CN101984088B - Method for preparing premelted refining slag by using converter slag and aluminum slag - Google Patents

Method for preparing premelted refining slag by using converter slag and aluminum slag Download PDF

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CN101984088B
CN101984088B CN2010105458130A CN201010545813A CN101984088B CN 101984088 B CN101984088 B CN 101984088B CN 2010105458130 A CN2010105458130 A CN 2010105458130A CN 201010545813 A CN201010545813 A CN 201010545813A CN 101984088 B CN101984088 B CN 101984088B
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slag
aluminium
converter
iron
aluminum
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CN101984088A (en
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闵义
姜茂发
刘承军
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Northeastern University China
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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
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Abstract

The invention relates to a method for preparing premelted refining slag by using converter slag and aluminum slag, which comprises the following steps: selecting raw materials according to the requirement that the content of metallic aluminum in the aluminum slag is greater than or equal to 20% in mass percent; proportioning the raw materials under the condition that the mass ratio of the converter slag to the aluminum slag is (2.0-2.5):1; controlling the smelting temperature of the premelted refining slag at 1500-1600 DEG C, adding the aluminum slag in three batches after the converter slag is completely molten down, and standing for 20-30min after the last batch of aluminum slag is added and stirred uniformly, thereby realizing the purpose of separating slag from iron in a molten pool; and cooling the prepared premelted refining slag to the normal temperature, crushing the prepared premelted refining slag to the particles of which the particle size range is within 5-30mm, and then, packaging the particles. On the basis of ensuring the refining effect, the method of the invention completely uses industrial slag materials as raw materials, thereby protecting the natural mineral resources, widening the utilization ways of the converter slag and the aluminum slag as resources, and partially realizing the cyclic utilization of the converter slag in iron and steel production processes.

Description

Utilize converter slag and aluminium slag to prepare the method for pro-molten refining slag
Technical field
The present invention relates to metallurgy and environmental technology field, relate to metallurgical industry solid waste resource recovery utilization technology, be specifically related to a kind of method of utilizing converter slag and aluminium slag to prepare pro-molten refining slag.
Background technology
Converter slag mainly contains CaO, SiO 2, FeO, Fe 2O 3, MnO, Al 2O 3, MgO, P 2O 5With compositions such as S, be mainly derived from the oxidation of element such as aluminium silicomanganese in adding, molten iron and the steel scrap of slag formers such as lime in the converter steelmaking process, rhombspar, iron ore and iron scale and erosion of fire proof material of furnace lining etc.With ton steel converter slag quantity discharged is that 10～15kg calculates, and world's converter steel output was 8.53 hundred million tons in 2009, produced 100,000,000 tons of converter slags approximately, and wherein, Chinese converter steel output is 500,000,000 tons, discharges converter slag approximately more than 6,000 ten thousand tons.
The recycling of converter slag is significant for the Sustainable development that alleviates carrying capacity of environment and metallurgical industry.At present; The recycling of converter slag is mainly reflected in the following aspects: inner at Steel Production Flow Chart, mainly comprise after the recovery of iron and steel stock in the converter slag as the converter steel scrap, utilize CaO in the converter slag, MgO component portion replacing lime stone as staflux, the alkalescence of utilizing converter slag and oxidisability as desiliconization and the dephosphorizing agent of hot metal pre process procedures and return converter and be used as slag former etc.Outside in the iron and steel flow process, converter slag mainly utilizes and produces cement, produces slag micro powder and is used as road-making material as concrete additive, after ageing is handled and produces material of construction; In addition, in the environmental protection field, converter slag can be used as waste water such as removing pollutant agent Treatment of Copper, chromium, arsenic and use as fume desulfurizing agent; At agriculture field, converter slag can be as soil improvement agent and production phosphate fertilizer and trace element fertilizer etc.
