JPH0249366B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides molten iron consisting essentially of quicklime powder containing calcium carbonate inside, obtained by fluidized roasting of diamide lime in an oxidizing atmosphere, carbon substances, and halides of alkali or alkaline earth metals. Regarding a desulfurizing agent for blowing. Here, molten iron refers to molten products such as pig iron, cast iron, and steel. As is well known, desulfurization of molten iron is an important technical issue in order to obtain steel products with excellent performance, and many proposals have been made regarding desulfurization agents and desulfurization methods. Calcium carbide has the best desulfurization performance as a desulfurization agent, and those containing calcium carbide as a main component are widely used. but,
Their production consumes a large amount of electricity, and in recent years, with rising energy costs, they are being forced to reconsider from an economic perspective. On the other hand, quicklime is one of the known inexpensive desulfurization agents, and quicklime is generally produced using equipment such as a co-fired standing kiln, heavy oil fired standing kiln, shaft kiln, rotary kilso, etc. , calcite, marble, shells, etc., are fired into lumps depending on the purpose of use, and then mechanically crushed.
Although it is used as the main component of desulfurization agents for molten iron, there are problems such as the desulfurization performance of the quicklime powder itself is extremely low. The requirements of the steel industry have not yet been met. Furthermore, well-known desulfurization methods include a method in which a desulfurizing agent is added to molten iron and mechanically stirred, and a method in which a powdered desulfurizing agent is blown into molten iron using gas. Among these desulfurization methods, the blow desulfurization method has recently become widely adopted due to its particularly excellent workability and excellent desulfurization efficiency. This blowing desulfurization method is a method in which a desulfurizing agent powder is entrained in a gas flow of a carrier gas such as dry nitrogen, and desulfurization is carried out by blowing into the molten iron through a lance immersed in the molten iron. In the blowing desulfurization method, for example, while transporting a mixed iron car that has received pig iron from a blast furnace to a steelmaking factory,
This method is a method in which the desulfurization agent is temporarily stopped at a desulfurization station and the powdered desulfurization agent is blown into the hot metal in the mixer car, replacing the mechanical stirring desulfurization method (so-called KR method with an open ladle). has come into widespread practical use. "Blowing desulfurization" as used herein is a technical term that is opposed to so-called "pour-in", etc., and specifically, desulfurization is carried out by injecting desulfurizing agent powder together with a carrier gas below the surface of the molten iron. It is called a method. In the above-mentioned blowing desulfurization method, there is an extremely close relationship between the desulfurization performance and the gas transportability of the desulfurization agent powder due to the carrier gas, and excellent desulfurization performance can be expected from the desulfurization agent powder, which has poor gas transportability. I can't. As mentioned above, in order to improve the desulfurization performance of quicklime, which does not exhibit sufficient desulfurization performance, raw limestone powder is calcined in a non-oxidizing atmosphere, and amorphous carbon is precipitated on the surface of the produced CaO primary crystals. Japanese Patent Application Laid-Open No. 1983-1983 using a desulfurization agent consisting essentially of quicklime and carbon.
No. 50414 and other proposals, JP-A-55 using quicklime powder added with a silicone surfactant to improve gas transportability.
- The proposal of No. 110712, the proposal of JP-A-52-111813 which uses quicklime particles with CaCO ₃ inside, the proposal of JP-A-55-73800 which uses powdered quicklime and powdered calcium carbonate. There are suggestions, etc. However, with the exception of the one proposed in JP-A No. 55-110712, these quicklime-based desulfurization agents do not necessarily have good gas conveyance through the carrier gas flow during blow desulfurization, and their desulfurization performance is also insufficient. I understand. As a result of extensive research in order to fully demonstrate the desulfurization performance of quicklime in the blow desulfurization method, the present inventor discovered that quicklime powder, which is obtained by fluidized roasting of diamide lime in an oxidizing atmosphere, is a fine powder with excellent gas transportability. In addition, the quicklime powder contains more than 15% by weight of calcium carbonate and less than 60% by weight, carbon substances, and halides of alkali or alkaline earth metals. We have made the surprising discovery that this agent exhibits extremely excellent desulfurization performance in the blow desulfurization method. In the present specification, "diamide lime" is used to mean a mixture of fine precipitated calcium carbonate and carbon that is precipitated from an aqueous solution or suspension by a chemical reaction. Diamide lime includes, for example, a mixture of calcium carbonate and carbon that is produced as a by-product when producing dicyandiamide from lime nitrogen, or when producing thiourea etc. from lime nitrogen. Preferably, dicyandiamide is produced from lime nitrogen. obtained when
A mixture of calcium carbonate and carbon is optimally used. Dicyandiamide is produced by reacting a lime nitrogen aqueous suspension with carbon dioxide.
