CN103801192A - Flue gas denitrification process for cement kiln - Google Patents
Flue gas denitrification process for cement kiln Download PDFInfo
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- CN103801192A CN103801192A CN201410060545.1A CN201410060545A CN103801192A CN 103801192 A CN103801192 A CN 103801192A CN 201410060545 A CN201410060545 A CN 201410060545A CN 103801192 A CN103801192 A CN 103801192A
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- slag
- flue gas
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- iron vitriol
- cement kiln
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Abstract
The invention discloses a flue gas denitrification process for a cement kiln. The flue gas denitrification process comprises the following steps: adding a dispersing agent before carrying out filter pressing on iron-titanium slag so as to obtain the iron-titanium slag with the good dispersibility, drying the iron-titanium slag by virtue of hot air from a grate cooler of the cement kiln, and adding vanadium-titanium slag to obtain a flue gas denitrification agent; carrying out denitrification on kiln tail gas by utilizing carbide slag, and collecting dust used as a building material. By utilizing industrial waste as a denitrification agent, the flue gas denitrification process has the characteristics of simplicity and low cost.
Description
Technical field
The present invention relates to a kind of environmental protection technology, particularly a kind of method of processing cement kiln flue gas.
Background technology
The generation of nitrogen oxide is a part for combustion reaction: the nitrogen oxide that burning generates is mainly NO and NO
2, be referred to as NOx.After NOx in atmosphere is water-soluble, can be generated as nitric acid rain, acid rain can bring harm widely to environment, causes huge economic loss, as: corrosion building and industrial equipment; Destroy outdoor cultural relics and historic sites; Damage plant leaf surface, cause forest death; Make fishes and shrimps death in lake; Spoiled soil composition, makes crop production reduction even dead; The underground water that drinking acid compound is polluted, can produce directly harm etc. to health.
Within 2010, China's cement output is 18.68 hundred million tons, nearly 5000 of cement production enterprise.Cement burning produces a large amount of nitrogen oxide, and concentration of emission is 300-2200mg/m
3, grog per ton approximately produces 1.5～1.8kg nitrogen oxide.Approximately 2,000,000 tons of national cement discharge nitrogen oxide in 2010, account for 10% of national discharged nitrous oxides total amount, are only second to the discharge capacity of power industry and motor-vehicle tail-gas, occupy the 3rd.China now carries out " cement industry atmosphere pollutants emission standards " (GB4915-2004) regulation NOx concentration of emission must not exceed 800mg/m
3.Must not stipulate and exceed 150mg/m3 in In Hangzhou Region of Zhe Jiang Province.Along with the raising of socioeconomic development and whole society's environmental consciousness, the NOx discharge standard of cement industry will be increasingly strict [thank to victory. research and the application [J] of nitrogen denitration technology, China environmental protection industry, 2013, (8): 25-29 fall in dore furnace fractional combustion].
The selective reducing process of denitration technology, low nitrogen grading combustion technology and the first two group technology etc. mainly applied at whole world cement industry at present.Mainly adopt ammonia to reduce to nitrogen oxide in selective reduction method, main chemical reaction has:
4NH
3+4NO+O
2→4N
2+6H
2O
2NH
3+NO+NO
2→2N
2+3H
2O
4NH
3+2NO
2+O
2→3N
2+6H
2O
[You Zhenfeng, fourth is bright, Fang Wencang, cement industry gas denitrifying technology summary and prospect [J], Guangdong building materials, 2013, (5): 29-33].Selective reduction method is divided into catalyst-free selective reduction method and catalyst selected deoxidizing method.Catalyst-free selective reduction method denitration rate is low, and operating cost is high.Catalyst selected deoxidizing method, is the highest gas denitrifying technology of current denitration rate, has the feature [Fang Jingrui such as high efficiency, high selectivity and economy, horse loyalty, Wang Lan. cement kiln fuel gas catalytic reduction denitration Research progress [J], Environmental Pollution and Control, 2013,35(2): 85-92].
In catalyst selected deoxidizing method, conventional catalyst has [Cui Suping, Luo little Gen, Guo Hongxia etc., a kind of low-temperature denitration catalysts that add auxiliary agent and preparation method thereof (patent documentation CN201310480494) such as iron oxide, titanium oxide, vanadium oxide; Wu Ning, Song Qiang, Yao Qiang etc., a kind of preparation of iron-based selective catalytic reduction denitration catalyst (patent documentation CN200810112624)].Therefore can in cement raw material, add vanadium titanium slag as catalyst.But catalyst selected deoxidizing method is owing to using ammoniacal liquor and catalyst, and the cost of denitration is still higher.