Aspect the converter slag recycling; The U.S., Japan and German utilization ratio are all above more than 90%; And the utilization ratio of Chinese converter current slag is merely about 10%; Along with increasing rapidly of output of steel in recent years, the accumulation of converter slag makes environmental stress increasing, and developing multiple comprehensive utilization technique is the key of dealing with problems.In above-mentioned converter slag utilisation technology; Be comparatively reasonable and economical wherein in inner the recycling of iron and steel flow process; The consumption that it promptly can reduce the nature raw mineral materials can reduce relative energy expenditure again, to environment and conservation of resources and energy-saving and cost-reducing significant.But so far, utilize method all to have the problem of harmful element circulation enrichments such as S, P in the flow process that adopts in the industrial production, particularly totally unfavorable for the smelting of Clean Steel, make its range of application and utilization receive certain limitation.
The staple of aluminium slag is a metallic aluminium, Al 2O 3, the oxide compound of Si, Mg and Fe, the muriate of K, Na, Ca and Mg etc., concrete composition is different different because of technological process.The aluminium slag be mainly derived from the following aspects: the one, the aluminium slag that produces in the primary aluminum production process, ton aluminium aluminium slag output is about 30～50kg, China's primary aluminum output was 1298.4 ten thousand tons in 2009, produced surplus the aluminium slag 50 ten thousand tons approximately; The 2nd, the aluminium slag that metallic aluminium produces in processes such as remelting, casting and processing, this process aluminium slag output is ton aluminium 30～40kg, the aluminium consumption of China in 2009 is 1,375 ten thousand tons, corresponding about 500,000 tons of the aluminium slags that produce approximately; The 3rd, the aluminium slag that the secondary aluminum process of manufacture produces, its ton aluminium aluminium slag generation is about 150～250kg, and China's secondary aluminum output was 3,100,000 tons in 2009, produced surplus the aluminium slag 60 ten thousand tons approximately.
As a kind of renewable resource, the recycling of aluminium slag mainly comprises: metallic aluminium reclaims, be used for highway pavement paver, seabed scavenging material, light-duty aggregate for building, building wall and finishing material behind the sintering, synthetic ink is used for trade effluent and sanitary wastewater processing etc. and the brown corundum of production and many kinds aluminum oxide with aluminum oxide, synthesized polymer aluminum chloride and is used for the metallurgy of aluminium a plurality of industries in addition.But China's aluminum current slag treatment technology falls behind, and resource utilization is low, becomes one of source of carrying capacity of environment increase, and exploitation aluminium slag for comprehensive utilizes technology, expands aluminium slag recycling channel for lightening the load, and it is significant to increase economic efficiency.
In Clean Steel was smelted, external refining was significant for improving the molten steel purity.Particularly in the LF refining process, for realizing the target of deep deoxidation and dark desulfurization, must carry out upgrading to ladle slag, modification agent and modifying process are most important for refining effect and refining cycle control.Pro-molten refining slag has that composition is even, fusing point is low, molten speed is fast and characteristics such as Sulfur capacity height; Be used with reductive agent and lime, can realize quick slag making and deep desulfuration, be beneficial to the absorption that promotes non-metallic inclusion; The refining cycle that shortens greatly, oneself is widely used in the ladle refining process at present.For reducing fluorine-containing slag to the erosion of ladle lining with to the pollution of environment, staple is 12CaO7Al 2O 3Or 3CaOAl 2O 3Pro-molten refining slag use the most extensively industrial production person, at present, this kind pro-molten refining slag is many to be feedstock production with natural mineral.Chinese patent 200910227945.6,200610011709.7 and 200610024191.0 is all to contain CaO, Al 2O 3, MgO Wingdale, alumine and magnesia etc. as starting material through batching, batch mixing, melting, broken preparation pro-molten refining slag.Chinese patent 200610039275.1 adopts lime and high purity Al 2O 3Produce ultra-clean steel with addition of the slag supplying agent that reduces fusing point and use pro-molten refining slag, above method all adopts the nature mineral as starting material, be unfavorable for the protection of natural resources, and energy consumption is higher.Chinese patent 03143306.5 adopts is that the tricalcium aluminate sosoloid of deep desilication technology association in the alumina by sintering production process is base-material; With addition of material prepn refining slags such as hydrated aluminum silicate, calcite, magnesia; Though used industrial slag charge, but with addition of about 30% natural mineral.