The by-product diamide lime, which is the excess residue at that time, generally contains 70 to 90% calcium carbonate, 5 to 15% carbon,
It also contains impurities such as aluminum oxide and silicon oxide, and is a mixture whose main components are extremely fine calcium carbonate and carbon. The method of torrefying the diamide lime described above used in the present invention involves fluidized roasting in an oxidizing atmosphere. In the specification of this application, "fluidized roasting in an oxidizing atmosphere" refers to a torrefaction heat source, For example, gaseous fuels such as carbon monoxide, natural gas, and propane, liquid fuels such as heavy oil, and solid fuels such as coke powder (the carbon present in the outer shell of diamide lime can also be used as fuel) can be completely annexed. It is used to mean roasting under conditions where there is an excess of oxygen than the required theoretical amount of oxygen. Preferably at least 1.05 times the theoretical amount of oxygen required for complete combustion of the torrefaction heat source, more preferably
1.1 to 2.5 times more oxygen, most preferably 1.1 to 2.2 times more oxygen is supplied to the torrefaction furnace. If the amount of oxygen is too small, such as less than 1.05 times, it is not preferable because the outside of the diamide lime is rapidly heated in a short period of time, making it difficult to convert it into quicklime. Therefore, calcium carbonate must remain in the quicklime powder of the present invention obtained by fluidized roasting diamide lime in an oxidizing atmosphere in an amount of more than 15% by weight and less than 60% by weight. If the content of calcium carbonate in the quicklime powder is less than 15% by weight, it is undesirable because the desulfurization performance in blow desulfurization will decrease, and if it exceeds 60% by weight, the amount of quicklime that participates in the desulfurization reaction will decrease. However, it is also undesirable because the desulfurization performance decreases, and from the viewpoint of desulfurization performance, the content of calcium carbonate in the fine quicklime powder is preferably more than 15% by weight and less than 45% by weight, more preferably more than 25% by weight. % by weight or less, most preferably greater than 30% by weight and 45% by weight
The following quicklime powder is good. The present inventors conducted extensive research using an electron microscope on the form of quicklime powder containing calcium carbonate, which is obtained by fluidized roasting diamide lime under various conditions in an oxidizing atmosphere. ,
As schematically shown in Figure 2, when the amount of calcium carbonate inside is less than 15% by weight, there are gas escape holes that reach the inside from the quicklime outer shell, that is, carbon dioxide generated by thermal decomposition of calcium carbonate. It was discovered that the gas escape hole was large and small when the amount exceeded 15% by weight. Because this gas vent hole is small, when the quicklime powder according to the present invention is blown into molten iron, the carbon dioxide gas generated by decomposition due to the rapid heating of the calcium carbonate remaining inside the quicklime in the outer shell. It is also presumed that it causes fine explosions, significantly increases the reaction interface area with molten iron, and thus exhibits excellent desulfurization performance. In addition, when the amount of calcium carbonate inside exceeds 60% by weight, in addition to reducing the amount of quicklime as a desulfurizing agent as described above, decomposition of calcium carbonate is an endothermic reaction, and it is necessary to balance with the temperature drop of molten iron. This is because the amount of carbon dioxide gas due to the decomposition of calcium carbonate is large, which increases the amount of molten iron being scattered by splash. Furthermore, the particle size of quicklime used in the present invention obtained by fluidized roasting diamide lime in an oxidizing atmosphere is as follows:
Mainly less than 60μ. In the specification of this application, "mainly particle size of 60μ or less" refers to powder with a particle size of 60μ or less.
