CN107312909A - A kind of desulfurization slag former - Google Patents
A kind of desulfurization slag former Download PDFInfo
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- CN107312909A CN107312909A CN201610290252.1A CN201610290252A CN107312909A CN 107312909 A CN107312909 A CN 107312909A CN 201610290252 A CN201610290252 A CN 201610290252A CN 107312909 A CN107312909 A CN 107312909A
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- slag former
- desulfurization slag
- desulfurization
- extractant
- carbonaceous
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
- C21C7/0645—Agents used for dephosphorising or desulfurising
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
The invention discloses a kind of desulfurization slag former, it is related to steel desulfurization technical field, it, for raw material, is added in the phosphorous chemical industry waste liquid handled through desiliconization with phosphorous chemical industry byproduct, red mud and converter dust-removing ash using calcium carbonate as carbonaceous extractant, the fluorine in waste liquid is extracted, and by silica filtration therein.Added using red mud as irony conditioning agent in gained calcirm-fluoride filtrate, obtain a kind of desulfurization slag former head product.It is added to using converter dust-removing ash as calcareous conditioning agent in desulfurization slag former head product, after evaporative crystallization, high-pressure molding, drying, screening, finally gives a kind of desulfurization slag former.Desulfurization slag former and its production method that the present invention is provided, realize the recycling of phosphatization byproduct, red mud and converter dust-removing ash, reduce the cost of slugging and desulfurization, improve the effect of slugging and desulfurization.
Description
Technical field
The invention belongs to environmental technology field, more particularly to a kind of method of molten steel desulfurizing slag former.
Background technology
, it is necessary to which the sulphur in molten steel is removed in converter steelmaking process.Desulfurizing agent composition classification include oxidant, fixative and
Fluxing agent (accelerator).Current desulfurizing agent composition based on iron oxide, calcium oxide and calcirm-fluoride, the present invention in, iron oxide by
Iron ore in red mud is provided, and calcium oxide is provided by converter dust-removing ash, and calcirm-fluoride is by the fluorite (main chemical compositions of fluorite：CaF2：
79%, SiO2：4%, S：0.01%) provide.There is the characteristics of oxidation susceptibility is excellent as the iron oxide of oxidant.It is used as fixation
The characteristics of calcium oxide of agent has with sulphur and strong phosphorous oxides binding ability.As fluxing agent calcirm-fluoride have reduction slag viscosity and
The fusing point of infusibility material, improves the dynamic conditions of slag, the features such as promoting desulfurizing agent rapid slagging in smelting process.However,
Natural limestone and fluorite resource occur in that the situation of exhaustion.
During slurry process production phosphorus ammonium fertilizer, a large amount of phosphorous chemical industry waste liquids containing fluosilicic acid can be produced, environment is polluted.If straight
Extraction fluosilicic acid is connect, fluosilicic acid cost is too high, and added value is not high.Fluosilicic acid in phosphorous chemical industry waste liquid and lime stone are reacted,
Artificial fluorite (calcirm-fluoride) is generated, fluorine resource not only can be effectively reclaimed, the consumption of Natural Fluorite is reduced, and phosphorous chemical industry can be prevented
Pollution of the waste liquid to environment.So, preparing artificial fluorite using phosphorous chemical industry waste liquid has important application value.
Red mud is gained solid residue after dissolution aluminum oxide during aluminum oxide industry, due to wherein usually containing the red of high level
Iron ore, traditionally referred to as red mud.The main component iron oxide of bloodstone is a kind of preferable oxidant.Average often produces 1t
Aluminum oxide, incidentally produces 1.0~2.0t red muds.With the development of aluminum oxide industry, the discharge capacity of red mud increasingly increases.A large amount of heaps
Huge construction cost and maintenance cost is not only lost in the red mud of field accumulation, and high alkalinity waste liquid can be caused to water resource and soil
How pollution, therefore, effectively comprehensively utilize red mud extremely urgent.
Converter dust-removing ash is the exhaust gas dust collected using dry method electric dust-removing process in convertor steelmaking process, and it contains active lime
Powder, iron oxide and a small amount of carbon, fine size, more than 80% granularity is 5.0~76.4 μm, belongs to high fine powder state material.These powder
Dirt not only contains ferro element, and larger pollution, if directly abandoning, is not only brought in part also containing elements such as zinc, potassium, sodium to environment,
And cause resource loss.The recycling that dust is produced in converter production process is very important ring in steel-smelting production process
Section, it is both, to the recycling containing dust, to reduce the effective ways of cost, while being also to reduce environmental pollution, development green
The important measures of recycling economy.