Summary of the invention
To the present situation of converter slag and the utilization of aluminium slag, the present invention provides a kind of method of utilizing converter slag and aluminium slag to prepare pro-molten refining slag.Purpose is the effective constituent that makes full use of in converter slag and the aluminium slag, replaces the nature mineral to prepare pro-molten refining slag fully, solves converter slag uses the P element in iron and steel flow process circulating inside enrichment problem simultaneously.
Essence of the present invention is CaO and the Al in the aluminium slag that utilizes in the converter slag 2O 3, and utilize the Fe in the metallic aluminium reduction converter slag in the aluminium slag 2O 3, FeO, MnO, P 2O 5And SiO 2Generate Al 2O 3, preparation CaO-Al 2O 3The type pro-molten refining slag.
Utilize the MgO in converter slag and the aluminium slag, guarantee that pro-molten refining slag has certain MgO content, thereby help reducing the melting loss of ladle lining; Through the reductive action of aluminium metal in the dreg aluminium, significantly reduce Fe in the converter slag 2O 3, FeO and MnO content, thereby reduce the oxidisability of converter slag, reduce SiO in the converter slag 2Content, improve its basicity, thereby guarantee that prepared pre-melted slag has good desulfurization thermodynamic condition; Through the reductive action of aluminium metal in the dreg aluminium, the P in the reduction converter slag 2O 5The simple substance P part of its generation is overflowed with flue dust with vapor form; Part gets in reduction product Fe-Si-Mn alloy, thereby significantly reduces the phosphorus content of prepared pre-melted slag, has solved converter slag effectively and has used the P enrichment problem that exists at iron and steel flow process internal recycle.In addition, in the heating and melting process, wherein part sulphur overflows with the form of sulphur steam converter slag under air conditions, and part gets in the metallographic phase, thereby effectively reduces the sulphur content of prepared pre-melted slag.Smelting temperature is higher than the muriatic boiling point of K, Na, Ca and Mg, and in the high melt process, such material will overflow slag with the form of steam in the aluminium slag, thereby can not impact the ladle refining process.
The concrete technological process for preparing pro-molten refining slag with converter slag and aluminium slag is following:
(1) choosing of raw material: the raw material of employing is converter slag and aluminium slag.Converter slag generally contains CaO, SiO 2, MgO, Al 2O 3, Fe 2O 3, FeO, MnO, P 2O 5With the S of trace etc., but in actual industrial production, owing to bessemerize the different of technology and slagging regime and residues processing technique, its composition fluctuates within the specific limits.The present invention does not have particular requirement to the converter slag composition, both can be the hot application slag, can be Water Quenching Slag yet, and whether the process iron and steel stock reclaims all can.Usually the converter slag composition is as shown in table 1.
Table 1 converter slag chemical ingredients (quality %)
Figure GDA0000119104210000021
For the aluminium slag, because smelting technology is different, its composition fluctuation range is bigger, and generally, by mass percentage, the composition of aluminium slag is mainly 10%～30%Al, 20%～40%Al 2O 3, 7%～15% Si, Mg and Fe oxide compound, the muriate of 15%～30% K, Na, Ca and Mg etc.If its metallic aluminium content is low excessively, will cause prepared product C aO and Al 2O 3Mass ratio is low excessively, thereby departs from the fusing point zone, thus the present invention require aluminium metal in the dreg aluminium content by mass ratio more than or equal to 20%.
