CN107551799A - A kind of method of dry-process cement rotary kiln flue gas desulfurization and denitrification integration - Google Patents
A kind of method of dry-process cement rotary kiln flue gas desulfurization and denitrification integration Download PDFInfo
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- CN107551799A CN107551799A CN201710945712.4A CN201710945712A CN107551799A CN 107551799 A CN107551799 A CN 107551799A CN 201710945712 A CN201710945712 A CN 201710945712A CN 107551799 A CN107551799 A CN 107551799A
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- carbide slag
- rice hull
- hull ash
- flue gas
- desulfurization
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Abstract
A kind of desulfurization and denitrification integral method of dry-process cement rotary kiln flue gas, belongs to cement industry flue gas pollutant control technology field.The present invention dries 12~24h at a temperature of rice hull ash and carbide slag are placed in into 60~105 DEG C first；Then by rice hull ash and carbide slag according to different volume ratios (1:1~9:1) it is well mixed；Finally at 800~900 DEG C, under conditions of oxygen concentration is 1%~5%, SO is carried out using rice hull ash and carbide slag2Removed while with NOx.Wherein, carbide slag can be matched as cement raw material, while the oxide ash in rice hull ash as the composition of cement, can not also interfere with the performance of cement.And and cans while desulfurization of the Ca in carbide slag promote the process of carbon nitrogen oxides reduction, rice hull ash provides bigger reaction compartment while using C denitrations for desulphurization denitration, makes reaction more abundant again.Present invention process is simple, and sorbing material cost is low, and desulfurization and denitration efficiency are high.
Description
Technical field
The invention belongs to cement industry flue gas pollutant control technology field, and in particular to one kind utilizes carbide slag/rice husk
The method that grey compound additive realizes desulfurization and denitrification integral in cement kiln dore furnace.
Background technology
SO2It is atmosphere pollution main in cement industry kiln furnace exhaust gas with NOx, is the main reason for causing acid rain, to remove
Outside this, NOx can also cause a series of environmental problems such as haze, photochemical pollution and greenhouse effects.With environmental requirement not
It is disconnected to improve,《Cement industry atmosphere pollutants emission standardses》Provided in (GB 4915-2013)：General regional SO2And NOx emission
Limitation is respectively 200mg/m3、400mg/m3, key area SO2It is respectively 100mg/m with NOx emission limitation3、320mg/m3, need
Strictly to control SO2And NOx emission.Therefore finding effectively reduces cement industry SO2It is most important with the method for NOx emission.
Cement industry is generally to SO at present2Removed respectively with NOx.The desulfurization of cement industry is mainly favourable at this stage
SO is absorbed with the lime stone in raw material2From emission-reduction technology and including dry method, wet method, semidry method and compound desulfurization technology single-candidate
Outer SO2Emission-reduction technology, but desulfuration efficiency is low, equipment investment is big or operating cost is high etc. mostly be present in existing desulfurization technology
Problem.On the other hand, the selective catalytic reduction technique of method of denitration (SCR) primarily now and SNCR skill
Art (SNCR), and both technologies are required for using ammonia or urea to be used as reducing agent, it is therefore desirable to extra storage ammonia (urea)
With spray ammonia (urea) device, and the escaping of ammonia phenomenon is there is also, cause secondary pollution.The desulfurization and denitrification integral skill used at present
Art is the joint of desulphurization and denitration two ways, i.e. SO mostly2Handled respectively with NOx.United desulphurization denitration technology, which exists, fixes
The problems such as investment is high, and flow is complicated, runs complex operation, and operation and maintenance cost is high.Flue gas desulfurization and denitrification integrated technique can be with
Realize desulfurization and denitration simultaneously in same set of system, shorten flow, equipment is simplified, and floor space is small, and capital expenditure is few, operation
Manage the conveniently advantage such as low with production cost, it has also become the research direction of frontier nature in Air Pollution Control field.
