CN101875987B - Method for smelting low chromium pig iron by utilizing chromium slag - Google Patents
Method for smelting low chromium pig iron by utilizing chromium slag Download PDFInfo
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- CN101875987B CN101875987B CN2009102497624A CN200910249762A CN101875987B CN 101875987 B CN101875987 B CN 101875987B CN 2009102497624 A CN2009102497624 A CN 2009102497624A CN 200910249762 A CN200910249762 A CN 200910249762A CN 101875987 B CN101875987 B CN 101875987B
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Abstract
The invention discloses a method for smelting low chromium pig iron by utilizing chromium slag, which is characterized in that low chromium pig iron is prepared by carrying out granulation after mixing the chromium slag, iron ore powder, coke powder and lime, sintering granules by a sintering machine to form sintered ores after granulation, and then sending the sintered ores into a blast furnace to smelt. The invention has the advantages that the chromium slag is adopted as raw materials and smelted to form the low chromium pig iron by utilizing the blast furnace, thereby treating the harmful waste chromium slag, also increasing the raw material source of the low chromium pig iron, providing a new economic and practical raw material source to industries of stainless steel, wear resistance cast and the like and changing waste into valuable.
Description
Technical field
The present invention relates to a kind of method of utilizing the low chromium pig iron of chromium slag melting.
Background technology
Sodium chromate is one of a kind of important Inorganic Chemicals, is the basic raw material of producing sodium dichromate 99, potassium bichromate, chromic anhydride, chrome green.Be used for that plating, process hides, printing and dyeing, medicine, grease are refining, the industry such as catalyzer, synthetic rubber, spices and stainless steel manufacturing.Along with the industrialization development of China and world other countries, its demand is more and more.But the production of Sodium chromate at present, the one, environmental pollution is serious, and the 2nd, production efficiency is low, and yield is low, is only 75%.Environmental pollution is particularly outstanding, and developed country imputes to developing country with this production technology one after another.In China, 1 ton of sodium dichromate 99 of every production just discharges 3 tons of chromium slags, if by producing 80000 tons of sodium dichromate 99s per year, discharges approximately 240,000 tons of chromium slags every year, existing still cumulative year after year.
Contain toxic large sexavalent chrome in the chromium slag, if it is stacked in outdoor, drench when soaking when being subject to sleet, sexavalent chrome is dissolved and permeates the ground water or enter surface water body, can cause serious environmental pollution, even cause pollution incident, it is a kind of serious main chemical industry solid waste that endangers.Prevent at present the chromium slag contaminated improvement of production process that mainly is, adopt without the few calcium sinter process of calcium and produce chromic salts, greatly to cut down chromium slag generation; But in the prior art, the generation of chromium slag is still inevitable.
The difficulty of governance of chromium slag is very big, China and countries in the world is devoted to the research for the treatment of of chromate slag so far from the sixties always, though get along with, effect is undesirable.Therefore, how to process the chromium slag, making it become useful materials is that present chromic acid is received the important topic that faces in producing.
Summary of the invention
The objective of the invention is in order to overcome deficiency of the prior art, provide a kind of use chromium slag as raw material, utilize the method for the low chromium pig iron of chromium slag melting.
For realizing above purpose, the present invention is achieved through the following technical solutions:
Utilize the method for the low chromium pig iron of chromium slag melting, it is characterized in that, granulation after chromium slag, powdered iron ore are mixed with coke powder, lime is sintered to agglomerate with sinter machine after granulation, then agglomerate is sent into the low chromium pig iron of blast-furnace smelting.
Water can be made during granulation, also tackiness agent can be used.
Preferably, the raw material of agglomerate comprises chromium slag, coke powder, lime and powdered iron ore, mass percent is chromium slag 20%～40%, coke powder 1%, lime 0.5%～5%, all the other are powdered iron ore, after mixing, granulation is bead, after granulation, particle diameter is 1.5～8mm, then sinters bead into agglomerate with sinter machine; Agglomerate is sent into blast furnace and the low chromium pig iron of chrome ore smelting production.
The coke powder that uses in the present invention is coke powder.
Preferably, described chromium slag ingredient by weight percentage composition comprise chromium sesquioxide 5%～35%.
Preferably, the raw material of agglomerate also comprises chromite ore fine, and described chromite ore fine is that the chromium sesquioxide weight percentage is the chromite ore fine more than 40%.
