CN101665844A - Method for preparing blast furnace slag micropowder by using sintering desulfuration byproducts as auxiliary materials - Google Patents
Method for preparing blast furnace slag micropowder by using sintering desulfuration byproducts as auxiliary materials Download PDFInfo
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- CN101665844A CN101665844A CN200910093646A CN200910093646A CN101665844A CN 101665844 A CN101665844 A CN 101665844A CN 200910093646 A CN200910093646 A CN 200910093646A CN 200910093646 A CN200910093646 A CN 200910093646A CN 101665844 A CN101665844 A CN 101665844A
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- slag
- desulfurization
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- sintering
- dry
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- 239000006227 byproduct Substances 0.000 title claims abstract description 53
- 239000002893 slag Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 26
- 238000005245 sintering Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 15
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000292 calcium oxide Substances 0.000 claims abstract description 12
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 235000010261 calcium sulphite Nutrition 0.000 claims abstract description 7
- 230000006641 stabilisation Effects 0.000 claims abstract description 6
- 238000011105 stabilization Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 230000003009 desulfurizing effect Effects 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000003818 cinder Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000010348 incorporation Methods 0.000 claims description 2
- 230000023556 desulfurization Effects 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- 238000011010 flushing procedure Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 239000004568 cement Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 239000010881 fly ash Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000002956 ash Substances 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 239000011404 masonry cement Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- -1 sulfur aluminate Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
一种以烧结脱硫副产物为辅料制备高炉矿渣微粉的方法，属于资源综合利用领域。将炼铁厂水冲渣池中输出的高炉矿渣按比例与烧结干法半干法脱硫副产物搅拌混匀，成为混合物料，搅拌的同时，矿渣中的游离水与脱硫副产物中的游离氧化钙发生反应，实现游离氧化钙的稳定化处理；随后混合物料进行烘干，在游离水脱除过程中，脱硫副产物中的亚硫酸钙发生氧化反应，生成硫酸钙；烘干后的物料通过粉磨形成高炉矿渣微粉。本发明在矿渣中掺入脱硫副产物后，由于脱硫副产物中氧化钙、硫酸钙的引入，改善了矿渣微粉的反应性能，能保证矿渣微粉性能达到国家标准相应规定，解决了干法脱硫副产物的综合利用难题。
The invention discloses a method for preparing blast furnace slag fine powder by using sintering desulfurization by-products as auxiliary materials, belonging to the field of comprehensive resource utilization. The blast furnace slag output from the water flushing slag pool of the ironworks is stirred and mixed with the sintering dry semi-dry desulfurization by-products in proportion to form a mixed material. While stirring, the free water in the slag and the free oxidation of the desulfurization by-products Calcium reacts to realize the stabilization of free calcium oxide; then the mixed material is dried, and in the process of free water removal, the calcium sulfite in the desulfurization by-product undergoes oxidation reaction to generate calcium sulfate; the dried material passes through Grinding to form blast furnace slag fine powder. After the present invention mixes the desulfurization by-products in the slag, due to the introduction of calcium oxide and calcium sulfate in the desulfurization by-products, the reaction performance of the slag micro-powder is improved, and the performance of the slag micro-powder can be guaranteed to meet the corresponding requirements of the national standard, and the side effects of dry desulfurization are solved. Comprehensive utilization of products is difficult.
Description
Technical field
The invention belongs to the comprehensive utilization of resources field, particularly relating to a kind of is the method that auxiliary material prepares blast-furnace cinder micro-powder with the sintering desulfuration by product, utilize existing Iron and Steel Production operation, on to dry method semi-dry desulphurization by product pre-treatment basis, be used for slag micropowder production preparation.
Background technology
Iron and steel enterprise is SO
2Discharging rich and influential family, and the SO of sintering process discharging
2Account for the whole SO of iron and steel enterprise
290% of total emission volumn.Along with improving constantly of China's Economic development and environmental requirement, steel enterprise sintering flue gas desulfurization is extremely urgent, carries out sintering flue gas desulfurization and administers for the SO of iron and steel enterprise
2Reduce discharging, improve the control of air quality and regional acid rain and have positive effect.