Activated carbon is in O2With vapor existing under the conditions of, adsorb flue gas in SO2It is heated or washs again after produces sulfuric acid
Give birth to and recycle.NH need to be added in activated carbon absorption desulfurizing system3NOx can be just removed simultaneously.Activated carbon method is due to can
Remove sulfur dioxide in flue gas simultaneously and widely paid close attention to the advantages that nitrogen oxides, adsorbent can regenerate.But its
Market cost is high, it is difficult to meets the needs that heavy industrialization uses.Elimination reaction temperature is low, and optimal reaction temperature is 100
~200 DEG C, it is not suitable for cement industry, and ammonia need to be added and can be only achieved denitration effect, complex process.Therefore price is found
Cheap and advantages of good adsorption effect adsorbent is always the effort of various countries researcher institute.Carbide slag is as reluctant industrial waste
Pollution of the thing to surrounding enviroment is more serious.It is flue gas desulfurization calcium-based desulfurizing agent using replacing carbide slag with lime masonry, both reduced
A large amount of exploitations of lime stone, and can solve problem of environmental pollution to carbide slag twice laid.Existing research shows,
The reactivity of carbide slag is better than lime stone in desulphurization reaction, and carbide slag moisture effusion when being thermally decomposed makes generation
CaO has compared with concrete dynamic modulus, is advantageous to gas-solid phase reaction progress, has good desulfurized effect.The more suitable burning of carbide slag
Temperature is at 900 DEG C or so, and desulfurization efficiency now is high, and the temperature meets the temperature of cement kiln dore furnace.Rice hull ash is rice husk combustion
Main By product after burning, rich in amorphous silica and carbon, and agriculturally caused major garbage.Its is cheap,
Substantial amounts, specific surface area is high, therefore reactivity is also higher, has certain value.It can not only be shown using rice hull ash
Write and improve industrialized development, while can also protect the environment from pollution.Carbide slag and rice hull ash can be with very low costs
Reach very high economic benefit, be the quality raw materials for realizing cement kiln flue gas desulfurization and denitrification integral.
The content of the invention
It is an object of the invention to propose that one kind is realized using carbide slag/rice hull ash compound additive in cement kiln dore furnace
The method of desulfurization and denitrification integral.Effectively SO can be removed simultaneously2And NOx.Said preparation prepares simple, easy to operate, Neng Goutong
When desulphurization denitration, and there is good removal effect.
The concrete technical scheme that the present invention uses is as follows：
A kind of method of dry-process cement rotary kiln flue gas desulfurization and denitrification integration, it is characterised in that comprise the following steps：First will
Rice hull ash and carbide slag dry 12~24h at a temperature of being placed in 60-105 DEG C；Then dried rice hull ash and carbide slag are pressed
According to rice hull ash and the volume ratio of carbide slag 1:1~9:It is well mixed between 1；It is finally 1% in oxygen concentration of volume percent
~5%, 1000ppmNO, 2000ppmSO2、N2For Balance Air, total gas flow rate is 900ml/min, 800~900 DEG C of condition
Under, carry out SO using rice hull ash and carbide slag2Removed while with NOx.
Further, it is 3 in rice hull ash and carbide slag volume ratio:1, oxygen concentration of volume percent is 1%~5%, temperature
For 900 DEG C when carry out SO2Removed while with NOx.
Wherein, carbide slag can be matched as cement raw material, while the oxide ash in rice hull ash can also be used as water
The composition of mud, the performance of cement is not interfered with.
Wherein, carbide slag desulfurization principle：
Ca(OH)2→CaO+H2O (1)
CaO+SO2→1/2O2+CaSO4 (2)
CaCO3→CaO+CO2 (3)
CaO+SO2→CaSO3 (4)
Carbonaceous material denitration principle：
C+NO→CO+1/2N2 (5)
C+2NO→CO2+N2 (6)
CO+NO→CO2+1/2N2 (7)
The present invention effect be：
(1) carbide slag efficient absorption SO is utilized2Can be reaction because rice hull ash has high-specific surface area while gas
More spaces and place are provided, so as to improve SO2Absorptivity；While using carbon nitrogen oxides reduction in rice hull ash,
Because research shows that Ca can promote C-NO reactions to carry out, CaO is considered as to be catalyzed the high active substance that C-NO reacts, therefore electricity
The main component CaO of rock ballast is that nitrogen oxides reduction serves certain catalytic action；Desulfurization and denitration reaction in the system
Mutually promote, can reach fine and obtain removal effect.
(2) without entering to existing cement kiln when the mixing material of carbide slag and rice hull ash being added into cement kiln dore furnace
Row transformation, cost of investment are low, simple to operate.Carbide slag and rice hull ash are all waste residues, are also solved while desulphurization denitration useless
The process problem of slag, obvious environment benefit.
(3) adding carbide slag and rice hull ash will not have an impact to the composition of cement raw material, can ensure that cement kiln is normal
Operation, harmful effect will not be also produced to the performance of clinker.
Embodiment
With reference to embodiment, the invention will be further described, but the present invention is not limited to following examples.
12~24h is dried at a temperature of rice hull ash and carbide slag are placed in into 60-105 DEG C first；The shell ash of following examples
All it is dried with carbide slag.
Embodiment 1
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 1%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 800 DEG C, rice hull ash and carbide slag are pressed 9:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 63.7%, and desulfurization degree reaches 93.7%.
Embodiment 2
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 1%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 900 DEG C, rice hull ash and carbide slag are pressed 9:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 63.2%, and desulfurization degree reaches 95.4%.
Embodiment 3
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 1%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 800 DEG C, rice hull ash and carbide slag are pressed 6:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 60.2%, and desulfurization degree reaches 94.1%.
Embodiment 4
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 1%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 900 DEG C, rice hull ash and carbide slag are pressed 6:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 60.2%, and desulfurization degree reaches 96.2%.
