CN111254278B - Oxidized pellet binder prepared from low-rank coal and preparation method and application thereof - Google Patents
Oxidized pellet binder prepared from low-rank coal and preparation method and application thereof Download PDFInfo
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- CN111254278B CN111254278B CN202010235639.3A CN202010235639A CN111254278B CN 111254278 B CN111254278 B CN 111254278B CN 202010235639 A CN202010235639 A CN 202010235639A CN 111254278 B CN111254278 B CN 111254278B
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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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
Abstract
The invention discloses an oxidized pellet binder prepared from low-rank coal and a preparation method and application thereof, wherein the oxidized pellet binder is prepared by crushing the low-rank coal, performing oxidative fermentation, adding solid caustic soda and water for blending slurry, and heating and stirring; and adding the oxidized pellet binder into iron ore powder for pelletizing to obtain the iron ore green pellets for the oxidized pellets. The invention takes low-rank coal as raw material, and obtains the oxidized pellet binder by simple oxidative fermentation and then synchronously extracting humic acid and mixing slurry, the raw material has the advantages of low price and wide source, simple process, low binder consumption, good binding property and strong applicability, and not only can obviously improve the balling property of the iron ore resource difficult to pelletize, but also does not influence the iron grade of the finished pellets.
Description
Technical Field
The invention relates to an oxidized pellet binder prepared from low-rank coal, and a preparation method and application thereof, and belongs to the technical field of ferrous metallurgy.
Background
The steel is an important basic material for national economic construction and social development, the yield of the Chinese crude steel is rapidly increased since 2000, and the yield of the Chinese crude steel is 1.27 hundred million tons in 2000, which only accounts for 15 percent of the total yield of the global crude steel. In 2018, the accumulated yield of Chinese crude steel reaches 9.28 hundred million tons, which accounts for more than half of the world steel yield.
With the continuous increase of the steel yield, the charging material structure produced by the method is also under continuous development. The main iron-containing raw materials for steel production include sinter, pellet and lump ore. With the increasing shortage of high-quality iron ore resources, lump ore resources meeting the requirements of iron making production are almost consumed, and most of iron ore powder or iron ore concentrate needs to be agglomerated (sintered or pelletized) to meet the production requirements. At present, the long flow of a blast furnace-converter is taken as a main part in steel production, sintered ores, pellets, coke and the like are taken as raw materials, molten iron is obtained after the iron making of the blast furnace, and the molten iron of the blast furnace is taken as the raw material to enter the converter for steel making.
The long-flow production of steel generally adopts high-alkalinity sinter ore and acid oxidation pellet ore as charging materials. Compared with sintered ore, the pellet ore has the advantages of high iron grade, good strength, uniform granularity, good reducibility and the like, the production energy consumption of the pelletizing process is low, and the energy consumption of the pelletizing process of advanced enterprises is only about 1/3 of that of the sintering process; the pollutant discharge amount is less, the harmful components in the waste gas are less, the subsequent tail end treatment cost is low, the pollutant discharge amount of the pelletizing process is far lower than that of the sintering process, and the dust, sulfur dioxide and nitrogen oxide discharge amounts to 1/7, 1/3 and 1/5 of the sintering process respectively. The proportion of the pellet ore in the blast furnace production in the foreign countries reaches more than 70 percent, even reaches 100 percent. In 2018, the domestic pellet yield is about 1.59 hundred million tons, the import quantity is 1850 ten thousand tons, the pellet yield cannot meet the steel production requirement, and the charging ratio of the pellets is only 14 percent, which is far lower than the world average level.
In the production process of iron ore concentrate pellets, the binder has important influence on the pellet preparation process and the pellet quality. The production of the pellet ore in China has the problems of large binder dosage, low iron grade and the like. Bentonite is generally adopted as a binder to prepare the oxidability pellets in steel plants in China. However, the bentonite in China has poor quality, the coarse fraction content of iron ore concentrate for pellet production is high, and the bentonite with high proportion needs to be added to meet the requirement of industrial production. Because the bentonite is added with a large amount of aluminosilicate and other impurities, the iron grade of the pellet ore is seriously reduced, and the energy consumption and the production cost of iron making are obviously increased.
In addition, with the increasing exhaustion of high-quality iron ore resources, more and more poor-quality iron ore resources which are difficult to pelletize are used for producing pellets, such as vanadium-titanium magnetite, specularite, magnetite, iron-containing dust and the like. In order to improve the balling performance or roasting performance of inferior iron ore resources, bentonite with a higher proportion needs to be added to meet the production requirement, but the bentonite cannot be used for preparing the pellets from part of inferior iron-containing resources.
Disclosure of Invention
The invention aims to provide a preparation method of an oxidized pellet binder prepared from low-rank coal, aiming at the problems of increased gangue content of pellets, reduced iron grade, increased energy consumption in steel production and incapability of pelletizing part of inferior iron ore resources by using a bentonite binder in the existing iron ore pellet production process.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a process for preparing the oxidized adhesive of pellet from low-rank coal includes such steps as breaking low-rank coal, oxidizing fermentation, adding solid caustic soda and water, stirring while heating.
Preferably, the content of humic acid in the low-rank coal is not less than 25%; further preferably, the content of humic acid in the low-rank coal is not less than 30 percent; crushing to a particle size of less than 10 mm.