The Eleventh Five-Year Plan outline clearly proposed, to national SO in 2010
2Total emission volumn cuts down 10% than " 15 " end of term.Point out in " national acid rain and sulfur dioxide pollution control Eleventh Five-Year Plan " that State Bureau of Environmental Protection is put into effect, implement 14 flue gas of sintering machine engineerings, work out steel industry sulfurous gas and reduce discharging planning, emphasis advances steel industry flue gas of sintering machine engineering, the Eleventh Five-Year Plan period, non-electric industry such as iron and steel forms 400,000 tons sweetening power, adjusted the emission standard of sintering gas flue gas sulfuric dioxide simultaneously, implement in full the pollutant discharging license system, the blue law responsibility, prevent and remedy pollution or the like, this all will promote to improve the emission standard of steel industry pollutent in accordance with the law, and it is imperative that sintering desulfuration is administered.
More sophisticated both at home and abroad at present sulfur removal technology has tens of kinds, but because the investment of dry sintering sulfur removal technology is low, occupation of land is little, water consumption is few, technology is simple, and overcome some problem and shortage that wet desulfurizing process exists well, become the main flow technology of steel enterprise sintering desulfurization gradually.But, had a strong impact on the comprehensive utilization of desulfurizing byproduct owing to contain higher calcium oxide and calcium sulfite in the sintering dry method semi-dry desulphurization by product.At present, also do not have both at home and abroad technology and the technology that can effectively handle and fully utilize preferably, cause desulfurizing byproduct mostly to store up disposal, this has not only taken a large amount of soils, and also surrounding enviroment has been caused serial problem in it is stored up.
Application number is that the patent " is the manufacture method of the cement of retardant with the desulfurization ash " of 200410015724.X has been described a kind of cement manufacturing method, with desulfurization ash as retardant, by cement clinker, desulfurization ash, flyash and blast-furnace slag with 80～98: 2～6: 0～15: 0～15 weight ratio prepares cement.
Application number is that 200610085414.4 patent " masonry cement " has been described a kind of desulphurize fly ash of utilizing the circular fluid bed discharging and prepared the method for inferior grade masonry cement for main raw material, and cement formula is: desulphurize fly ash 50%～70%, gypsum 2%～6%, cement clinker 24%～48%.
Application number is that 200610068783.2 patent " utilizing the Technology of desulphurize fly ash sintering sulfur aluminate cement " has been described a kind of Technology of utilizing desulphurize fly ash to prepare aluminosulfate cement by high-temperature calcination, this technology need not alumina, need not or only need a small amount of gypsum, just can realize the production of aluminosulfate cement.
Application number is that 200710003052.4 patent " is the method that raw material is made fiber with desulphurize fly ash calcium " and application number are that 200710003054.3 patent " a kind of desulphurize fly ash calcium fibre pulp and be the papermaking process of raw material " has been described and utilized desulphurize fly ash to prepare fibre pulp and be the papermaking process of raw material.
By retrieval, existing patent mainly concentrates on fields such as utilizing the preparation of power plant desulfurization ash cement setting retarder, masonry cement and cement baking, does not retrieve the relevant patent of utilizing power plant desulfurization ash preparation slag micropowder; Find no and close the patent of invention that sinter fume dry method semi-dry desulphurization byproduct comprehensive utilizes.
Summary of the invention
The object of the present invention is to provide a kind of is the method that auxiliary material prepares blast-furnace cinder micro-powder with the sintering desulfuration by product, utilize existing Iron and Steel Production operation, with the sintering dry desulphurization by product as auxiliary material, be used for slag micropowder production, use the sintering dry desulphurization by product to produce slag micropowder as auxiliary material, the stabilization of calcium oxide and the oxide treatment of calcium sulfite have been realized in process of production, improved the reactivity worth of slag powders, solve the comprehensive utilization difficult problem of dry desulfurization by product, can realize the extensive utilization of steel enterprise sintering dry desulfurization by product.
