rate of heat addition is controlled at 5～35 ℃/min, and activation 0.5～4h makes active sludge carbon;
3. prepare flue gas desulfurization, denitration with chitin modified active sludge carbon
2～10g active sludge carbon is immersed above-mentioned steps 1. in the solution, stir 1～5h after, take out, through suction filtration, drying is cleaned to neutral with the 0.01mol/L sodium hydroxide solution, drying at room temperature makes flue gas desulfurization, denitration with chitin modified active sludge carbon.
4. according to the preparation method of the modified sewage sludge absorbent charcoal that is used for desulfurizing low concentration fume, denitration of claim 3, it is characterized in that, described step preferred version 1. is dissolved in the acetic acid solution (1vol%) of 10mL for shitosan 0.15g, the distilled water that adds is 5mL, ultrasonic dispersion 6h makes the homogeneous solution of 2.0wt%.
5. according to the preparation method of the modified sewage sludge absorbent charcoal that is used for desulfurizing low concentration fume, denitration of claim 3, it is characterized in that described step preferred version 2. is that carbonization temperature is 400 ℃, carbonization time 1h, activation temperature is 500 ℃, soak time 1h.
6. according to the preparation method of the modified sewage sludge absorbent charcoal that is used for desulfurizing low concentration fume, denitration of claim 3, it is characterized in that described step preferred version 3. stirs 3h for the 5g active sludge carbon immerses in the solution.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934221A (en) * | 2010-10-14 | 2011-01-05 | 厦门大学 | Modified adsorbent and preparation method thereof |
| CN101940914A (en) * | 2010-09-27 | 2011-01-12 | 宁波天韵生态治理工程有限公司 | Method for producing adsorbent by using polyphosphoric sodium phosphate-coupled chitosan and bamboo charcoal |
| CN104226251A (en) * | 2014-09-29 | 2014-12-24 | 镇江华域环保设备制造有限公司 | Oxidization modified active carbon adsorbent and preparation method thereof |
| CN104741008A (en) * | 2015-04-21 | 2015-07-01 | 湖南有色冶金劳动保护研究院 | Desulfuration film and application thereof in natural gas or petrochemical engineering gas purification |
| CN105126922A (en) * | 2015-07-10 | 2015-12-09 | 山东海润环保科技有限公司 | Vanadium-free SCR denitration catalyst and preparation method thereof |
| CN105797686A (en) * | 2016-03-28 | 2016-07-27 | 柳州联海科技有限公司 | Adsorption material for desulfuration of liquefied petroleum gas and preparation method |
| CN107744832A (en) * | 2017-09-30 | 2018-03-02 | 华中科技大学 | A kind of sludge organism Pd/carbon catalyst of polymer modification, it is prepared and application |
| CN108607529A (en) * | 2018-05-08 | 2018-10-02 | 中国科学院烟台海岸带研究所 | A kind of purification filtrate of Organic-inorganic composite contaminant water and its preparation method and application |
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| CN101543763A (en) * | 2009-03-31 | 2009-09-30 | 天津城市建设学院 | Modified sludge activated carbon for desulfurization and denitration of flue gas and preparation method thereof |
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Patent Citations (1)
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| CN101543763A (en) * | 2009-03-31 | 2009-09-30 | 天津城市建设学院 | Modified sludge activated carbon for desulfurization and denitration of flue gas and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940914A (en) * | 2010-09-27 | 2011-01-12 | 宁波天韵生态治理工程有限公司 | Method for producing adsorbent by using polyphosphoric sodium phosphate-coupled chitosan and bamboo charcoal |
| CN101934221A (en) * | 2010-10-14 | 2011-01-05 | 厦门大学 | Modified adsorbent and preparation method thereof |
| CN104226251A (en) * | 2014-09-29 | 2014-12-24 | 镇江华域环保设备制造有限公司 | Oxidization modified active carbon adsorbent and preparation method thereof |
| CN104741008A (en) * | 2015-04-21 | 2015-07-01 | 湖南有色冶金劳动保护研究院 | Desulfuration film and application thereof in natural gas or petrochemical engineering gas purification |
| CN105126922A (en) * | 2015-07-10 | 2015-12-09 | 山东海润环保科技有限公司 | Vanadium-free SCR denitration catalyst and preparation method thereof |
| CN105797686A (en) * | 2016-03-28 | 2016-07-27 | 柳州联海科技有限公司 | Adsorption material for desulfuration of liquefied petroleum gas and preparation method |
| CN107744832A (en) * | 2017-09-30 | 2018-03-02 | 华中科技大学 | A kind of sludge organism Pd/carbon catalyst of polymer modification, it is prepared and application |
| CN108607529A (en) * | 2018-05-08 | 2018-10-02 | 中国科学院烟台海岸带研究所 | A kind of purification filtrate of Organic-inorganic composite contaminant water and its preparation method and application |
| CN108607529B (en) * | 2018-05-08 | 2021-02-09 | 中国科学院烟台海岸带研究所 | Organic-inorganic composite polluted water purification filter material and preparation method and application thereof |
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