Ammonium jarosite slag (abbreviation iron vitriol slag) is a kind of discarded object producing in Zinc Hydrometallurgy Process, if it is not processed land occupation, contaminated environment [Chen Yongming, Tang Motang, the interim state non-ferrous metal journal Yang Sheng of the 19th volume the 7th sea etc., NaOH decomposes containing indium iron vitriol slag new technology [J], China YouSe Acta Metallurgica Sinica, 2009,19(7): 1322-1331].
At present, the method for iron vitriol slag processing is mainly and adopts high-temperature calcination and alkali decomposition additive processing, the complex process of alkaline cleaning, the waste residue obtaining, waste liquid to be difficult to process.High-temperature calcination technique is simple, produces without waste residue, waste gas, waste liquid.
Iron vitriol slag high-temperature calcination processing is mainly and adopts rotary kiln heating and calcining, according to the thermal property of ammonium jarosite, in heat temperature raising process, thermal decomposition occurs, the product difference that different temperatures is decomposed; At 290-479 ℃, the intermediate product that the product of decomposition is iron oxide and ammonia; More than 650 ℃, obtain iron oxide and sulfur oxide final decomposition, and reaction equation is as follows:
[hot acid leaches the processing method [J] of iron vitriol slag in zinc hydrometallurgy, Hunan non-ferrous metal, 1994,10(3 for Qiu electricity Yun, Ma Rongjun): 158-162].Though existing method can be processed iron vitriol slag, need to build special equipment, external energy heats iron vitriol slag, and separating of the ammonia of generation and sulfur oxide is more difficult, is unfavorable for reclaiming
Vanadium titanium slag is to carry smelting vanadium and smelting the waste residue producing after titanium; in slag, contain a small amount of vanadium and titanium; catalyst with it as reduction of nitrogen oxide; a small amount of vanadium titanium slag add to the performance of cement do not have harmful effect [Wang Zhiwei. the Pan Gang of Pan Gang group vanadium company's steel slag processing and utilizing present situation and development trend [J]. metallurgy environment protection; 2011, (1): 34-36].
Carbide slag is for calcium carbide being raw material while preparing acetylene, the waste residue of generation, and the main component of carbide slag is calcium hydroxide.Calcium hydroxide in carbide slag and sulfur oxide reaction, generate calcium sulfate, can be used as construction material.
Summary of the invention
The object of this invention is to provide a kind of flue gas that utilizes method that ammonia that iron vitriol slag decomposites reduces to nitrogen oxide to process cement kiln.
For reaching above object, the present invention takes following technical scheme to be achieved:
A technique for cement kiln denitrating flue gas, is characterized in that, comprises the steps:
(1) in the discarded object iron vitriol slag producing at zinc hydrometallurgy, add dispersant, after stirring, iron vitriol slag is carried out to press filtration, after press filtration, dry, obtain the iron vitriol slag of favorable dispersibility; Wherein, dispersant adopts the one in rosin soap, alkyl benzene calcium sulfonate, calcium lignosulfonate, polycarboxylic acids calcium or oxidized paraffin wax soap, and addition is the 0.1-0.5% of iron vitriol slag quality; The thermal source of drying use is the waste heat that cement-kiln grate-cooler is got rid of, and temperature is 200-250 ℃;
(2) in the iron vitriol slag of drying, add the vanadium titanium slag powder of iron vitriol slag quality 1-5%, mix, obtain smoke denitrifier;
(3) in the rotary system of cement, add smoke denitrifier, addition is cement raw meal quality 0.1%;
(4) before kiln tail high-temperature blower, install a desulfurizing tower and dust-precipitator additional, the sulphur in tail gas is reclaimed with carbide slag, the dust of collecting is as construction material.
In such scheme, the oven dry of described iron vitriol slag is smoked 1-2 hour with rotary dryer.The particle diameter of described vanadium titanium slag powder is less than 80 μ m.The implantation site that adds of described denitrfying agent is that the top of cement kiln end partial solution stove adds.
