CN119433112B - High-sulfur iron concentrate pellet desulfurizing agent and method for strengthening high-sulfur iron concentrate pellet desulfurization - Google Patents
High-sulfur iron concentrate pellet desulfurizing agent and method for strengthening high-sulfur iron concentrate pellet desulfurization Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B3/00—General features in the manufacture of pig-iron
- C21B3/02—General features in the manufacture of pig-iron by applying additives, e.g. fluxing agents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
- C22B1/20—Sintering; Agglomerating in sintering machines with movable grates
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- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
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- C22B1/242—Binding; Briquetting ; Granulating with binders
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Abstract
本发明公开了一种高硫铁精矿球团脱硫剂及强化高硫铁精矿球团脱硫的方法，属于铁矿球团生产技术领域。高硫铁精矿球团脱硫剂包括过氧化钙粉末、直接还原铁粉灰尘和二氧化锰粉末，脱硫剂参与含硫铁矿造球，所得生球依次经过鼓风干燥、预热和焙烧，得到成品球团。该方法利用脱硫剂可以显著加快高硫铁精矿球团在干燥预热过程的脱硫效率，同时去掉抽风干燥可避免球团干燥时大量吸附SO2而在球团表面形成硫酸盐外壳导致球团强度降低的技术问题。该方法操作方法简单、生产成本低、环境友好，满足工业化生产要求。
The invention discloses a high-sulfur iron concentrate pellet desulfurizer and a method for strengthening the desulfurization of high-sulfur iron concentrate pellets, and belongs to the technical field of iron ore pellet production. The high-sulfur iron concentrate pellet desulfurizer includes calcium peroxide powder, direct reduced iron powder dust and manganese dioxide powder. The desulfurizer participates in the pelletization of sulfide-containing iron ore, and the obtained green balls are sequentially subjected to blast drying, preheating and roasting to obtain finished pellets. The method utilizes the desulfurizer to significantly accelerate the desulfurization efficiency of high-sulfur iron concentrate pellets in the drying and preheating process. At the same time, removing the exhaust drying can avoid the technical problem that a large amount of SO2 is adsorbed during pellet drying to form a sulfate shell on the surface of the pellets, resulting in a decrease in the strength of the pellets. The method has a simple operation method, low production cost, and is environmentally friendly, meeting the requirements of industrial production.
Description
Technical Field
The invention relates to a desulfurizing agent, in particular to a desulfurizing agent for high-sulfur iron concentrate pellets, and also relates to a method for reinforcing the desulfurization of the high-sulfur iron concentrate pellets by using the desulfurizing agent, belonging to the technical field of iron ore pellet production.
Background
With the development of the iron and steel industry, the demand for iron concentrates is increasing, but the reserves of high-grade iron concentrates are gradually decreasing. Numerous iron and steel enterprises use complex ores on a large scale as the main direction of future development, including high-sulfur iron concentrates.
The high-sulfur iron concentrate is an iron concentrate with a high sulfur content, wherein sulfur elements are present in the iron concentrate in the form of pyrite/pyrrhotite. In the production process of the high-sulfur iron concentrate pellets, most of pyrite/pyrrhotite is rapidly decomposed in a preheating section and releases SO 2, and enters the flue gas. However, when the proportion of high-sulfur iron concentrate in the pellets is too high, the desulfurization rate of the pellets in the drying and preheating section needs to be improved. In addition, when pellets are produced by a grate-kiln process or a belt roasting process, the pellets are generally dried in a pumping section using the high-temperature flue gas of the preheating II as a heat source. Therefore, the green pellets which are not completely dried in the forced air drying section are continuously dried and dehydrated in the pumping section, so that the pellets are completely dried. When the pellets are subjected to air draft drying by utilizing high-temperature flue gas from the preheating II, SO 2 in the flue gas is quickly combined with water vapor to generate H 2SO4, SO that the H 2SO4 further reacts with alkali metal compounds on the surface layers of the pellets to form a layer of sulfate to be deposited in the pellets. When the pellets enter the rotary kiln, the easily-decomposed sulfate is rapidly decomposed to reduce the surface strength of the pellets, and the powder on the surface of the pellets falls off in the movement friction process of the pellets, so that the ring formation in the rotary kiln is serious.
Disclosure of Invention
Aiming at the technical problems of low desulfurization efficiency of a preheating drying section, pellet quality reduction caused by SO 2 circulating enrichment, serious ring formation in a rotary kiln and the like existing in the process of producing pellets by high-sulfur iron ore concentrate.