Adding chrome ore is in order to regulate the chromium content in low chromium pig iron.Chromium content in chromium pig iron as low in need is higher, and the chromium sesquioxide in the chromium slag is when not enough, adds chrome ore can improve chromium content in low chromium pig iron.
Preferably, described powdered iron ore is selected from the iron ore powder of iron-holder more than 50%.
Preferably, during described blast-furnace smelting, blast furnace coke ratio is 0.8～1.3, is preferably 0.90～1.15.Coke ratio of the present invention refers to produce the weight of coke that one ton of low chromium pig iron consumes.
Preferably, during blast-furnace smelting, the coke that uses is low reductibility coke, i.e. CRI≤25%.
More preferably, the weight percentage of described coke sulphur is less than 0.6%, and the phosphorus weight percentage is less than 0.01%, and coke particle diameter is 20-40mm.
The coke ratio of selecting because of the present invention is high, therefore, and the coke that selective reaction is weak, the CO that hyperergic coke blast furnace cold zone occurs
2The reaction aggravation of+C=2CO is helpless to the reduction of chromium, and reactive weak coke can enlarge the combustion zone, is conducive to reaction smoothly; Can make again heat concentrate on bottom house, favourable to reduction and the raising rate of recovery of chromium.
When smelting in blast furnace, can add one or both in silica, lime, adding of silica and lime is slag dual alkalinity and the polynary basicity that produces after blast-furnace smelting in order to adjust, and its add-on needs to determine according to the component concentration of each component concentration in silica and slag.The slag dual alkalinity is 0.4～1.3, is preferably 0.95～1.1.Polynary basicity is 0.4～0.8, is preferably 0.5～0.7.
Dual alkalinity of the present invention refers to CaO/SiO in slag
2Weight ratio.
Polynary basicity of the present invention refers to (Al in slag
2O
3+ MgO)/(CaO+SiO
2+ Al
2O
3+ MgO) weight ratio.
Preferably, the temperature during blast-furnace smelting is 1700 ℃～1800 ℃.
Preferably, in granulation process, make water do the tackiness agent granulation.Water mixes with lime and has certain viscosity, utilizes the viscosity granulation of water and lime, can increase granule strength, reduces powder.
In the blast-furnace smelting step, the chromium in slag, iron are reduced into the low chromium pig iron of metal under reductive agent exists, utilize the proportion of ferrochrome different from the proportion of slag.Ferrochrome sinks to bottom house, and slag is upper, after reduction reaction is ended, goes out scum silica frost after first going out ferrochrome, is mixed on a small quantity the cooling rear natural separation of bits in product.Coke at high temperature has very strong reductibility, and the sexavalent chrome in the chromium slag can be by coke and carbon monoxide reduction in sintering process and smelting process.
Its reaction principle can represent with following equation:
2C+O
2＝2CO↑ (1)
2Na
2CrO
4+3CO＝Cr
2O
3+2Na
2O+3CO
2↑ (2)
Cr
2O
3+3C＝2Cr+3CO↑ (3)
Cr
2O
3+3CO＝2Cr+3CO
2↑ (4)
FeO·Cr
2O
3+4C＝Fe+2Cr+4CO↑ (5)
The present invention is owing to adopting TYPE MINI-PELLET SINTERING TECHNIQUE, and pellet sintering is a kind of measure of intensified-sintered process, be compound is all made be limited to 6～8mm, under be limited to 1.5～2.0mm bead carry out the method for sintering.Be basically to eliminate in the compound particle diameter with the difference of general sintering and less than the powder of 1.5mm, all made bead; Become agglomerate by liquid bonding phase on sinter machine, rather than be consolidated into pellet.Because needs are made bead to whole sintered materials, therefore must strengthen the pelletizing process, adopt lime and water that compound is processed or use the way such as tackiness agent, improve the balling property of compound.
Beneficial effect of the present invention is: the present invention adopt the chromium slag as raw material, utilize blast-furnace smelting to hang down chromium pig iron.Namely processed harmful waste chromium slag, can increase again the raw material sources of low chromium pig iron, for the industries such as stainless steel industry, wear resistance castings provide a kind of new economic and practical raw material sources, realized turning waste into wealth simultaneously.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail:
Utilize the method for the low chromium pig iron of chromium slag melting, with chromium slag, powdered iron ore and after coke powder, lime mix, add the entry granulation, granulation is bead, and the bead median size is 1.5～8mm; Be sintered to agglomerate with sinter machine after granulation, then agglomerate sent into blast furnace and chrome ore and coke powder smelt the low chromium pig iron of production, during blast-furnace smelting, add according to circumstances silica.