The advantage of technique of the present invention is that the present invention utilizes the waste heat in cement plant to be dried iron vitriol slag, has reduced iron vitriol slag processing cost.The iron oxide producing also can be used as catalyst and the required iron-bearing material of manufacture of cement of reduction of nitrogen oxide.The present invention has also added the catalyst of vanadium titanium slag powder (containing a small amount of vanadium and titanium) as reduction of nitrogen oxide simultaneously.Iron vitriol slag decomposes the sulphur producing, and a part is reacted and entered clinker with the calcium oxide of decomposition of limestone generation, the gypsum in can part place of cement; Part is got rid of from kiln tail, reclaims with carbide slag, as construction material.The present invention had both accomplished twice laid, had protected again environment, and the construction of recycling economy is had to important positive effect.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
A technique for cement kiln denitrating flue gas, comprises the steps:
(1) in the time of Zinc Hydrometallurgy Process, before iron vitriol slag press filtration, add dispersant, after stirring, iron vitriol slag is carried out to press filtration, obtain the iron vitriol slag of favorable dispersibility; Iron vitriol slag after press filtration is dried with rotary dryer.Wherein, dispersant is the one in rosin soap, alkyl benzene calcium sulfonate, calcium lignosulfonate, polycarboxylic acids calcium or oxidized paraffin wax soap, and addition is that the 0.1-0.5%(of iron vitriol slag quality is referring to table 1); The thermal source of drying use is the waste heat that cement-kiln grate-cooler is got rid of, and temperature is 200-250 ℃, and the time of staying of iron vitriol slag in dryer is 1-2 hour.
(2) become particle diameter to be less than the grinding of 80 μ m vanadium titanium slag grinding, it is mixed with iron vitriol slag, obtain smoke denitrifier.Wherein, the addition of vanadium titanium slag is that the 1-5%(of iron vitriol slag quality is referring to table 1).
(3) in rotary cement kiln system, the top of kiln afterbody dore furnace adds smoke denitrifier, and addition is cement slurry 0.1%.
(4) before kiln tail high-temperature blower, install a desulfurizing tower and dust-precipitator additional, the sulphur in tail gas is reclaimed with carbide slag, the dust of collecting is as construction material.
The eliminating efficiency of the middle nitrogen oxide of the present invention to flue gas is: embodiment 1 is that 80%, embodiment 2 is that 90%, embodiment 3 is that 82%, embodiment 4 is that 83%, embodiment 5 is that 86%, embodiment 6, embodiment 7, embodiment 8 are 90%.
Table 1
Claims (4)
1. a technique for cement kiln denitrating flue gas, is characterized in that, comprises the steps:
(1) in the discarded object iron vitriol slag producing at zinc hydrometallurgy, add dispersant, after stirring, iron vitriol slag is carried out to press filtration, after press filtration, dry, obtain the iron vitriol slag of favorable dispersibility; Wherein, dispersant adopts the one in rosin soap, alkyl benzene calcium sulfonate, calcium lignosulfonate, polycarboxylic acids calcium or oxidized paraffin wax soap, and addition is the 0.1-0.5% of iron vitriol slag quality; The thermal source of drying use is the waste heat that cement-kiln grate-cooler is got rid of, and temperature is 200-250 ℃;
(2) in the iron vitriol slag of drying, add the vanadium titanium slag powder of iron vitriol slag quality 1-5%, mix, obtain smoke denitrifier;
(3) in the rotary system of cement, add smoke denitrifier, addition is cement raw meal quality 0.1%;
(4) before kiln tail high-temperature blower, install a desulfurizing tower and dust-precipitator additional, the sulphur in tail gas is reclaimed with carbide slag, the dust of collecting is as construction material.
2. the technique of cement kiln denitrating flue gas as claimed in claim 1, is characterized in that, the oven dry of described iron vitriol slag is smoked 1-2 hour with rotary dryer.
3. the technique of cement kiln denitrating flue gas as claimed in claim 1, is characterized in that, the particle diameter of described vanadium titanium slag powder is less than 80 μ m.
