CN103537185B - It is a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient and removal methods - Google Patents
It is a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient and removal methods Download PDFInfo
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- CN103537185B CN103537185B CN201310529912.3A CN201310529912A CN103537185B CN 103537185 B CN103537185 B CN 103537185B CN 201310529912 A CN201310529912 A CN 201310529912A CN 103537185 B CN103537185 B CN 103537185B
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Abstract
The present invention provides a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient and removal methods, it is respectively 50%~80%, 5%~30%, 5%~30% mixing by mass percentage by three kinds of acid cleaning waste slag, calcium hydroxide and calcium hypochlorite fine powders, then desulfurization denitrification agent slurries are made in mass ratio 1: 95~1: 99.5 10~60min of addition water stirring into mixture；The gas to be removed that temperature is 110~140 DEG C is entered the fluidization equipment that a corundum ball filling height is 1.5~4m by bottom, and the gas superficial flow velocity based on bed sectional area is 0.01~1.0m/s；Slurries are set the spray equipment above the fluidization equipment Bed level at 0.5~3m and are uniformly sprayed at corundum ball surface, and sprinkle density is 1~10m3/(m2·h).Present invention can apply to steel, electric power, the energy and field of environment protection.
Description
Technical field
The present invention relates to a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient and removal methods, more particularly to one
Kind using steel plant's acid cleaning waste slag to sulfide and the nitride scavenger and method that are removed in boiler smoke, belong to steel
Iron, electric power, the energy, chemical industry and field of environment protection.
Background technology
SO in boiler smoke2And NOXIt is the main component of atmosphere pollution, the issuing and implementation in China《Atmosphere pollution
Comprehensive discharge standard》(GB 16297-1996)、《Emission standard of air pollutants for boilers》(GB 13271-2001)、《Industrial furnace
Kiln atmosphere pollutants emission standards》(GB 9078-1996)、《Fossil-fuel power plant atmospheric pollutant emission standard》(GB 13223-2003)
In equal series standards and regulation, there is specific restriction to its content.Due to SO2And NOXIt exists simultaneously in flue gas, if to it
Take the method removed respectively that will bring the problem that equipment is various, complicated for operation.From SO2And NOXFrom the point of view of feature, they are all acid
Property oxide, while they remove feasible, there is also some Industrial demonstrations and comercial operation device at present.Currently
The integrated method of flue gas desulfurization and denitrification is broadly divided into wet desulphurization denitration, dry desulfurization denitration and semi-dry desulfurization and denitrification three
Kind.Generally speaking, wet method removal effect is good, but waste liquor contamination is serious；Dry removal effect is good, but operating cost is high；Semidry method
The advantages of having both dry method and wet method, but the problem of there is also fluctuation of service.During preparing integration desulfurization denitration agent,
The method that majority formula carries out mixed preparing using various pure active principles, it is higher to thereby result in desulfurization denitrification agent cost.
Steel surface cleans using hydrochloric acid or sulfuric acid solution in most of steel mill of China, in the pickle liquor after cleaning
Typically contain the H of 0.05~5g/L+With the Fe of 60~250g/L2+And Fe3+And if treated that waste liquid do not recycle and the meeting of utilizing
It results in waste of resources and environmental pollution.The method of recycling treatment pickle liquor mainly has recycling molysite, prepares ferromagnetic stream at present
Body prepares inorganic polymer flocculant etc..Although the research report of pickle liquor recycling treatment is more, due to operation letter
The factors such as single, of low cost, many steel mills still use traditional quick lime, calcium hydroxide or lime stone neutralisation, thus generate
Waste residue (referred to as " acid cleaning waste slag ") reprocessing difficulty it is larger, while occupying a large amount of soil and resulting in waste of resources and secondary dirt
Dye.The research that the industrial waste residue resources such as white clay, red mud, carbide slag utilize is more, and has been obtained in terms of boiler flue gas desulfurization
Arrived attention and application, but acid cleaning waste slag report in this respect it is less.