Agglomerate raw material weight percentage in each embodiment is each raw material consumption during blast-furnace smelting when:
Chromium slag main component weight in average percentage composition:
| Cr 2O 3 | CaO | MgO | Fe | Al 2O 3 | SiO 2 | Cr 6+ |
| 13.54％ | 9.58％ | 13.10％ | 26.12％ | 13.87％ | 4.82％ | 0.5％ |
Iron level adjustment in the low chromium pig iron that the consumption of powdered iron ore can be produced according to wherein iron level and final needs.
The iron ore powder of the preferred iron-holder of powdered iron ore more than 50%.Powdered iron ore Contents of Main Components in above embodiment is:
| Project | Fe | SiO 2 | CaO | Al 2O 3 | MgO |
| Powdered iron ore | 63.76％ | 6.56％ | 0.85％ | 1.44％ | 0.44％ |
In each embodiment, various data such as the following table measured in production process:
To using the slag, gas ash, the sack dust that discharge in the inventive method production process, detect, as following table:
| Project | Cr | Cr 6+ | Cr 2O 3 |
| Grain slag (%) | 0.67～0.69 | 0.00 | 0.61～0.69 |
| Dried slag (%) | 0.50～0.68 | 0.00 | 0.68～0.76 |
| Gravitational dust collection ash (%) | 0.09～3.32 | 0.00 | 2.90～3.32 |
| Bag-type dust ash (%) | 0.19～2.27 | 0.00 | 2.27～2.55 |
[0047]As can be seen from the above table, poisonous sexavalent chrome all is converted to simple substance chromium and trivalent chromium.
Predominant quantity percentage composition in the low chromium pig iron of final production is as shown in the table:
| Embodiment | Cr | Si | P | Mn | C | S | Fe | Contain Cr in the slag that blast-furnace smelting produces 2O 3 | Chromium utilization ratio % |
| 1 | 11.05 | 1.10 | 0.04 | 0.94 | 5.96 | 0.02 | 70.13 | 0.275 | 86 |
| 2 | 20.08 | 1.08 | 0.05 | 0.68 | 6.32 | 0.01 | 68.64 | 0.475 | 90 |
| 3 | 21.01 | 0.88 | 0.03 | 0.55 | 6.33 | 0.01 | 66.92 | 1.275 | 92 |
| 4 | 17.14 | 0.93 | 0.04 | 0.78 | 6.40 | 0.01 | .68.76 | 0.95 | 93 |
| 5 | 16.36 | 1.01 | 0.04 | 0.92 | 6.24 | 0.01 | 71.27 | 1.705 | 90 |
| 6 | 14.86 | 0.78 | 0.05 | 1.12 | 6.35 | 0.01 | 74.54 | 1.49 | 83 |
Embodiment in the present invention only is used for that the present invention will be described, does not consist of the restriction to the claim scope, and other substituting of being equal in fact that those skilled in that art can expect are all in protection domain of the present invention.
Claims (10)
1. utilize the method for the low chromium pig iron of chromium slag melting, it is characterized in that, then granulation after chromium slag, powdered iron ore are mixed with coke powder, lime is sintered to agglomerate with sinter machine, then agglomerate is sent into the low chromium pig iron of blast-furnace smelting;
Wherein, the raw material of agglomerate comprises chromium slag, coke powder, lime and powdered iron ore, mass percent is chromium slag 20%～40%, coke powder 1%, lime 0.5%～5%, all the other are powdered iron ore, after mixing, granulation is bead, after granulation, particle diameter is 1.5～8mm, then sinters bead into agglomerate with sinter machine; Agglomerate is sent into blast furnace and the low chromium pig iron of chrome ore smelting production.
2. the method for utilizing the low chromium pig iron of chromium slag melting according to claim 1, is characterized in that, during agglomerate processed, its raw material also comprises chromite ore fine, and described chromite ore fine is that the chromium sesquioxide weight percentage is the chromite ore fine more than 40%.
3. the method for utilizing the low chromium pig iron of chromium slag melting according to claim 1, is characterized in that, described chromium slag ingredient percentage composition by weight comprises chromium sesquioxide 5%～35%.