Technical scheme of the present invention be with the sintering dry desulphurization by product as auxiliary material, be used to prepare blast-furnace cinder micro-powder, the incorporation of desulfurizing byproduct is no more than 10% of blast-furnace slag (dry state), desulfurizing byproduct gross weight, makes the SO in the slag micropowder
3Content satisfies the requirement of national standard relevant regulations.
The blast-furnace slag water ratio of exporting from iron work flush slag pond is 10%～40%, with the blast-furnace slag exported in the iron work flush slag pond in proportion with sintering desulfuration by product stirring and evenly mixing, become mixture, when stirring, free-water in the slag and the free calcium oxide in the desulfurizing byproduct react, and realize the stabilization treatment of free calcium oxide; Mixture is dried subsequently, and in the free water removal process, the calcium sulfite generation oxidizing reaction in the desulfurizing byproduct generates calcium sulfate; Material after the oven dry carries out grinding, finally forms blast-furnace cinder micro-powder.
The slag micropowder of being produced, its chemical ingredients and reactivity worth satisfy the requirement of national standard relevant regulations.
The invention has the advantages that:
(1) utilizes existing Iron and Steel Production operation, in the certain working procedure that slag micropowder is produced, add the sintering dry desulphurization by product, because the mixing of dry method semi-dry desulphurization by product reduced the water ratio of water before the slag drying, reduced the production energy consumption of slag micropowder, promoted the development of recycling economy.
(2) utilize original slag micropowder production process, desulfurizing byproduct is mixed with moisture slag and drying after, realized the stabilization of calcium oxide in the dry desulfurization by product and the oxide treatment of calcium sulfite, for large utilization of desulfurizing byproduct is laid a good foundation.
(3) in slag, mix desulfurizing byproduct after because the introducing of calcium oxide, calcium sulfate in the desulfurizing byproduct, improved the reactivity worth of slag micropowder, can guarantee the slag micropowder performance respective specified that is up to state standards.
Description of drawings
Be illustrated in figure 1 as involved in the present invention a kind of be the process flow sheet that auxiliary material prepares blast-furnace cinder micro-powder with the sintering desulfuration by product.
Embodiment
In conjunction with Fig. 1 the specific embodiment of the present invention is described below:
Add desulfurizing byproduct in the slag of in iron work flush slag pond, exporting (moisture 10%～40%), and stir, in this process, realized the stabilization treatment of calcium oxide in the desulfurizing byproduct; The hygrometric state grain slag that is mixed with desulfurizing byproduct is dried, and under the high temperature in drying course, the oxidizing atmosphere, has realized the oxide treatment of calcium sulfite in the desulfurizing byproduct, generates calcium sulfate; Material after the oven dry generates slag micropowder by grinding.Because the introducing of calcium oxide, calcium sulfate in the desulfurizing byproduct, improved the reactivity worth of slag micropowder, can guarantee the slag micropowder performance respective specified that is up to state standards.
Embodiment 1
Simulated above-mentioned industrial application process by experiment:
With desulfurizing byproduct is that 20% water mixes towards slag in 0 (A sample), 3% (B sample), 7% (C sample), 10% (D sample), 12% (E sample) ratio and water ratio respectively, the material ratio is all calculated with butt weight of material ratio, 105 ℃ of following constant temperature 4 hours, material grinding to the specific surface area after will drying at last was 410m then
2/ kg.
Analyzed the influence of pure slag powder sample (A sample), 3% desulfurizing byproduct volume (B sample), 7% desulfurizing byproduct volume (C sample), 10% desulfurizing byproduct volume (D sample), 12% desulfurizing byproduct volume (E sample) to chemical ingredients, reactive behavior and the stability of slag micropowder.
" cement normal consistency water consumption, time of coagulation, the stability method of inspection " (GB/T 1346-2001) standard of employing is measured stability.
Activity index is measured: adopt the ultimate compression strength of " Test method for strength of hydraulic cement mortar (ISO method) " (GB/T 17671-1999) mensuration sample 7d, 28d, by contrasting the calculated activity index with the benchmark sample.