By to acid cleaning waste slag carry out XRF detections the result shows that, acid cleaning waste slag mainly contains CaSO4、Ca(OH)2、
CaCO3、Fe3O4And SiO2, followed by Mg, Al, Ti, Mn and Zr etc. is micro-, wherein Ca (OH)2、CaCO3Etc. being desulphurization denitration
Active ingredient, oxide of Fe etc. has significant facilitation to Desulfovibrio process.Acid cleaning waste slag is carried out by BET method
Test the result shows that, the shape in acid cleaning waste slag particle hole is cylindrical shape, pore size based on mesoporous, micropore and macropore compared with
It is few, it further calculates to obtain, in total pore volume distribution, micropore accounts for 2.65%, and mesoporous to account for 83.3%, macropore accounts for 14.05%, compares table
Area reaches 43.94m2/ g, hence it is evident that higher than the specific surface area that lime stone and shell make desulfurization denitrification agent.Therefore, from acid cleaning waste slag
From the point of view of ingredient and particle hole characteristic, the requirement of boiler flue gas desulfurization denitration disclosure satisfy that.
From the point of view of the active constituent content of acid cleaning waste slag desulphurization denitration, active ingredient mass percentage be 25%~
30% or so, carry out desulphurization denitration, under the premise of meeting higher denitrification efficiency, unit according to single acid cleaning waste slag
Removing amount needs a large amount of acid cleaning waste slag, to need larger equipment and higher operating cost.Therefore, it may be considered that with acid
It is major ingredient to wash waste residue, then adds the compound scavenger of auxiliaries of a certain amount of desulphurization denitration, to realize acid cleaning waste slag recycle,
Achieve the purpose that the treatment of wastes with processes of wastes against one another.
Invention content
It is an object of the present invention to realize the secondary use of steel plant's acid cleaning waste slag, provided for boiler flue gas desulfurization denitration
A method of preparing simple, low-cost scavenger and efficient removal.
The purpose of the present invention is realized by following approach：
It is a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient, it is characterised in that major ingredient is useless for steel plant's pickling
Slag, auxiliary material are calcium hydroxide and calcium hypochlorite；On three kinds of material proportions, the acid cleaning waste slag mass percentage is 50%
~80%, the mass percentage of the calcium hydroxide is 5%~30%, and the mass percentage of the calcium hypochlorite is
5%~30%.
The acid cleaning waste slag is steel plant's hydrochloric acid pickling waste liquor or sulfuric acid pickling waste liquid after calcium hydroxide neutralisation treatment
Waste residue product, polished fine powder diameter are less than 200 μm；The calcium hydroxide and calcium hypochlorite is the powder that grain size is less than 100 μm
Body, purity are 90%~99%.
It is a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent removal methods of major ingredient, it is characterised in that by desulfurization denitrification agent
It is stirred evenly with water under room temperature, normal pressure and slurries is made, the mass ratio of desulfurization denitrification agent and water is 1: 95~1: 99.5, when stirring
Between be 10~60min；Denitration gas to be desulfurization is entered the fluidization equipment that an inside is filled with corundum ball, slurries warp by bottom
Spray equipment in fluidization equipment upper space is set and is uniformly sprayed at corundum ball surface, denitration gas to be desulfurization be adhered to
The desulfurization denitrification agent of corundum ball surface carries out an elimination reaction, and the denitration gas to be desulfurization after primary first-order equation flows out fluidization
After bed secondary elimination reaction is carried out with the slurry liquid contacts of bed superjacent air space；Gas after desulphurization denitration and partial desulfurization denitration
Solid product is set the gas-solid separating device separation exported in fluidization equipment.