With society the demand of high-quality steel grade is continuously increased and steel-smelting technology continuous progress, in order to improve the cleanliness factor of molten steel,
How a kind of efficient steel desulfurization slag former is prepared as a urgent and important job using industrial waste.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of steel desulfurization slag former, using phosphorous chemical industry byproduct, red mud and turn
Stove dedusting ash prepares desulfurization slag former, realizes the purpose of industrial waste recycling.
The present invention provides the production method of desulfurization slag former, comprising：
Be added to using calcium carbonate as carbonaceous extractant in the phosphorous chemical industry waste liquid handled through desiliconization, extract waste liquid in fluorine, and by its
In silica filtration.Added using red mud as irony conditioning agent in gained calcirm-fluoride filtrate, at the beginning of obtaining a kind of desulfurization slag former
Product.Using converter dust-removing ash be added to as calcareous conditioning agent in desulfurization slag former head product, through evaporative crystallization, high-pressure molding,
After drying, screening, a kind of desulfurization slag former is finally given.
A kind of desulfurization slag former, it is characterised in that the preparation process of the calcirm-fluoride is：The phosphorous chemical industry waste liquid after desiliconization processing is taken,
Carbonaceous extractant is added, the addition of carbonaceous extractant is controlled in calcium carbonate and Na2SiF6Material amount ratio be 3.0~5.5,
95~125 DEG C are heated to, is kept stirring for 2.0~4.5 hours, stir speed (S.S.) is 350~650r/min, filtering obtains calcirm-fluoride
Filtrate.
A kind of desulfurization slag former, it is characterised in that the main component of the carbonaceous extractant is calcium carbonate, and carbonaceous extractant is stone
One or several kinds of combinations in lime stone, dolomite, marble, stalactite, white marble, calcite.
A kind of desulfurization slag former, it is characterised in that the red mud main chemical compositions are：Fe2O3：35.16~38.86%, Al2O3：
18.35~20.45%, SiO2：11.65~14.15%, CaO：13.85~17.25%, TiO2：3.09~7.01%, Na2O：
1.0~1.6%.
A kind of desulfurization slag former, it is characterised in that a large amount of active calcium oxides present in the converter dust-removing ash, converter dust-removing ash
Main chemical compositions are：TFe：32.26~62.12%, FeO：12.84~15.51%, Fe：4.68~5.02%, CaO：2.56~
4.13%, SiO2：0.89~1.21%, Na2O：0.12~0.39%.
Now the desulfurization principle of this desulfurization slag former is summarized as follows：
Desulfurization is exothermic reaction, therefore is conducive to the progress of reaction of Salmon-Saxl under cryogenic, and in slag (FeO) the more, i.e. clinker
Oxidisability is stronger, is more conducive to the oxidation of sulphur.Low temperature, suitable alkalinity, high oxidation iron (hyperoxia gesture) clinker are conducive to desulfuration,
But (CaO) and (FeO) should have certain ratio, could obtain good result.
The advantage of molten steel desulfurizing is：High alkalinity, high oxidation iron (hyperoxia gesture), low temperature；Increase stirring intensity, promote lime
Scorification.The addition of calcirm-fluoride can suitably reduce slag melting and viscosity, improve the effect of molten steel desulfurizing.
Novel desulphurization slag former prepared by the present invention takes full advantage of the fluorine composition in phosphate fertilizer waste residue to prepare calcirm-fluoride, and is fluorinated
The addition of calcium reduces the fusing point and viscosity of slugging, meanwhile, take full advantage of the ferro element resource and active stone in converter dust-removing ash
Ash component, the preparation for novel desulphurization slag former provides technical feasibility, also saves substantial amounts of natural stone, improves two
The added value of the secondary utilization of resources.
Brief description of the drawings
Accompanying drawing 1 is the production technological process of fluorine extraction process of the present invention
Accompanying drawing 2 is the technological process of production of desulfurization slag former provided in an embodiment of the present invention
Specific embodiment
The present invention is described in further detail below by way of the embodiment of the present invention, but it is not considered that the inventive method be only limitted to it is following
Embodiment.
The chemical composition of the phosphorous chemical industry waste liquid handled through desiliconization used of the embodiment of the present invention is：Na：321.9mg/L, F：340.2
Mg/L, Al：270.6mg/L, Fe：99.0mg/L.