(2) ratio of components: selected raw material is carried out composition analysis.According to converter slag composition analysis result, according to Fe 2O 3, FeO, MnO and P 2O 5Be reduced SiO fully 21/2nd are reduced calculating metallic aluminium requirement, and then calculate the theoretical add-on of aluminium slag according to aluminium slag ingredient analytical results, in the production reality, consider that the aluminium slag adds the scaling loss in the fusion converter slag process, and the aluminium slag need excessive adding.Generally, converter slag and aluminium slag mass ratio are (2.0～2.5): 1.Each oxide compound reduction needs the aluminium amount to calculate by reaction equation (1)～(5):
Fe 2O 3+Al＝Al 2O 3+Fe (1)
3FeO+2Al＝Al 2O 3+3Fe (2)
3MnO+2Al＝Al 2O 3+3Mn (3)
3P 2O 5+10Al＝5Al 2O 3+6P (4)
3SiO 2+4Al＝2Al 2O 3+3Si (5)
(3) melting: converter slag is melted in High Temperature Furnaces Heating Apparatus, be the flowability that guarantees that it is good, temperature is controlled to be 1500～1600 ℃.After treating that converter slag melts clearly fully; The inferior in three batches aluminium slag that adds; Each batch add-on is respectively 50%, 25% and 25% of total add-on by mass ratio, and the timed interval between each batch is 3～5min, and a collection of aluminium slag of every adding all stirs with nitrogen; The assurance reduction reaction is even, promotes the raising of speed of response.
(4) slag iron is told: after treating that last batch of aluminium slag adds and stir, leave standstill 20～30min, slag iron is realized separating in the molten bath in, and enforcement slag iron is told operation.If High Temperature Furnaces Heating Apparatus is equipped with the end to go out device, then taps a blast furnace earlier and afterwards slag tap; If High Temperature Furnaces Heating Apparatus does not have the end and goes out device, then slag tap earlier and afterwards tap a blast furnace.
Slag promptly refers to pro-molten refining slag, and iron promptly refers to by product of the present invention: the phosphorous low silicon Fe-Si-Mn alloy of reduzate.
(5) pro-molten refining slag is handled: prepared pro-molten refining slag is cooled to normal temperature, and being crushed to size range is 5～30mm, packs.
The phosphorous low silicon Fe-Si-Mn alloy of reduzate can be used as the reductive agent use that smelting reduction process is produced ferrophosphorus.The method such as the Chinese patent 96100944.6 of smelting reduction process production ferrophosphorus are said.
The present invention proposes to utilize the two to prepare the method for pro-molten refining slag according to converter slag and aluminium slag ingredient characteristics.This method uses industrial slag charge as raw material on the basis that guarantees refining effect fully, has promptly protected natural Mineral resources, has widened the recycling approach of converter slag and aluminium slag again, and part has realized that converter slag is in inner the recycling of iron and steel flow process.Advantage is following:
(1) uses converter slag and aluminium slag to prepare pro-molten refining slag fully, improved its utilization of resources level greatly as raw material.Preparation technology is simple, and product cost is low, and added value is high, compares as starting material with using the nature mineral fully, and ton slag cost can reduce by 300～400 yuans.If use the fusion converter slag directly to produce, will further reduce energy cost.
(2) made full use of Al in CaO in the converter slag, MgO and the aluminium slag 2O 3Etc. effective constituent, prepared pro-molten refining slag composition is even, and compact structure, thing are stable mutually (to be mainly 12CaO7Al 2O 3), temperature of fusion low (less than 1400 ℃), burn-off rate fast (less than 50s), 1500 ℃ of viscosity be less than 1Pas, and then effectively guaranteed refining effect.
(3) made full use of the reducing power of aluminium slag metal in the dreg aluminium; Converter slag has been carried out effective upgrading; Effectively reduce in the converter slag oxidisability composition and removed detrimental impurity such as phosphorus sulphur; Efficiently solve the problem of converter slag, and the phosphorous low silicon Fe-Si-Mn alloy of reduction by-product can utilize again at metallurgical process internal recycle use phosphorus sulphur impurity enrichment of element.