Embodiment 5
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 1%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 800 DEG C, rice hull ash and carbide slag are pressed 3:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 78.4%, and desulfurization degree reaches 97.5%.
Embodiment 6
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 1%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 900 DEG C, rice hull ash and carbide slag are pressed 3:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 79.3%, and desulfurization degree reaches 98.7%.
Embodiment 7
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 1%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 800 DEG C, rice hull ash and carbide slag are pressed 1:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 62.8%, and desulfurization degree reaches 97.1%.
Embodiment 8
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 1%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 900 DEG C, rice hull ash and carbide slag are pressed 1:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 60.2%, and desulfurization degree reaches 98.3%.
Embodiment 9
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 2%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 900 DEG C, rice hull ash and carbide slag are pressed 3:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 75.2%, and desulfurization degree reaches 97.3%.
Embodiment 10
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 3%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 900 DEG C, rice hull ash and carbide slag are pressed 3:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 73.6%, and desulfurization degree reaches 97.8%.
Embodiment 11
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 4%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 900 DEG C, rice hull ash and carbide slag are pressed 3:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 73.4%, and desulfurization degree reaches 98.2%.
Embodiment 12
It is 1000ppmNO, 2000ppmSO in flue gas condition2, 5%O2, N2For Balance Air, total gas flow rate is 900ml/
Min, when temperature conditionss are 900 DEG C, rice hull ash and carbide slag are pressed 3:A diameter of 3cm is added to after 1 volume ratio is well mixed
Tube furnace in, denitration rate reaches 71.7%, and desulfurization degree reaches 98.6%.
The desulphurization denitration rate of 1 each embodiment of table
Claims (2)
- A kind of 1. method of dry-process cement rotary kiln flue gas desulfurization and denitrification integration, it is characterised in that comprise the following steps：First by rice Shell ash and carbide slag dry 12~24h at a temperature of being placed in 60-105 DEG C；Then by dried rice hull ash and carbide slag according to Rice hull ash and the volume ratio of carbide slag are 1:1~9:It is well mixed between 1；Finally oxygen concentration of volume percent be 1%~ 5%, 1000ppmNO, 2000ppmSO2、N2For Balance Air, total gas flow rate is 900ml/min, under conditions of 800~900 DEG C, SO is carried out using rice hull ash and carbide slag2Removed while with NOx.
- 2. according to a kind of method of dry-process cement rotary kiln flue gas desulfurization and denitrification integration described in claim 1, it is characterised in that： Rice hull ash and carbide slag volume ratio are 3:1, oxygen concentration of volume percent is 1%~5%, temperature carries out SO when being 900 DEG C2 Removed while with NOx.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108310960A (en) * | 2018-03-06 | 2018-07-24 | 浙江哲丰能源发展有限公司 | A kind of method of desulphurization in circulating fluidized bed boiler |
| CN108654315A (en) * | 2018-05-08 | 2018-10-16 | 北京工业大学 | A kind of preparation method of rice hull ash/carbide slag system flue gas desulfurization and denitrification absorbent |
| CN109603505A (en) * | 2019-01-25 | 2019-04-12 | 广东万引科技发展有限公司 | A kind of method of denitration of the dry-process cement rotary kiln flue gas with biomass bamboo charcoal |
| CN111606400A (en) * | 2020-04-24 | 2020-09-01 | 北京中冶设备研究设计总院有限公司 | Low-cost desulfurization wastewater pretreatment method |
| CN114367269A (en) * | 2022-03-02 | 2022-04-19 | 四川大学 | Flue gas pollutant adsorbent and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108310960A (en) * | 2018-03-06 | 2018-07-24 | 浙江哲丰能源发展有限公司 | A kind of method of desulphurization in circulating fluidized bed boiler |
| CN108654315A (en) * | 2018-05-08 | 2018-10-16 | 北京工业大学 | A kind of preparation method of rice hull ash/carbide slag system flue gas desulfurization and denitrification absorbent |
| CN108654315B (en) * | 2018-05-08 | 2020-11-27 | 北京工业大学 | Preparation method of flue gas desulfurization and denitrification absorbent of rice hull ash/carbide slag system |
| CN109603505A (en) * | 2019-01-25 | 2019-04-12 | 广东万引科技发展有限公司 | A kind of method of denitration of the dry-process cement rotary kiln flue gas with biomass bamboo charcoal |
| CN111606400A (en) * | 2020-04-24 | 2020-09-01 | 北京中冶设备研究设计总院有限公司 | Low-cost desulfurization wastewater pretreatment method |
| CN114367269A (en) * | 2022-03-02 | 2022-04-19 | 四川大学 | Flue gas pollutant adsorbent and preparation method thereof |
| CN114367269B (en) * | 2022-03-02 | 2023-02-28 | 四川大学 | Flue gas pollutant adsorbent and preparation method thereof |
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