Case study on implementation 1
The preparation method of desulfurization slag former used is in embodiment：It is added to what is handled through desiliconization using calcium carbonate as carbonaceous extractant
In phosphorous chemical industry waste liquid, the fluorine in waste liquid is extracted, and by silica filtration therein.Institute is added using red mud as irony conditioning agent
Obtain in calcirm-fluoride filtrate, obtain a kind of desulfurization slag former head product.Desulfurization is added to using converter dust-removing ash as calcareous conditioning agent to make
In slag agent head product, after evaporative crystallization, high-pressure molding, drying, screening, a kind of desulfurization slag former is finally given.
The main component of the carbonaceous extractant be calcium carbonate, carbonaceous extractant be lime stone, dolomite, marble, stalactite,
One or several kinds of combinations in white marble, calcite.
The red mud main chemical compositions are：Fe2O3：36.86%, Al2O3：19.03%, SiO2：13.86%, CaO：14.58%,
TiO2：6.54%, Na2O：1.49%.
A large amount of active calcium oxides present in converter dust-removing ash, converter dust-removing ash main chemical compositions are：TFe：60.05%,
FeO：14.41%, Fe：4.98%, CaO：3.68%, SiO2：1.03%, Na2O：0.31%.
The desulfurization slag former that patent of the present invention is provided is used with Fluorite pellet on high temperature carbon shirt-circuiting furnace, carry out desulfurized effect to having a competition
Test.To ensure the reliability of experimental data, reduce experimental error to greatest extent, using static doctor treatment.It is in steel sample weight
430 ± 5g, temperature is under conditions of 1540 DEG C, to be separately added into 10% desulfurization slag former and two kinds of slagging agents of Fluorite pellet, slugging
Agent 2g, 5 after slagging agent is added, 10,20, the separately sampled detection desulfurized effects of 30min, keep that furnace temperature is constant to last takes
Sample terminates.Molten steel adds the molten steel sulfur content at two kinds of each moment of slagging agent at a temperature of 1540 DEG C and is shown in Table 1.
The desulfurized effect contrast (w%) of two kinds of slagging agent heats is added during 1. 1540 DEG C of table
| Time (min) | 0 | 5 | 10 | 20 | 30 |
| Fluorite pellet (10%) | 0.023 | 0.019 | 0.015 | 0.013 | 0.013 |
| This product (10%) | 0.023 | 0.015 | 0.011 | 0.012 | 0.010 |
The desulfurized effect of the desulfurization slag former provided using the present invention is better than Fluorite pellet.Within the specific limits, desulfurized effect is at any time
Between increase and strengthen, improve smelting process in desulfurized effect, greatly improve desulfurization rate, slugging effect is obvious.
Case study on implementation 2
The preparation method of desulfurization slag former used is in embodiment：The preparation method of desulfurization slag former used is in embodiment：With carbon
Sour calcium is added in the phosphorous chemical industry waste liquid handled through desiliconization as carbonaceous extractant, extracts the fluorine in waste liquid, and by dioxy therein
SiClx is filtered.Added using red mud as irony conditioning agent in gained calcirm-fluoride filtrate, obtain a kind of desulfurization slag former head product.With
Converter dust-removing ash is added in desulfurization slag former head product as calcareous conditioning agent, through evaporative crystallization, high-pressure molding, drying, sieve
After point, a kind of desulfurization slag former is finally given.
The main component of the carbonaceous extractant be calcium carbonate, carbonaceous extractant be lime stone, dolomite, marble, stalactite,
One or several kinds of combinations in white marble, calcite.
The red mud main chemical compositions are：Fe2O3：36.86%, Al2O3：19.03%, SiO2：13.86%, CaO：14.58%,
TiO2：6.54%, Na2O：1.49%.
A large amount of active calcium oxides present in converter dust-removing ash, converter dust-removing ash main chemical compositions are：TFe：60.05%,
FeO：14.41%, Fe：4.98%, CaO：3.68%, SiO2：1.03%, Na2O：0.31%.
The desulfurization slag former that patent of the present invention is provided is used with Fluorite pellet on high temperature carbon shirt-circuiting furnace, carry out desulfurized effect to having a competition
Test.To ensure the reliability of experimental data, reduce experimental error to greatest extent, using static doctor treatment.It is in steel sample weight
430 ± 5g, temperature is under conditions of 1570 DEG C, to be separately added into 10% desulfurization slag former and two kinds of slagging agents of Fluorite pellet, slugging
Agent 2g, 5 after slagging agent is added, 10,20, the separately sampled detection desulfurized effects of 30min, keep that furnace temperature is constant to last takes
Sample terminates.Molten steel adds the molten steel sulfur content at two kinds of each moment of slagging agent at a temperature of 1570 DEG C and is shown in Table 2.