80% by weight or more, preferably 90% by weight or more,
Particularly preferably 80% by weight of powder with a particle size of 46μ or less
As mentioned above, it is most preferably used in the meaning of 90% by weight or more. If the particle size is too coarse, mainly exceeding 60μ, gas transportability will decrease, fluctuations in the concentration of the desulfurization agent in the carrier gas during injection will increase, and the desulfurization performance of quicklime powder will not be fully demonstrated. I don't like it because it becomes a thing. The reason why the molten iron desulfurization agent of the present invention exhibits excellent gas transportability and desulfurization performance in blow desulfurization is that it itself is fine particles, has a large surface area per weight, and has good contact with molten iron. In addition to being excellent in
It is also presumed that various effects act synergistically based on moderate stirring of molten iron by carbon dioxide gas generated by thermal decomposition of calcium carbonate. Thus, according to the present invention, quicklime powder is obtained by fluidized roasting diamide lime in an oxidizing atmosphere, and the quicklime powder contains 15% by weight of calcium carbonate.
65-93% by weight of quicklime powder containing more than 60% by weight, 5-20% by weight of carbon substances, and 2-15% by weight of one or more halides of alkali and alkaline earth metals (however, the above polymerized amount % is based on the total weight of quicklime powder, carbon material and halides), and said quicklime powder,
A desulfurizing agent for molten iron for blow desulfurization is provided, in which the carbon material and one or more halides of alkali and alkaline earth metals mainly have a particle size of 60 μm or less. The desulfurizing agent of the present invention is
Not only does it exhibit excellent desulfurization performance, but it also has the effect of facilitating slag removal after desulfurization. Examples of the above-mentioned carbon materials include graphite, coal coke, petroleum coke, charcoal, etc., and any of them can be used without any particular limitations on the type or properties thereof. However, from the viewpoint of quality, it is desirable that it has a low sulfur content, and that it is dry and has low moisture content from the viewpoint of being used in combination with quicklime powder. Furthermore, coke is preferable in consideration of availability, price, etc. In order not to impede the excellent gas transportability and desulfurization reactivity of the quicklime powder according to the present invention, the particle size is mainly determined by the particle size as in the quicklime powder described above.
Preferably, the diameter is 60μ or less. In addition, halides of alkali and alkaline earth metals include fluorite, cryolite, NaF, KF, etc., and one or more of these can be used, but among these, , for example, contains 80-98% by weight of CaF ₂ and up to about 16% by weight of SiO ₂ as other impurities, etc.
Fluorite containing Fe ₂ O ₃ , MgO, etc. can be suitably used.
Furthermore, the particle size is preferably 60 μm or less, like the above-mentioned carbon material. The reason why the amount of carbon material added is limited to 5 to 20% by weight is that the amount of carbon material added is 5% to 20% by weight.
If it is less than 20% by weight, the improvement in desulfurization performance will be small; on the other hand, if it exceeds 20% by weight, the amount of carbon substances in the exhaust gas emitted from, for example, an iron mixer vehicle will increase due to the blowing desulfurization method. This is because problems such as an increase in the temperature of the gas, ignition, and an increase in carbon monoxide occur, making the working environment dangerous, which is undesirable. Furthermore, regarding the amount of one or more halides of alkali and alkaline earth metals, the reason why the amount of the halides is 2 to 15% by weight is that the amount of the halides added is less than 2% by weight. If so, there will be little improvement in desulfurization performance and slagging removal after desulfurization, and if it exceeds 15% by weight, it is undesirable because damage to refractories of pig iron trucks and the like will be significant. In order to improve desulfurization performance, maintain a safe working environment, improve slag removal after desulfurization, etc., the carbon content is 8 to 15% by weight, and one or more alkali and alkaline earth metal halides are used. It is preferable that the amount added is within the range of 5 to 10% by weight. The desulfurizing agent for molten iron of the present invention has extremely excellent gas transportability unlike the conventionally used quicklime powder, so it can be used alone or in combination with the desulfurizing agents mentioned above. In blow desulfurization, not only does pipe clogging not occur, but also there is almost no pulsation (variation) during the supply of desulfurization agent, so extremely stable desulfurization operation can be performed. The desulfurizing agent for molten iron of the present invention can be injected into the molten iron using a carrier gas, such as by supplying the desulfurizing agent from a hopper containing the desulfurizing agent to the injection pipe using a rotary valve, or by supplying the desulfurizing agent into the molten iron in a pressure vessel. Method of fluidizing the desulfurizing agent and blowing it in with carrier gas