The denitration gas inlet temperature to be desulfurization is 110~140 DEG C, the gas based on fluidization equipment bed sectional area
Body apparent velocity is 0.01~1.0m/s；The fluidization equipment is bubbling bed, turbulent bed or spouted bed, bed filling height
For 1.5~4m；The corundum ball grain size is 0.5~3mm；The space length of the spray equipment and fluidized-bed bed boundary
For 0.5~3m, the desulfurization denitrification agent slurries sprinkle density based on fluidization equipment bed sectional area is 1~10m3/(m2·h)。
Compared with prior art, the present invention in the presence of obvious advantage is that：
(1) secondary use for realizing acid cleaning waste slag, has achieved the purpose that the treatment of wastes with processes of wastes against one another；(2) desulfurization denitrification agent is at low cost
Honest and clean, preparation and removal methods are simple；(3) purpose of boiler smoke dedusting can also be realized simultaneously during desulphurization denitration.
Description of the drawings
Attached drawing is inventive desulfurization denitrfying agent River Bank Stability and desulphurization denitration flow diagram.
Specific implementation mode
Below by specific embodiment and in conjunction with attached drawing, the present invention will be described in detail.
A：Desulphurization denitration River Bank Stability flow
Referring to attached drawing, it will crush, grinding, sieve from the acid cleaning waste slag of Hebei Bazhou steel plant, and weigh grain size and be less than
200 μm of fine powder mass M 1=18kg, then weigh respectively purity be 95%, diameter of particle be respectively less than 100 μm, quality be respectively M2
The calcium hydroxide and calcium hypochlorite of=M3=6kg, then the water that quality is M4=3000kg is weighed, by the acid cleaning waste slag weighed, hydrogen
Blender is added in calcium oxide, calcium hypochlorite, water, stirs after 30min that be put into storage tank spare under room temperature, normal pressure.
B：Desulphurization denitration flow
Referring to attached drawing, the fluidization equipment of desulphurization denitration uses bubbling bed, and it is 2mm that bubbling bed body interior, which is filled with grain size,
Corundum ball, filling height be 1.5m；1 sprinkle nozzle spray equipment is installed at 2m above the corundum ball charge level.It is to be removed
Gas is boiler smoke, wherein SO2Content is 3600mg/m3, NO contents are 1200mg/m3, NO2Content is 800mg/m3, flue gas
Bubbling bed desulfuring and denitrifying apparatus is entered by bottom, feeding temperature is 120 DEG C, and the apparent velocity based on bubbling bed section is 0.1m3/
s.Prepared desulfurization denitrification agent slurries are sprayed into through sprinkle nozzle spray equipment in bubbling bed, are accumulated based on bubbling bed main body section
Sprinkle density be 1.0m3/(m2·h).Flue gas and the desulfurization denitrification agent for being adhered to corundum ball surface carry out an elimination reaction,
After flue gas outflow bed after primary first-order equation secondary elimination reaction is carried out with the slurry liquid contacts of bed superjacent air space；Desulphurization denitration
Flue gas and partial desulfurization denitration solid product afterwards be set bubbling bed body exit gas-solid separating device separation, flue gas into
Enter aftertreatment systems, solid product is collected.Exit gas concentration is detected using flue gas analyzer, testing result is aobvious
Show, using desulfurization denitrification agent provided by the invention and removal methods, desulfurization degree is 90%~98%, denitrification rate is 65%~
81%.
Finally it should be noted that：Above example is only to illustrate the present invention and not limits technology described in the invention
Scheme；Therefore, although this specification with reference to above-mentioned each embodiment to present invention has been detailed description, this
Field it is to be appreciated by one skilled in the art that still can modify or equivalently replace the present invention；And all are not departed from
The technical solution of the spirit and scope of the present invention and its improvement, are intended to be within the scope of the claims of the invention.
Claims (4)
1. a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient, it is characterised in that major ingredient is steel plant's acid cleaning waste slag,
Auxiliary material is calcium hydroxide and calcium hypochlorite；On three kinds of material proportions, the acid cleaning waste slag mass percentage be 50%~
80%, the mass percentage of the calcium hydroxide is 5%~30%, and the mass percentage of the calcium hypochlorite is
5%~30%.