The desulfurized effect contrast (w%) of two kinds of slagging agent heats is added during 2. 1570 DEG C of table
| Time (min) | 0 | 5 | 10 | 20 | 30 |
| Fluorite pellet (10%) | 0.023 | 0.018 | 0.014 | 0.013 | 0.011 |
| This product (10%) | 0.023 | 0.014 | 0.013 | 0.011 | 0.009 |
The desulfurized effect of the desulfurization slag former provided using the present invention is better than Fluorite pellet.Within the specific limits, desulfurized effect is at any time
Between increase and strengthen, improve smelting process in desulfurized effect, greatly improve desulfurization rate, slugging effect is obvious.
Case study on implementation 3
The preparation method of desulfurization slag former used is in embodiment：It is added to what is handled through desiliconization using calcium carbonate as carbonaceous extractant
In phosphorous chemical industry waste liquid, the fluorine in waste liquid is extracted, and by silica filtration therein.Institute is added using red mud as irony conditioning agent
Obtain in calcirm-fluoride filtrate, obtain a kind of desulfurization slag former head product.Desulfurization is added to using converter dust-removing ash as calcareous conditioning agent to make
In slag agent head product, after evaporative crystallization, high-pressure molding, drying, screening, a kind of desulfurization slag former is finally given.
The main component of the carbonaceous extractant be calcium carbonate, carbonaceous extractant be lime stone, dolomite, marble, stalactite,
One or several kinds of combinations in white marble, calcite.
The red mud main chemical compositions are：Fe2O3：36.86%, Al2O3：19.03%, SiO2：13.86%, CaO：14.58%,
TiO2：6.54%, Na2O：1.49%.
A large amount of active calcium oxides present in converter dust-removing ash, converter dust-removing ash main chemical compositions are：TFe：60.05%,
FeO：14.41%, Fe：4.98%, CaO：3.68%, SiO2：1.03%, Na2O：0.31%.
The desulfurization slag former that patent of the present invention is provided is used with Fluorite pellet on high temperature carbon shirt-circuiting furnace, carry out desulfurized effect to having a competition
Test.To ensure the reliability of experimental data, reduce experimental error to greatest extent, using static doctor treatment.It is in steel sample weight
430 ± 5g, temperature is under conditions of 1540 DEG C, to be separately added into 8% desulfurization slag former and two kinds of slagging agents of Fluorite pellet, slagging agent
1.55g, 5 after slagging agent is added, 10,20, the separately sampled detection desulfurized effects of 30min, keep that furnace temperature is constant to last takes
Sample terminates.Molten steel adds the molten steel sulfur content at two kinds of each moment of slagging agent at a temperature of 1540 DEG C and is shown in Table 3.
The desulfurized effect contrast (w%) of two kinds of slagging agent heats is added during 3. 1540 DEG C of table
| Time (min) | 0 | 5 | 10 | 20 | 30 |
| Fluorite pellet (10%) | 0.023 | 0.020 | 0.017 | 0.016 | 0.015 |
| This product (10%) | 0.023 | 0.016 | 0.014 | 0.013 | 0.012 |
The desulfurized effect of desulfurization slag former is better than Fluorite pellet.Within the specific limits, desulfurized effect strengthens with the increase of time,
Improve desulfurized effect in smelting process, greatly improve desulfurization rate, slugging effect is obvious.
Case study on implementation 4
The preparation method of desulfurization slag former used is in embodiment：It is added to what is handled through desiliconization using calcium carbonate as carbonaceous extractant
In phosphorous chemical industry waste liquid, the fluorine in waste liquid is extracted, and by silica filtration therein.Institute is added using red mud as irony conditioning agent
Obtain in calcirm-fluoride filtrate, obtain a kind of desulfurization slag former head product.Desulfurization is added to using converter dust-removing ash as calcareous conditioning agent to make
In slag agent head product, after evaporative crystallization, high-pressure molding, drying, screening, a kind of desulfurization slag former is finally given.
The main component of the carbonaceous extractant be calcium carbonate, carbonaceous extractant be lime stone, dolomite, marble, stalactite,
One or several kinds of combinations in white marble, calcite.
The red mud main chemical compositions are：Fe2O3：36.86%, Al2O3：19.03%, SiO2：13.86%, CaO：14.58%,
TiO2：6.54%, Na2O：1.49%.