The invention aims to provide a high-sulfur iron concentrate pellet desulfurizer which can strengthen the desulfurization efficiency of high-sulfur concentrate pellets in a drying and preheating section, reduce the sulfur content in iron ore pellets and improve the metallurgical performance of the high-sulfur iron concentrate pellets.
The second object of the invention is to provide a method for strengthening desulfurization of high-sulfur iron concentrate pellets, which strengthens desulfurization of the high-sulfur iron concentrate pellets by using a desulfurizing agent, and simultaneously avoids adsorption of SO 2 in flue gas by raw pellets in the process of suction drying by omitting a suction drying section by optimizing a pellet drying procedure, thereby preventing sulfate shells from being formed on the surfaces of the pellets, and achieving the purposes of improving pellet quality and preventing looping in a rotary kiln.
In order to achieve the technical aim, the invention provides a high-sulfur iron concentrate pellet desulfurizer which comprises, by mass, 85-93% of direct reduced iron powder dust, 5-10% of calcium peroxide powder and 2-5% of manganese dioxide powder.
In the desulfurizing agent, the calcium peroxide powder, the direct reduced iron powder and the manganese dioxide powder are subjected to complex oxidation heat release in the oxidizing roasting process, so that the internal temperature field of the high-sulfur iron concentrate pellets is increased, and meanwhile, pyrite/pyrrhotite in the high-sulfur iron concentrate pellets is catalyzed and promoted to accelerate conversion to realize desulfurization, so that the desulfurizing efficiency is greatly improved, meanwhile, the iron grade of the high-sulfur iron concentrate pellets can be increased due to the introduction of the direct reduced iron powder, and the technical problem of iron grade reduction of the iron ore pellets caused by the introduction of the desulfurizing agent is avoided.
The high-sulfur iron concentrate pellet desulfurizer of the invention takes direct reduced iron powder dust as a main component, and calcium peroxide powder and manganese dioxide powder as secondary components, mainly for improving the desulfurization efficiency of the sulfur iron concentrate pellets and simultaneously ensuring the higher iron grade of the iron ore pellets.
As a preferable scheme, the mass content of Fe of the direct reduced iron powder dust is 50-80%, and the mass content of SiO 2 is 1.5-2.5%. The direct reduced iron dust has a high Fe content, and the iron grade of the iron ore pellets is not reduced by taking the direct reduced iron dust as a main component of the desulfurizing agent.
As a preferable mode, the particle size of the direct reduced iron powder dust, the calcium peroxide powder and the manganese dioxide powder satisfies the mass ratio of-10 μm particle size fraction to 90% or more. The components in the desulfurizing agent keep finer granularity, can ensure that the green pellet strength is not reduced, are uniformly distributed in the pellets, and better play a desulfurizing effect.
The invention also provides a method for strengthening desulfurization of the high-sulfur iron concentrate pellets, which comprises the steps of mixing the desulfurizing agent with sulfur-containing iron concentrate and a binder, pelletizing, and sequentially carrying out blast drying, preheating I, preheating II and roasting on the obtained green pellets by adopting a grate-rotary kiln system to obtain finished pellets.
According to the method for strengthening the desulfurization of the high-sulfur iron concentrate pellets, on one hand, a special desulfurizing agent is introduced into the pellets, SO that deep desulfurization of raw pellets in the drying and preheating process can be promoted, on the other hand, an induced draft drying section is omitted, the blast dried pellets directly enter the preheating section, sulfur dioxide is concentrated in the preheating section to be removed, and the condition that high-concentration sulfur dioxide flue gas in the preheating section is circularly introduced into the induced draft drying process to enrich SO 2 on the surfaces of the pellets is avoided, SO that the quality of the pellets is improved, and ring formation in a rotary kiln is avoided.
As a preferable scheme, the mass of the desulfurizing agent accounts for 1.0-2.5% of the total mass of the desulfurizing agent, the sulfur-containing iron concentrate and the binder. When the dosage of the desulfurizing agent is higher, the desulfurizing efficiency of the high-sulfur iron concentrate can be improved, but the iron grade of the pellets can be reduced. Therefore, the proper mixing amount can ensure the desulfurization efficiency and the iron grade of the high-sulfur iron concentrate pellets.
As a preferable scheme, the TFe mass content of the sulfur-containing iron ore concentrate is 58% -66%, and the sulfur mass content is 0.5% -1.5%.
As a preferable scheme, the binder is bentonite, wherein the mass content of TFe is 2.0% -3.5%, and the content of SiO 2 is 50% -56%. Preferably, bentonite is used as a binder, so that the forming performance and uniformity of the green pellets can be improved, the performance of the green pellets in the drying and roasting processes is optimized, and the compression strength and high temperature resistance of the pellets can be further improved by controlling the bentonite components.