2. according to claim 1 a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient, it is characterised in that institute
The acid cleaning waste slag stated is the waste residue product of steel plant's hydrochloric acid pickling waste liquor or sulfuric acid pickling waste liquid after calcium hydroxide neutralisation treatment, warp
Fine powder diameter is less than 200 μm after grinding；The calcium hydroxide and calcium hypochlorite is the powder that grain size is less than 150 μm, and purity is
90%~99%.
3. a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent removal methods of major ingredient, it is characterised in that desulfurization denitrification agent exists
It is stirred evenly with water under room temperature, normal pressure and slurries is made, the mass ratio of desulfurization denitrification agent and water is 1: 95~1: 99.5, mixing time
For 10~60min；Denitration gas to be desulfurization is entered the fluidization equipment that an inside is filled with corundum ball by bottom, and slurries are through setting
It sets the spray equipment in fluidization equipment upper space and is uniformly sprayed at corundum ball surface, denitration gas to be desulfurization and be adhered to just
The desulfurization denitrification agent of beautiful ball surface carries out an elimination reaction, and the denitration gas to be desulfurization after primary first-order equation flows out fluidized-bed
After layer secondary elimination reaction is carried out with the slurry liquid contacts of bed superjacent air space；Gas and partial desulfurization denitration after desulphurization denitration is solid
Body product is set the gas-solid separating device separation exported in fluidization equipment.
4. it is according to claim 3 a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent removal methods of major ingredient, it is special
Sign is that the denitration gas inlet temperature to be desulfurization is 110~140 DEG C, the gas based on fluidization equipment bed sectional area
Apparent velocity is 0.01~1.0m/s；The fluidization equipment is bubbling bed, turbulent bed or spouted bed, and bed filling height is
1.5~4m；The corundum ball grain size is 0.5~3mm；The spray equipment and the space length of fluidized-bed bed boundary are
0.5~3m, the desulfurization denitrification agent slurries sprinkle density based on fluidization equipment bed sectional area are 1~10m3/(m2·h)。
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| CN201310529912.3A CN103537185B (en) | 2013-10-30 | 2013-10-30 | It is a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient and removal methods |
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| CN107573980A (en) * | 2017-09-11 | 2018-01-12 | 天津市职业大学 | A kind of coal supply chain combustion adjuvant and preparation method thereof |
| CN108905615A (en) * | 2018-08-31 | 2018-11-30 | 江苏绿景环保设备有限公司 | Smoke processing system and method after a kind of dangerous waste incineration |
| CN114082288A (en) * | 2020-06-08 | 2022-02-25 | 广东赛珐生物科技有限公司 | New application of folic acid wastewater |
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| CN101703886A (en) * | 2009-10-29 | 2010-05-12 | 太原理工大学 | Desulfuration method by directly utilizing magnesium slags in circulating fluidized bed boiler |
| CN101791622A (en) * | 2010-03-17 | 2010-08-04 | 上海天顿环境工程有限公司 | Process method for converting metal magnesium slag into desulphurizer of boiler |
| CN201832558U (en) * | 2010-11-03 | 2011-05-18 | 中国新型建筑材料工业杭州设计研究院 | Dry-process flue gas desulphurization device using steel slag as absorbent |
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Patent Citations (7)
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| CN1268387A (en) * | 1999-03-29 | 2000-10-04 | 青岛海洋大学 | Method for removing sulfur oxides from flue-gas by utilizing waste sludge of soda plant |
| JP2003251142A (en) * | 2002-02-28 | 2003-09-09 | Setec:Kk | Dry type waste gas desulfurization system |
| CN101249374A (en) * | 2008-03-28 | 2008-08-27 | 廖宗文 | Preparation of composite reclaiming agent and uses thereof |
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| CN101703886A (en) * | 2009-10-29 | 2010-05-12 | 太原理工大学 | Desulfuration method by directly utilizing magnesium slags in circulating fluidized bed boiler |
| CN101791622A (en) * | 2010-03-17 | 2010-08-04 | 上海天顿环境工程有限公司 | Process method for converting metal magnesium slag into desulphurizer of boiler |
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