4. the method for utilizing the low chromium pig iron of chromium slag melting according to claim 1, is characterized in that the powdered iron ore of described powdered iron ore chosen from Fe content more than 50%.
5. the method for utilizing the low chromium pig iron of chromium slag melting according to claim 1, is characterized in that, the slag dual alkalinity that produces after blast-furnace smelting is 0.4～1.3.
6. the method for utilizing the low chromium pig iron of chromium slag melting according to claim 1, is characterized in that, the polynary basicity of the slag that produces after blast-furnace smelting is 0.4～0.8.
7. the method for utilizing the low chromium pig iron of chromium slag melting according to claim 1, is characterized in that, during described blast-furnace smelting, blast furnace coke ratio is 0.8～1.3.
8. the method for utilizing the low chromium pig iron of chromium slag melting according to claim 1, is characterized in that, during blast-furnace smelting, the coke powder that uses is low reductibility coke powder.
9. the method for utilizing the low chromium pig iron of chromium slag melting according to claim 1, is characterized in that, makes water or tackiness agent in granulation process.
10. the method for utilizing the low chromium pig iron of chromium slag melting according to claim 1, is characterized in that, the temperature during blast-furnace smelting is 1700 ℃～1800 ℃.
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| CN101875987B true CN101875987B (en) | 2013-06-05 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103361484A (en) * | 2012-03-26 | 2013-10-23 | 云南曲靖越钢集团有限公司 | Harmless treatment method of chromium slag generated by preparation of chromium salt employing little calcium roasting method, and application of method |
| CN102816923A (en) * | 2012-09-10 | 2012-12-12 | 泰州振昌工业废渣综合利用有限责任公司 | Agglomeration method for industrial solid waste |
| CN104017927B (en) * | 2014-06-03 | 2015-11-25 | 中信锦州金属股份有限公司 | A kind of chromium slag melting that utilizes is containing the method for chromium pig iron |
| CN105861833B (en) * | 2016-06-08 | 2017-12-15 | 江苏省冶金设计院有限公司 | A kind of method of Combined Treatment copper ashes and chromium slag |
| CN106086429A (en) * | 2016-06-08 | 2016-11-09 | 江苏省冶金设计院有限公司 | A kind of Combined Treatment chromium slag and the method for copper ashes |
| CN106500106B (en) * | 2016-09-19 | 2019-06-07 | 中信锦州金属股份有限公司 | A method of detoxified using sintering technology leached-out chromium residue |
| CN106319200A (en) * | 2016-10-25 | 2017-01-11 | 重庆文渠环保科技有限公司 | Method for harmlessly treating chromium-containing waste by utilizing rotary kiln technology |
| CN108865316B (en) * | 2017-09-28 | 2023-07-11 | 华北理工大学 | Preparation method of biomass fuel applied to iron ore sintering |
| CN114150148A (en) * | 2021-12-10 | 2022-03-08 | 四川鑫鼎新材料有限公司 | Method for extracting chromium-containing alloy from iron-chromium solid tailings to manufacture stainless steel product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035848A (en) * | 1988-03-21 | 1989-09-27 | 冶金工业部钢铁研究总院 | Vanadium chromium leaches tailings ironmaking comprehensive utilization process |
| CN1059370A (en) * | 1990-08-31 | 1992-03-11 | 黄石市无机盐厂 | Chromium residue detoxifying, smelting contain the method for chromium pig iron |
| CN101709369A (en) * | 2009-08-21 | 2010-05-19 | 新疆沈宏集团股份有限公司 | Method for jointly producing chromium salt and ferrochromium alloy by sintering with wet and fire methods |
-
2009
- 2009-12-02 CN CN2009102497624A patent/CN101875987B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035848A (en) * | 1988-03-21 | 1989-09-27 | 冶金工业部钢铁研究总院 | Vanadium chromium leaches tailings ironmaking comprehensive utilization process |
| CN1059370A (en) * | 1990-08-31 | 1992-03-11 | 黄石市无机盐厂 | Chromium residue detoxifying, smelting contain the method for chromium pig iron |
| CN101709369A (en) * | 2009-08-21 | 2010-05-19 | 新疆沈宏集团股份有限公司 | Method for jointly producing chromium salt and ferrochromium alloy by sintering with wet and fire methods |
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