As a preferable scheme, the condition of the forced air drying is that the temperature is 360-500 ℃ and the time is 7-10 min. The drying temperature is properly increased and the drying time is prolonged in the forced air drying process, SO that the green pellets can be fully dried on the premise of canceling the induced draft drying, the problem of surface sulfate enrichment caused by the adsorption of SO 2 by the undried green pellets in the subsequent preheating process is avoided, and the quality and metallurgical performance of the pellets are improved.
As a preferable scheme, the preheating I is carried out under the conditions that the temperature is 620-700 ℃ and the time is 3.0-4.0 min. As a preferable scheme, the condition of the preheating II is that the temperature is 920-950 ℃ and the time is 4.0-5.5 min. The temperature steps of the preheating I and the preheating II are increased gradually, SO that the explosion of pellets is avoided, sulfur dioxide is mainly concentrated in the discharge of the preheating II, and particularly, the pellets are ensured to be heated uniformly before roasting by precisely controlling the temperature and the time of the preheating stage, the surface enrichment of SO 2 is reduced, and the high compressive strength and the low reduction expansion rate of finished pellets are ensured.
As a preferable scheme, the roasting condition is that the temperature is 1250-1280 ℃ and the time is 10-20 min.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) The desulfurizing agent provided by the invention can increase the desulfurizing efficiency of the pellets in the drying and preheating section on the basis of not reducing the grade of the pellets.
2) According to the method for strengthening desulfurization of the high-sulfur iron concentrate pellets, provided by the invention, by using a special desulfurizing agent, canceling the traditional air draft drying design, optimizing conditions such as temperature and time of forced air drying and preheating, the green pellets can be uniformly heated in the drying and preheating processes, SO that enrichment of SO 2 on the surfaces is reduced, the strength of finished pellets is effectively improved, and the influence of SO 2 on equipment and environment is reduced.
3) The method for strengthening desulfurization of the high-sulfur iron concentrate pellets reduces equipment complexity and maintenance cost, is easy to implement in operation flow, has higher production efficiency and economic benefit, and is suitable for large-scale industrial application.
Drawings
Fig. 1 is an SEM image of the preheated pellets prepared in example 3 of the present invention, and it can be seen from the figure that when the pellets of high-sulfur iron concentrate use 1.5% of desulfurizing agent and the distribution of S content elements in the pellets after removal of the suction drying section in the drying process is low, it is indicated that the desulfurization of the preheated pellets is more thorough, and only a small amount of S elements are combined with alkali metal and remain in the preheated pellets.
Fig. 2 is an SEM image of the preheated pellets prepared in comparative example 2 of the present invention, and it can be seen from the image that when the amount of the desulfurizing agent added is 0.5%, a large amount of S element and Fe element are combined together, which indicates that the oxidative decomposition efficiency of pyrite/pyrrhotite in the high-sulfur iron concentrate pellets is low.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the claims.
In the following examples and comparative examples, both CaO 2 and MnO 2 are commercially available in a purity of >98.8%. The Fe content of the direct reduced iron dust is 61%, the SiO 2 content is 2.3%, and the CaO 2 reagent, the MnO 2 reagent and the direct reduced iron dust particle size all meet the mass ratio of-10 mu m particle size grade to 93%. The high-sulfur iron concentrate comprises the components of TFe 64.34%, siO 2 1.65%, caO 2.04%, mgO 1.64%, al 2O3 1.02%, S0.84%, na 2 O0.09, K 2 O0.10%, bentonite containing SiO 2 55.95%, caO 2.58%, mgO 0.41%, al 2O3 1.45%, na 2 O2.36%, K 2 O0.74% and TFe 3.0% by mass.
In the following specific embodiment, a grate-rotary kiln system is adopted in the pellet heat treatment process, and the specific pellet production process comprises the steps of conveying a desulfurizing agent, high-sulfur iron ore and bentonite to a mixing bin through a belt, granulating in a disc granulator after fully and uniformly mixing, and controlling the moisture content of green pellets to be 8% through externally adding water to obtain the green pellets. And then, the green pellets enter a grate machine and pass through a forced air drying section to obtain completely dried pellets, and the dried pellets are directly preheated by preheating I and preheating II and finally enter a rotary kiln for roasting.
Example 1:
the weight ratio of the high-sulfur iron concentrate to bentonite to the desulfurizing agent (direct reduced iron powder dust: calcium peroxide powder: manganese dioxide powder=90:7:3) is 97:2.0:1.0.
The temperature of the air-blast drying was 360 ℃ for 7min.
The temperature of the preheating I is 680 ℃ and the time is 3min.