Embodiment
Embodiment 1,2 and 3 is a raw material with three kinds of converter slags respectively, is respectively converter smelting endpoint and directly cools off converter slag (handling without deironing), water-cooled converter slag (handling through deironing) and hot application converter slag (handling through deironing), and its composition is as shown in table 2.The aluminium slag is selected from secondary aluminum process for processing product, and its composition is as shown in table 3.
Table 2 embodiment is with converter slag composition (quality %)
Figure GDA0000119104210000031
Table 3 embodiment 1,2 and 3 used aluminium slag ingredients (quality %)
Figure GDA0000119104210000032
The pro-molten refining slag composition (quality %) of table 4 embodiment preparation
Figure GDA0000119104210000033
The pro-molten refining slag performance of table 5 embodiment preparation
Figure GDA0000119104210000034
Embodiment 1
The concrete technological process for preparing pro-molten refining slag with converter slag and aluminium slag is following:
(1) raw material chooses
The converter slag that is adopted, aluminium slag ingredient are shown in table 2, table 3.
(2) ratio of components
Converter slag and aluminium slag mass ratio are 2.5: 1.
(3) melting: converter slag is melted in High Temperature Furnaces Heating Apparatus, be the flowability that guarantees that it is good, temperature is controlled to be 1550 ℃.After treating that converter slag melts clearly fully; The inferior in three batches aluminium slag that adds; Each batch add-on is respectively 50%, 25% and 25% of total add-on by mass ratio, and the timed interval between each batch is 5min, and a collection of aluminium slag of every adding all stirs with nitrogen; The assurance reduction reaction is even, promotes the raising of speed of response.
(4) slag iron is told: after treating that last batch of aluminium slag adds and stir, leave standstill 25min, slag iron is realized separating in the molten bath in, and enforcement slag iron is told operation.The High Temperature Furnaces Heating Apparatus that uses is equipped with the end to go out device, taps a blast furnace earlier and afterwards slags tap.
(5) pro-molten refining slag is handled: prepared pro-molten refining slag is cooled to normal temperature, and being crushed to size range is 5～30mm, packs.
The composition of prepared pro-molten refining slag is as shown in table 4, and performance index are as shown in table 5.
The pro-molten refining slag of embodiment 1 preparation is applied to the ladle refining process of X65 pipe line steel, substitute that certain Iron And Steel Plant uses with the pro-molten refining slag of natural mineral as raw material production, refining slag adding system and refinery practice remain unchanged.Carried out the commerical test of two heats altogether, test-results is as shown in table 6.
Table 6X65 pipeline steel smelting commerical test procedure component analytical results (quality %)
Before the LF refining, two heat of molten steel S content respectively 0.0054% and 0.0056% are compared with converter terminal S content, and desulfurization degree reaches 27.0% and 34.9% respectively in advance, and use the nature mineral close as the on average preparatory desulfurization aluminium 30% of raw material; After the LF refining finished, molten steel S content met the steel grade controlled target less than 0.002%.The LF refining cycle of two heats is respectively 45min and 48min, and average refining cycle 50min is close with former technology.
Can find out from the refining result, use converter slag and aluminium slag to be the feedstock production pro-molten refining slag, can realize the ultra-low sulphur smelting target fully.
Embodiment 2
The concrete technological process for preparing pro-molten refining slag with converter slag and aluminium slag is following:
(1) raw material chooses
The converter slag that is adopted, aluminium slag ingredient are shown in table 2, table 3.
(2) ratio of components
Converter slag and aluminium slag mass ratio are 2.3: 1.
(3) melting: converter slag is melted in High Temperature Furnaces Heating Apparatus, be the flowability that guarantees that it is good, temperature is controlled to be 1600 ℃.After treating that converter slag melts clearly fully; The inferior in three batches aluminium slag that adds; Each batch add-on is respectively 50%, 25% and 25% of total add-on by mass ratio, and the timed interval between each batch is 4min, and a collection of aluminium slag of every adding all stirs with nitrogen; The assurance reduction reaction is even, promotes the raising of speed of response.