-31518), and the latter method is particularly preferred. In this way, when the molten iron desulfurization agent of the present invention is used for desulfurization of molten iron, the desulfurization performance is high, so the amount added (unit consumption) is small, and therefore there is no loss of molten iron due to slag entrainment, etc. It also has many advantages, including vast improvements. Next, details of the fluidized roasting method for producing quicklime powder used in the present invention from diamide lime will be explained. As the heat medium used in the fluidized roasting method of diamide lime, non-binder, non-combustible, infusible solid media are used, such as quicklime, silica sand, alumina silica sand, clinker, gypsum granules, feldspar, and pottery stone. , Rouseki, Coccule, Zhangite, Zircon, Betalite, Shamotsuto, Mullite, Cordierite, Sillimalite,
Examples include kyanite, andariusite, shale, calcium silicate compounds, refractory bricks, metal powders, metal oxide powders, glass powders, and quicklime is preferably used. These heat transfer media form a fluidized bed and supply the necessary amount of heat for the thermal decomposition reaction of the outer shell of the introduced raw material diamide lime, and also jump out of the fluidized bed before the fluidized roasting of the diamide lime is insufficient. This function prevents the quicklime powder from forming and increasing the particle size due to agglomeration, and makes the particle size uniform. In order to perform fluidized roasting that fully achieves these effects and imparts excellent desulfurization performance to the resulting quicklime powder, the particle size of the heating medium should be at least 0.3 to 2.0 mm. It is necessary to account for 70% by weight, preferably 80% by weight or more, and preferably 0.3 to 1.5 mm.
It is preferable that the amount of carbon dioxide is at least 70% by weight, preferably 80% by weight or more. If the heating medium is too large (more than 2.0 mm), it often happens that uniformly fired lime powder cannot be obtained, and if it is too small (less than 0.3 mm), the heating medium may scatter out of the fluidized bed. , undesirable. Good results are obtained when the diamide lime is fed into the fluidized bed formed by the heating medium at a rate of 0.2 to 2.5 times the weight of the heating medium/hour, preferably 0.5 to 1.5 times/hour. If the amount is too high (more than 2.5 times/hour), there is a strong tendency for non-uniform fluidized roasting, and if it is less than 0.2 times/hour, the diamide lime will be fluidized excessively and the calcium carbonate remaining inside will be reduced. As a result, the desulfurization performance of the obtained quicklime powder during blow desulfurization tends to decrease. Further, the height of the fluidized bed is preferably 0.5 m or more, preferably in the range of 1.5 to 3.0 m. As mentioned above, the particle size of the heat transfer medium is within a specific range, and the diamide lime introduced into the fluidized roasting furnace is defined within a specific range relative to the amount of heat transfer medium, and furthermore, the residence time and combustion are within a specific range as described below. The gas superficial velocity condition is a particularly important condition, whereby quicklime powder exhibiting significantly improved gas transportability and desulfurization performance can be obtained more effectively than raw diamide lime. The superficial velocity of the combustion gas is an important factor in forming a stable fluidized bed, imparting particle size uniformity to the obtained quicklime powder, and forming an internal structure of calcium carbonate of more than 15% by weight and less than 60% by weight. However, the superficial velocity must be within the range of 1.1 to 2.7 m/sec, and preferably a superficial velocity of 1.2 to 2.5 m/sec. In this specification, "superficial velocity" refers to the time when the gas (e.g. air and carbon monoxide) supplied to the fluidized torrefaction furnace is directly heated to a predetermined furnace temperature (e.g. 850°C) and expands. Total supply amount (m ³ /