The temperature of preheat II was 950℃for 4.6min.
The baking temperature is 1260 ℃ and the baking time is 13min.
The S content of the surface layer of the obtained preheated ball is 0.57%, the S content of the inner layer is 0.54%, the compressive strength of the finished pellets is 240N, and the S content is 0.002%.
Example 2:
the weight ratio of the high-sulfur iron concentrate to bentonite to the desulfurizing agent (direct reduced iron powder dust: calcium peroxide powder: manganese dioxide powder=90:7:3) is 97:2.0:1.0.
The temperature of the air-blast drying was 420 ℃ and the drying time was 7min.
The temperature of the preheating I was 660℃and the time was 3.5min.
The temperature of preheat II was 940℃for a period of 5.0min.
The calcination temperature was 1250℃and the time was 15min.
The S content of the surface layer of the obtained preheated pellet is 0.21%, the S content of the inner layer is 0.10%, the compressive strength of the finished pellet is 2550N, and the S content is 0.008%.
Example 3:
High sulfur iron concentrate, bentonite and desulfurizing agent (direct reduced iron dust: calcium peroxide powder: manganese dioxide powder=85:10:5) in a weight ratio of 96.5:2.0:1.5.
The temperature of the air-drying was 500℃and the time was 8min.
The temperature of the preheating I is 680 ℃ and the time is 3min.
The temperature of preheat II was 950℃for 4.6min.
The baking temperature is 1260 ℃ and the baking time is 13min.
The S content of the surface layer of the obtained preheated pellet is 0.20%, the S content of the inner layer is 0.24%, the compressive strength of the finished pellet is 2501N, and the S content is 0.013%.
Example 4:
High sulfur iron concentrate, bentonite and desulfurizing agent (direct reduced iron dust: calcium peroxide powder: manganese dioxide powder=90:7:3) in a weight ratio of 96:1.5:2.5.
The temperature of the air-drying was 450 ℃ and the time was 10min.
The temperature of the preheating I is 680 ℃ and the time is 3min.
The temperature of preheat II was 950℃for 4.6min.
The calcination temperature was 1250℃and the time was 20min.
The S content of the surface layer of the obtained preheated pellet is 0.26%, the S content of the inner layer is 0.22%, the compressive strength of the finished pellet is 2446N, the S content is 0.015%, and the iron grade is 63.52%.
Comparative example 1:
The only difference compared to example 1 is that the forced draught drying is provided while the forced draught drying parameters are adjusted. The method is characterized in that the temperature of the forced air drying is 310 ℃, the time is 3.4min, the temperature of the induced air drying is 400 ℃, the time is 5min, and the hot air of the induced air drying is derived from a preheating two-stage.
Other operations and condition controls are described in example 1.
The S content of the surface layer of the obtained preheated ball is 0.92%, the S content of the inner layer is 0.62%, the compressive strength of the finished pellets is 2100N, and the S content is 0.015%.
Compared with the embodiment 1, after the process of the air draft drying section is added, the sulfur content of the surface layer of the preheated pellets is rapidly increased, the pellet strength is reduced by 300N, and the oxidation consolidation of the pellets is not facilitated.
Comparative example 2:
The only difference from example 2 is that the weight ratio of high sulfur iron concentrate, bentonite and desulfurizing agent (direct reduced iron dust: calcium peroxide powder: manganese dioxide powder = 90:7:3) is 97.5:2.0:0.5. Other operations and condition controls are described in example 2.
The S content of the surface layer of the obtained preheated pellet is 0.43%, the S content of the inner layer is 0.36%, the compressive strength of the finished pellet is 2294N, and the S content is 0.012%.
Compared with the example 2, other process conditions are the same, except that the addition amount of the desulfurizing agent is reduced by 0.5%, the S content in the preheated pellets is increased by 0.26%, and the strength of the finished pellets is reduced by 256N. Therefore, the lower addition of the desulfurizing agent is unfavorable for the desulfurization of the preheating balls and reduces the strength of the balls.
Comparative example 3:
The only difference from example 3 is that the temperature of the forced air drying section is 340℃and the time is 8 min. Other operational and condition controls are described in example 3.
The S content of the surface layer of the obtained preheated pellet is 0.46%, the S content of the inner layer is 0.49%, the compressive strength of the finished pellet is 2265N, and the S content is 0.016%. After the drum drying temperature was reduced, the sulfur content of the inner layer of the preheated pellets was increased by 0.25% and the pellet strength was reduced by 236N as compared with example 3. The lower drying temperature is unfavorable for pellet desulfurization, which leads to delay of desulfurization and influences pellet oxidation efficiency.