(4) slag iron is told: after treating that last batch of aluminium slag adds and stir, leave standstill 30min, slag iron is realized separating in the molten bath in, and enforcement slag iron is told operation.The High Temperature Furnaces Heating Apparatus that uses is equipped with the end to go out device, taps a blast furnace earlier and afterwards slags tap.
(5) pro-molten refining slag is handled: prepared pro-molten refining slag is cooled to normal temperature, and being crushed to size range is 5～30mm, packs.
The composition of prepared pro-molten refining slag is as shown in table 4, and performance index are as shown in table 5.
Embodiment 3
The concrete technological process for preparing pro-molten refining slag with converter slag and aluminium slag is following:
(1) raw material chooses
The converter slag that is adopted, aluminium slag ingredient are shown in table 2, table 3.
(2) ratio of components
Converter slag and aluminium slag mass ratio are 2.1: 1.
(3) melting: converter slag is melted in High Temperature Furnaces Heating Apparatus, be the flowability that guarantees that it is good, temperature is controlled to be 1500 ℃.After treating that converter slag melts clearly fully; The inferior in three batches aluminium slag that adds; Each batch add-on is respectively 50%, 25% and 25% of total add-on by mass ratio, and the timed interval between each batch is 3min, and a collection of aluminium slag of every adding all stirs with nitrogen; The assurance reduction reaction is even, promotes the raising of speed of response.
(4) slag iron is told: after treating that last batch of aluminium slag adds and stir, leave standstill 20min, slag iron is realized separating in the molten bath in, and enforcement slag iron is told operation.The High Temperature Furnaces Heating Apparatus that uses does not have an end and goes out device, slags tap earlier and afterwards taps a blast furnace.
(5) pro-molten refining slag is handled: prepared pro-molten refining slag is cooled to normal temperature, and being crushed to size range is 5～30mm, packs.
The composition of prepared pro-molten refining slag is as shown in table 4, and performance index are as shown in table 5.

Claims (4)

1. method of utilizing converter slag and aluminium slag to prepare pro-molten refining slag is characterized in that step is following:
(1) choosing of raw material: the raw material of employing is converter slag and aluminium slag, require aluminium metal in the dreg aluminium content by mass ratio more than or equal to 20%;
(2) ratio of components: converter slag and aluminium slag mass ratio are (2.0～2.5): 1;
(3) melting: converter slag is melted in High Temperature Furnaces Heating Apparatus, and temperature is controlled to be 1500～1600 ℃, treat that converter slag is molten clear fully after, time add the aluminium slag in three batches, the timed interval between each batch is 3～5min, a collection of aluminium slag of every adding all stirs with nitrogen;
(4) slag iron is told: after treating that last batch of aluminium slag adds and stir, leave standstill 20～30min, slag iron is realized separating in the molten bath in, and enforcement slag iron is told operation;
(5) pro-molten refining slag is handled: prepared pro-molten refining slag is cooled to normal temperature, and being crushed to size range is 5～30mm, packs.
2. according to the described method of utilizing converter slag and aluminium slag to prepare pro-molten refining slag of claim 1, it is characterized in that in the step (3), the inferior in three batches aluminium slag that adds, each batch add-on is respectively 50%, 25% and 25% of total add-on by mass ratio.
3. according to the described method of utilizing converter slag and aluminium slag to prepare pro-molten refining slag of claim 1, it is characterized in that in the step (4) that implement slag iron and tell operation, High Temperature Furnaces Heating Apparatus is equipped with the end to go out device, taps a blast furnace earlier and afterwards slags tap.
4. according to the described method of utilizing converter slag and aluminium slag to prepare pro-molten refining slag of claim 1, it is characterized in that in the step (4), implement slag iron and tell operation that High Temperature Furnaces Heating Apparatus does not have an end and goes out device, slags tap earlier and afterwards taps a blast furnace.
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