The sample measurement result sees Table 1:
Table 1 sample performance measurement result
| Sample | Desulfurizing byproduct volume/% | 7d activity index/% | 28d activity index/% | ??SO 3/％ | Stability |
| The A sample | ??0 | ??102 | ??113 | ??3.00 | Qualified |
| The B sample | ??3 | ??111 | ??119 | ??3.18 | Qualified |
| The C sample | ??7 | ??107 | ??115 | ??3.42 | Qualified |
| The D sample | ??10 | ??101 | ??110 | ??3.60 | Qualified |
| The E sample | ??12 | ??94 | ??106 | ??3.72 | Qualified |
As shown in table 1, be 3%, 7%, 10% o'clock at the desulfurizing byproduct volume, 7d, 28d activity index all are better than benchmark sample A sample, and are 12% o'clock at the desulfurizing byproduct volume, and then activity index is relatively poor than the benchmark sample.Each sample SO
3Content and stability all meet the relevant national standard requirement.
Therefore, the present invention can be not more than at 10% o'clock at the desulfurizing byproduct volume, and prepared composite powder performance satisfies the relevant national standard requirement.
Claims (3)
1, a kind of is the method that auxiliary material prepares blast-furnace cinder micro-powder with the sintering desulfuration by product, it is characterized in that: with the blast-furnace slag exported in the iron work flush slag pond in proportion with sintering dry method semi-dry desulphurization by product stirring and evenly mixing, become mixture, when stirring, free-water in the slag and the free calcium oxide in the desulfurizing byproduct react, and realize the stabilization treatment of free calcium oxide; Mixture is dried subsequently, and in the free water removal process, the calcium sulfite generation oxidizing reaction in the desulfurizing byproduct generates calcium sulfate; Material after the oven dry carries out grinding, finally forms blast-furnace cinder micro-powder.
2, in accordance with the method for claim 1, it is characterized in that: the incorporation of desulfurizing byproduct is no more than 10% of dry state blast-furnace slag, desulfurizing byproduct gross weight, makes the SO in the slag micropowder
3Content satisfies the requirement of national standard relevant regulations.
3, in accordance with the method for claim 1, it is characterized in that: the scoriaceous weight in wet base of pulling out in the described iron work flush slag pond is 10%～40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100936468A CN101665844B (en) | 2009-10-14 | 2009-10-14 | A method for preparing blast furnace slag micropowder by using sintering desulfurization by-products as auxiliary materials |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100936468A CN101665844B (en) | 2009-10-14 | 2009-10-14 | A method for preparing blast furnace slag micropowder by using sintering desulfurization by-products as auxiliary materials |
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| Publication Number | Publication Date |
|---|---|
| CN101665844A true CN101665844A (en) | 2010-03-10 |
| CN101665844B CN101665844B (en) | 2010-12-01 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708753A (en) * | 2013-12-06 | 2014-04-09 | 马钢(集团)控股有限公司 | Applications of semi-dry desulphurization product and usage method |
| CN105384375A (en) * | 2015-12-14 | 2016-03-09 | 文登蓝岛建筑工程有限公司 | Active admixture for building materials |
| CN106064172A (en) * | 2016-05-31 | 2016-11-02 | 武汉钢铁股份有限公司 | CaSO in a kind of Desulphurization3stabilization method |
-
2009
- 2009-10-14 CN CN2009100936468A patent/CN101665844B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708753A (en) * | 2013-12-06 | 2014-04-09 | 马钢(集团)控股有限公司 | Applications of semi-dry desulphurization product and usage method |
| CN105384375A (en) * | 2015-12-14 | 2016-03-09 | 文登蓝岛建筑工程有限公司 | Active admixture for building materials |
| CN106064172A (en) * | 2016-05-31 | 2016-11-02 | 武汉钢铁股份有限公司 | CaSO in a kind of Desulphurization3stabilization method |
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| Publication number | Publication date |
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| CN101665844B (en) | 2010-12-01 |
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Address after: 100041 Shijingshan Road, Shijingshan District, Shijingshan District, Beijing Patentee after: SHOUGANG GROUP Co.,Ltd. Address before: 100041 Shijingshan Road, Shijingshan District, Shijingshan District, Beijing Patentee before: SHOUGANG Corp. |
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