A large amount of active calcium oxides present in converter dust-removing ash, converter dust-removing ash main chemical compositions are：TFe：60.05%,
FeO：14.41%, Fe：4.98%, CaO：3.68%, SiO2：1.03%, Na2O：0.31%.
The desulfurization slag former that patent of the present invention is provided is used with Fluorite pellet on high temperature carbon shirt-circuiting furnace, carry out desulfurized effect to having a competition
Test.To ensure the reliability of experimental data, reduce experimental error to greatest extent, using static doctor treatment.It is in steel sample weight
430 ± 5g, temperature is under conditions of 1570 DEG C, to be separately added into 8% desulfurization slag former and two kinds of slagging agents of Fluorite pellet, slagging agent
1.55g, 5 after slagging agent is added, 10,20, the separately sampled detection desulfurized effects of 30min, keep that furnace temperature is constant to last takes
Sample terminates.Molten steel adds the molten steel sulfur content at two kinds of each moment of slagging agent at a temperature of 1570 DEG C and is shown in Table 4.
The desulfurized effect contrast (w%) of two kinds of slagging agent heats is added during 4. 1570 DEG C of table
| Time (min) | 0 | 5 | 10 | 20 | 30 |
| Fluorite pellet (10%) | 0.023 | 0.019 | 0.017 | 0.015 | 0.013 |
| This product (10%) | 0.023 | 0.015 | 0.013 | 0.012 | 0.011 |
The desulfurized effect of the desulfurization slag former provided using the present invention is better than Fluorite pellet.Within the specific limits, desulfurized effect is at any time
Between increase and strengthen, improve smelting process in desulfurized effect, greatly improve desulfurization rate, slugging effect is obvious.
It should be noted last that, above embodiment is merely illustrative of the technical solution of the present invention and unrestricted, although ginseng
According to the facts the present invention is described in detail example, it will be understood by those within the art that, can be to technical side of the invention
Case is modified or equivalent substitution, and without departing from the spirit and scope of technical solution of the present invention, it all should cover the present invention's
Among right.
Claims (5)
1. a kind of desulfurization slag former, it is characterised in that production method is：Using calcium carbonate as carbonaceous extractant, add at desiliconization
In phosphorous chemical industry waste liquid after reason, the fluorine in waste liquid is extracted, precipitated silica therein is filtered；Using red mud as irony conditioning agent,
Add in gained calcirm-fluoride filtrate, obtain a kind of desulfurization slag former head product；Using converter dust-removing ash as calcareous conditioning agent, add
In desulfurization slag former head product, resulting solution obtains a kind of desulfurization slag former after evaporative crystallization, high-pressure molding, drying, screening.
2. a kind of desulfurization slag former as claimed in claim 1, it is characterised in that the preparation process of described calcirm-fluoride filtrate is：
The phosphorous chemical industry waste liquid after desiliconization processing is taken, carbonaceous extractant is added, the addition of carbonaceous extractant is controlled in calcium carbonate and Na2SiF6
Material amount ratio be 3.0~5.5, be heated to 95~125 DEG C, be kept stirring for 2.0~4.5 hours, stir speed (S.S.) be 350~
650r/min, filtering, obtains calcirm-fluoride filtrate.
3. a kind of desulfurization slag former as claimed in claim 1, it is characterised in that the carbonaceous extractant main component is carbon
Sour calcium, is one or several kinds of combinations in lime stone, dolomite, marble, stalactite, white marble, calcite.
4. a kind of desulfurization slag former as claimed in claim 1, it is characterised in that the main chemical compositions of the red mud are：Fe2O3：
35.16~38.86%, Al2O3：18.35~20.45%, SiO2：11.65~14.15%, CaO：13.85~17.25%, TiO2：
3.09~7.01%, Na2O：1.0~1.6%.
5. a kind of desulfurization slag former as claimed in claim 1, it is characterised in that largely lived present in the converter dust-removing ash
Property calcium oxide；The grey main chemical compositions of the converter dust-removing are：TFe：32.26~62.12%, FeO：12.84~15.51%,
Fe：4.68~5.02%, CaO：2.56~4.13%, SiO2：0.89~1.21%, Na2O：0.12~0.39%.
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| CN112522509A (en) * | 2020-10-26 | 2021-03-19 | 广西三秋树环保科技有限公司 | Preparation process of cold-pressed red mud pellets, and product and application thereof |
| KR102274035B1 (en) * | 2020-01-22 | 2021-07-08 | 한양대학교 에리카산학협력단 | Desulfurization method of molten steel using fluorite replaced flux |
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