Comparative example 4:
The only difference from example 4 is that the temperature of the forced air drying is 450 ℃ and the time is 4 min. Other operations and condition controls are described in example 4.
The S content of the surface layer of the obtained preheated pellet is 0.39%, the S content of the inner layer is 0.37%, the compressive strength of the finished pellet is 2187N, and the S content is 0.021%.
Compared with example 4, after the blast drying time was shortened, the sulfur content of the inner layer of the preheated pellets was increased by 0.15%, and the pellet strength was reduced by 259N. The shorter drying time reduces the desulfurization rate of drying, which results in rapid desulfurization in the preheating section and is unfavorable for the oxidative consolidation of pellets.
Comparative example 5:
The only difference from example 4 is that the high sulfur iron concentrate, bentonite and desulfurizing agent (direct reduced iron dust: calcium peroxide powder: manganese dioxide powder = 80:15:5) are in a weight ratio of 96:1.5:2.5. Other operations and condition controls are described in example 4.
The S content of the surface layer of the obtained preheated pellet is 0.37%, the S content of the inner layer is 0.52%, the compressive strength of the finished pellet is 2237N, the S content is 0.015%, and the iron grade is 62.14%.
Compared with the example 4, the dosage of the reduced iron powder dust in the desulfurizing agent is reduced, the sulfur content of the inner layer of the preheated pellet is increased by 3.0%, the pellet strength is reduced by 209N, and the iron grade is reduced by 1.38%. The lower reduced iron dust and higher calcium peroxide dosage of the desulfurizing agent affect the total iron content and oxidative consolidation in the pellets, resulting in the reduction of the grade and strength of the pellets.
Claims (4)
1. A method for strengthening desulfurization of high-sulfur iron concentrate pellets is characterized in that a desulfurizing agent, sulfur-containing iron concentrate and a binder are mixed and pelletized, and the obtained green pellets are subjected to forced air drying, preheating I, preheating II and roasting in sequence by adopting a grate-rotary kiln system, so that finished pellets are obtained;
the mass of the desulfurizing agent accounts for 1.0-2.5% of the total mass of the desulfurizing agent, the sulfur-containing iron concentrate and the binder;
The condition of the forced air drying is that the temperature is 360-500 ℃ and the time is 7-10 min;
the preheating I is carried out at 620-700 ℃ for 3.0-4.0 min;
the condition of the preheating II is that the temperature is 920-950 ℃ and the time is 4.0-5.5 min;
The roasting condition is that the temperature is 1250 ℃ to 1280 ℃ and the time is 10min to 20min;
The desulfurizing agent comprises the following components in percentage by mass:
85-93% of direct reduced iron powder dust;
5-10% of calcium peroxide powder;
2-5% of manganese dioxide powder.
2. The method for strengthening desulfurization of high-sulfur iron concentrate pellets according to claim 1, which is characterized in that:
the mass content of Fe of the direct reduced iron powder dust is 50-80%, and the mass content of SiO 2 is 1.5-2.5%.
3. The method for strengthening desulfurization of high-sulfur iron concentrate pellets according to claim 1, which is characterized in that:
The particle sizes of the direct reduced iron powder dust, the calcium peroxide powder and the manganese dioxide powder all meet the mass ratio of-10 mu m particle size fraction to be more than 90 percent.
4. The method for strengthening desulfurization of high-sulfur iron concentrate pellets according to claim 1, which is characterized in that:
The adhesive is bentonite, the TFe mass content of the adhesive is 2.0% -3.5%, and the SiO 2 content is 50% -56%.
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| CN105112647A (en) * | 2015-09-06 | 2015-12-02 | 中南大学 | Sulfur fixation method of roasting low-grade molybdenite concentrate through lime method |
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| US4946658A (en) * | 1986-11-06 | 1990-08-07 | Florida Institute Of Phosphate Research | Addition of pyritic materials to feed mix for desulfurization of phosphogypsum |
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| CN110016549B (en) * | 2019-05-21 | 2021-02-09 | 中南大学 | A composite additive for strengthening the direct reduction of laterite nickel ore and its application |
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| CN115386725B (en) * | 2022-08-31 | 2024-03-26 | 武汉钢铁有限公司 | Resource treatment method for metallurgical iron-containing desulfurization solid waste |
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| CN102242254A (en) * | 2011-06-29 | 2011-11-16 | 中南大学 | High sulfide pyrite pellet reinforced roasting consolidation technology |
| CN105112647A (en) * | 2015-09-06 | 2015-12-02 | 中南大学 | Sulfur fixation method of roasting low-grade molybdenite concentrate through lime method |
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