hr) divided by the cross-sectional area of the fluidized bed (m ² ) (m/
hr) converted into m/sec units. If the superficial velocity is too slow, less than 1.1 m/sec, the quicklime powder tends to harden and the desulfurization performance is reduced, which is undesirable. If the superficial velocity is too fast, exceeding 2.7 m/sec, the contamination of unfired products increases. In addition to this, it is also undesirable that particle size non-uniformity increases. In order to achieve a particularly good fluidized roasting effect, in addition to the conditions mentioned above, it is necessary that the roasting temperature is 800 to 900°C and the residence time in the fluidized bed is 5 to 20 seconds. . If the roasting temperature is too low (less than 800°C), incompleteness of firing will increase, which is undesirable; if it exceeds 900°C, which is too high, there will be a tendency for excessive fluidized roasting to occur, which is undesirable. Further, if the residence time is too long (more than 20 seconds), the desulfurization performance tends to deteriorate, and if the residence time is too short, less than 5 seconds, calcium carbonate will remain excessively inside, which is not preferable. As the roasting heat source, gaseous fuels such as carbon monoxide, natural gas, propane, and city gas, liquid fuels such as heavy oil, and solid fuels such as coke powder, and if desired, these may be used in combination as appropriate. can. In the fluidized roasting method, the oxygen necessary for complete combustion of the fuel is generally secured by supplying air, but in the present invention, diamide lime is fluidized in an oxidizing atmosphere as described above. For this purpose, it is desirable that the amount of oxygen in the air be at least 1.05 times, preferably 1.1 to 2.5 times, more preferably 1.1 to 2.2 times, the theoretical amount of oxygen required for complete combustion of the fuel. . These oxygen content ranges, i.e.
When diamide lime is fluidized and roasted under a specific excess of oxygen, the resulting powder exhibits extremely excellent gas transportability and desulfurization performance, although the reason is not clear as described above. In this way, quicklime powder that has been fluidized and roasted into a fine powder in an oxidizing atmosphere with a specific amount of calcium carbonate inside it can be roasted without damaging its fine powder state. It is taken out from the furnace and collected using a carry-over method, and various known methods can be used for this collection method.
It is possible to use a method in which quicklime powder is collected by a single cyclone or a combination of cyclones, and the like. Next, the basics of the fluidized roasting method and equipment in the method for producing quicklime powder used in the present invention will be explained using the accompanying drawings. In FIG. 1, diamide lime and heat medium are supplied to a fluidized roasting furnace main body 1 from hoppers 2 and 2'.
As the supply method, a transportation method such as a pneumatic transportation method or a screw feeder method is appropriately adopted. Carbon monoxide,
Fuel, such as heavy oil or coke, sent from the fuel tank 3 passes from the filter 6 through a perforated plate or a nozzle plate 5 equipped with a large number of nozzles, and is then delivered to the burner port by air flowing from the bottom of the furnace to the top of the furnace. 4, it burns in an oxidizing atmosphere and becomes a combustion gas. Furnace body 1
The quicklime powder that has been fluidized and roasted in the furnace passes through the exhaust pipe 7 from the top of the furnace in a carry-over method along with the exhaust air, and most of the quicklime powder is collected by a cyclone 8 and enters the product hopper 10. The exhaust air from cyclone 8 is
Furthermore, it is led to a back filter (not shown) through an exhaust pipe 9, and some of the accompanying quicklime powder is removed. Hereinafter, the present invention will be explained in more detail with reference to Reference Examples, Comparative Reference Examples, Examples, and Comparative Examples. (Manufacture of desulfurization agent by fluidized roasting) Reference Examples 1 to 5 and Comparative Reference Examples 1 to 2 Using a fluidized roasting furnace with an inner diameter of 500 mm and a height of 3000 mm shown in Figure 1, a particle size of 0.25 to 1.0 mm was 85 mm. Diamide lime was roasted under the conditions shown in Table 2 at a furnace temperature of 780 to 950°C (measured at the top of the furnace) using % by weight of quicklime as a heat medium, and quicklime powder was obtained from a cyclone. The chemical composition and particle size distribution of the diamide lime used are those in Table 1.