4. the technique of cement kiln denitrating flue gas as claimed in claim 1, is characterized in that, the implantation site that adds of described denitrfying agent is that the top of cement kiln end partial solution stove adds.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039712A (en) * | 2015-08-14 | 2015-11-11 | 陕西理工学院 | Technology for recycling valuable metal from jarosite slag |
| CN105567961A (en) * | 2016-01-18 | 2016-05-11 | 西南科技大学 | Method for separating iron and sulfur in jarosite slag through biological technique |
| CN107469847A (en) * | 2017-10-23 | 2017-12-15 | 李俊霞 | A kind of preparation method of denitrating catalyst |
| CN107551799A (en) * | 2017-10-12 | 2018-01-09 | 北京工业大学 | A kind of method of dry-process cement rotary kiln flue gas desulfurization and denitrification integration |
| CN107552062A (en) * | 2017-10-23 | 2018-01-09 | 李俊霞 | A kind of cheap denitrating catalyst and preparation method thereof |
| CN107649144A (en) * | 2017-10-23 | 2018-02-02 | 李俊霞 | A kind of preparation method of novel denitration catalyst |
| CN107744819A (en) * | 2017-10-23 | 2018-03-02 | 李俊霞 | A kind of preparation method of Environmentally-friedenitration denitration catalyst |
| CN108380212A (en) * | 2018-03-09 | 2018-08-10 | 北京工业大学 | A kind of inorganic porous material and its application method for cement kiln dore furnace denitrating flue gas |
| CN114367179A (en) * | 2021-12-03 | 2022-04-19 | 首钢集团有限公司 | Denitration carbon-fixing agent taking steel slag as raw material and preparation method and application thereof |
| CN114682085A (en) * | 2022-03-08 | 2022-07-01 | 天津水泥工业设计研究院有限公司 | Method for preparing cement kiln synergistic desulfurization and denitrification agent by resource utilization of hazardous waste and solid waste |
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| JP2007160223A (en) * | 2005-12-14 | 2007-06-28 | Sumitomo Osaka Cement Co Ltd | Exhaust gas neutralizer using molten slag |
| CN101559318A (en) * | 2009-05-25 | 2009-10-21 | 天津城市建设学院 | Thermal carbon composite denitration method for coal-fired boiler |
| CN102658008A (en) * | 2012-05-14 | 2012-09-12 | 华电电力科学研究院 | Combined device and method for desulfurization, denitrification and heavy metal ion removal |
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Patent Citations (3)
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| JP2007160223A (en) * | 2005-12-14 | 2007-06-28 | Sumitomo Osaka Cement Co Ltd | Exhaust gas neutralizer using molten slag |
| CN101559318A (en) * | 2009-05-25 | 2009-10-21 | 天津城市建设学院 | Thermal carbon composite denitration method for coal-fired boiler |
| CN102658008A (en) * | 2012-05-14 | 2012-09-12 | 华电电力科学研究院 | Combined device and method for desulfurization, denitrification and heavy metal ion removal |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039712A (en) * | 2015-08-14 | 2015-11-11 | 陕西理工学院 | Technology for recycling valuable metal from jarosite slag |
| CN105567961A (en) * | 2016-01-18 | 2016-05-11 | 西南科技大学 | Method for separating iron and sulfur in jarosite slag through biological technique |
| CN105567961B (en) * | 2016-01-18 | 2017-10-03 | 西南科技大学 | A kind of method that iron and sulphur in iron vitriol slag are separated with biotechnology |
| CN107551799A (en) * | 2017-10-12 | 2018-01-09 | 北京工业大学 | A kind of method of dry-process cement rotary kiln flue gas desulfurization and denitrification integration |
| CN107649144A (en) * | 2017-10-23 | 2018-02-02 | 李俊霞 | A kind of preparation method of novel denitration catalyst |
| CN107552062A (en) * | 2017-10-23 | 2018-01-09 | 李俊霞 | A kind of cheap denitrating catalyst and preparation method thereof |
| CN107469847A (en) * | 2017-10-23 | 2017-12-15 | 李俊霞 | A kind of preparation method of denitrating catalyst |
| CN107744819A (en) * | 2017-10-23 | 2018-03-02 | 李俊霞 | A kind of preparation method of Environmentally-friedenitration denitration catalyst |
| CN107552062B (en) * | 2017-10-23 | 2020-06-09 | 山东鲁南渤瑞危险废物集中处置有限公司 | Cheap denitration catalyst and preparation method thereof |
| CN107649144B (en) * | 2017-10-23 | 2020-07-14 | 中耐控股集团有限公司 | Preparation method of denitration catalyst |
| CN107744819B (en) * | 2017-10-23 | 2020-08-21 | 安徽金森源环保工程有限公司 | Preparation method of environment-friendly denitration catalyst |
| CN108380212A (en) * | 2018-03-09 | 2018-08-10 | 北京工业大学 | A kind of inorganic porous material and its application method for cement kiln dore furnace denitrating flue gas |
| CN114367179A (en) * | 2021-12-03 | 2022-04-19 | 首钢集团有限公司 | Denitration carbon-fixing agent taking steel slag as raw material and preparation method and application thereof |
| CN114682085A (en) * | 2022-03-08 | 2022-07-01 | 天津水泥工业设计研究院有限公司 | Method for preparing cement kiln synergistic desulfurization and denitrification agent by resource utilization of hazardous waste and solid waste |
| CN114682085B (en) * | 2022-03-08 | 2024-01-02 | 天津水泥工业设计研究院有限公司 | Method for preparing cement kiln synergistic desulfurization and denitrification agent by recycling hazardous waste and solid waste |
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