[Table] CaO, internal CaCO ₃ , C and SiO ₂ ,
Other chemical compositions and particle size distributions such as Al ₂ O ₃ , Fl ₂ O ₃ , MgO, etc. are shown in Table 3. Examples 1 to 5 show the results of testing the desulfurization performance and gas transportability of the quicklime powder obtained in Reference Examples 1 to 5 and Comparative Reference Examples 1 to 2, and the desulfurization agent prepared by blending fluorite and carbon with the quicklime powder. 5, and Comparative Examples 1 to 7
It was shown to. (Performance test of desulfurization agent) Examples 1 to 5 and Comparative Examples 1 to 7 A 350T capacity torpedo ladle filled with 270 to 330T of hot metal with a sulfur content of 0.037 to 0.045% was used as described in JP-A-49-31518. Desulfurization was carried out by blowing the desulfurizing agent shown in Table 4 into the hot metal from a lance at a blowing rate of 80 to 150 kg/min using dry nitrogen gas as a carrier gas. The results are shown in Table 4. The fluorite and carbon used in Table 4 are as follows. 1 Carbon: Use pulverized commercial coke,
Its chemical composition or C content is 90% by weight.2 Fluorite: commercially available fluorite is crushed, and its chemical composition is CaF ₂ 88% by weight, SiO ₂ 9% by weight,
Fl ₂ O ₃ 1% by weight and other 2% by weight,
The particle size distribution of the above carbon and fluorite is as follows.

[Table] The meanings of the terms used in Table 4 are as follows. (a) Basic unit: Weight of desulfurization agent injected into hot metal (Kg) / Weight of hot metal (
T) (B) Carrier gas/desulfurization agent: Flow rate of carrier gas used (Nl/min)/Blowing speed of desulfurization agent (Kg/min) (C) Blowing pressure: Desulfurization agent powder is entrained in carrier gas and blown into hot metal. The pressure of the carrier gas connected to the discharge part (Kg/cm ² ) during loading (JP-A-49
- In Figure 2 of Specification No. 31518, discharge hole 4
corresponds to a relatively low pressure P ₃ connected to. (d) Desulfurization performance: S ₁ = Sulfur content in hot metal before desulfurization (%) S ₂ = Sulfur content in hot metal after desulfurization (%) S ₁ - S ₂ (=△S) / Basic unit comparison Example 8 The chemical composition of quicklime, the raw material for industrial carbide, is
CaCO3 ₃ % by weight, CaO91% by weight, particle size 100μ or less is 50
Comparative Example 1~ except that % by weight of quicklime powder was used.
Desulfurization was carried out according to 5, but even if the carrier gas/quicklime powder was 70Nl/Kg or more, it was impossible to inject it. As shown in Table 4, the desulfurization agent of the present invention showed excellent performance in desulfurization performance and gas transportability.

【table】

【table】

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a diagram showing the principle of an apparatus for fluidized roasting of diamide lime in an oxidizing atmosphere, in which 1 is the furnace body, 2 is a raw material hopper, 2' is a hopper for heat medium, 3 is a fuel tank, 4 is a burner port, 5 is a perforated plate, 6 is an air filter, 7 is an exhaust pipe, 8 is a cyclone, 9 is an exhaust pipe, and 10 is a product hopper. Figure 2 shows the cross-sectional state of gas vent holes formed from the outer shell of quicklime to the inside of quicklime containing about 10% by weight of calcium carbonate, which was obtained by excessive fluidized roasting of diamide lime in an oxidizing atmosphere. This is shown schematically, and 20 is a quicklime outer shell, and 21 is a gas vent hole.

Claims (1)

[Claims] 1 Quicklime powder obtained by fluidized roasting of diamide lime in an oxidizing atmosphere, which contains 65 to 93% by weight of quicklime powder containing more than 15% by weight and less than 60% by weight of calcium carbonate, and carbon substances. 5 to 20% by weight and 2 to 15% by weight of one or more halides of alkali and alkaline earth metals.
(However, the above weight percentage is based on the total weight of quicklime powder, carbon material, and halide), and the quicklime powder, carbon material, and one or two halides of alkali and alkaline earth metals. All of the above mainly have a particle size of 60μ
A desulfurizing agent for molten iron for blow desulfurization, which is as follows.