Preferably, the temperature of the oxidative fermentation is 80-200 ℃, the time is 2-10 h, and after the oxidative fermentation is finished, the low-rank coal is further ground until the content of particles with the particle size of less than 0.1mm reaches more than 70%.
Preferably, the addition amount of the solid caustic soda accounts for 20-30% of the mass of the low-rank coal; the addition amount of water is 2-5 times of the mass of the low-rank coal.
Preferably, the heating and stirring temperature is 50-100 ℃, and the time is 1-5 h.
The invention also provides the oxidized pellet binder prepared by the preparation method, which has high content of organic components, good binding performance and strong applicability.
The invention also provides application of the oxidized pellet binder, and the oxidized pellet binder is added into iron ore powder for pelletizing to obtain iron ore green pellets for oxidized pellets.
The oxidized pellet binder can be used for poor-quality iron ore resources which are difficult to pelletize and have poor pelletizing performance, such as vanadium-titanium magnetite ore, magnetic hematite mixed ore and the like, can enhance the surface hydrophilicity of the poor-quality iron ore which is difficult to pelletize, and is beneficial to pelletizing iron ore particles.
Preferably, the iron ore powder is subjected to wet grinding or high-pressure roller grinding and then is pelletized, so that the green pellet strength can be further improved.
Preferably, the addition amount of the oxidized pellet binder accounts for 1-4% of the mass of the iron ore powder, and the humic acid amount in the oxidized pellet binder accounts for 0.2-0.5% of the mass of the iron ore powder.
The humic acid contains carboxyl, hydroxyl and benzene ring structures and has a binder molecular structure. The low-rank coal is a main source for extracting humic acid, but the content difference of the humic acid is large, the existing extraction method generally comprises the working procedures of extraction, evaporation, drying, grinding and the like, the problems of high energy consumption, long flow, low extraction rate and the like exist, and the prepared humic acid product is in a solid state, is difficult to disperse when used for producing oxidized pellets, and is limited in binding action. According to the invention, the humic acid content of low-rank coal is increased by 1.2-2 times through pre-oxidation fermentation, then humic acid is synchronously extracted and size mixing is carried out to obtain an oxidized pellet binder, the oxidized pellet binder is directly mixed with iron ore powder to prepare green pellets, the dissolved humic acid forms a colloidal solution and can uniformly cover the surfaces of iron ore particles, the surface hydrophilicity of the iron ore particles is obviously improved, and the surface tension of the iron ore is increased; and the iron ore particles are connected through the long chain bridge forming effect of the surface binder of the iron ore particles, so that the iron ore particles can form balls, and the green ball strength is improved.
Compared with the prior art, the invention has the advantages that:
(1) because the iron ore resources in China are poor, impure, fine and have poor pelletizing performance, the bentonite addition amount is larger when the bentonite binder is used for preparing the iron ore pellets. The prepared binder has good bonding property, can improve the pelletizing property of iron ore, has strong product adaptability, can be suitable for poor iron ore pellets which are difficult to pelletize, and obviously improves the pelletizing strength.
(2) The bentonite is used as a binder, most of the bentonite is used as an inorganic component, and the bentonite is remained in the finished product balls after the green balls are roasted, so that the iron grade in the finished product balls is reduced. According to the blast furnace production practice, the iron grade in finished pellets fed into the furnace is improved by 1 percent, the blast furnace coke ratio is reduced by 2 percent, the ironmaking yield is improved by 3 percent, and the blast furnace slag amount is reduced by 20kg/t, so the production cost of ironmaking is greatly improved and the production efficiency is reduced by adopting the bentonite binder. The binder prepared by the invention is an organic binder, has high content of organic components, and the organic components are completely combusted and volatilized in the preheating and roasting processes of the oxidized pellets, so that the iron grade of finished pellets is not influenced.
(3) According to the invention, low-rank coal is subjected to oxidative fermentation to obviously improve the content of humic acid in the coal, then humic acid is synchronously extracted and size-mixed to obtain the oxidized pellet binder, and the oxidized pellet binder is directly mixed with iron ore powder to prepare green pellets, so that the content of the humic acid effective component is high, and the humic acid is not required to be matched with other binders for use; the extracted humic acid components do not need to be prepared into powder products, the process steps of slurry drying, crushing, grinding and the like are omitted, and the method is short in flow, low in energy consumption and high in process efficiency.
Detailed Description
The invention is further explained and illustrated below. In the embodiment of the invention, low-order lignite is selected as a raw material, and the humic acid content of the low-order lignite is 32 wt%. Crushing lignite to be less than 10mm, fully oxidizing and fermenting for 6 hours at the temperature of 120 ℃, and further grinding the lignite to enable the mass of particles with the particle size of less than 0.1mm to account for 85% of the total mass of the pulverized coal; adding solid caustic soda accounting for 25% of the coal powder and water accounting for 400% of the coal powder into the coal powder to prepare coal slurry, heating the coal slurry to 95 ℃, and continuously stirring for 3 hours to obtain the oxidized pellet binder.
In the embodiment of the invention, vanadium-titanium magnetite which is difficult to pelletize is selected as an iron ore raw material. The vanadium titano-magnetite has the main components shown in the table 1, and is pelletized by adding the prepared binder.
TABLE 1 vanadium titano-magnetite major chemical composition/problem wt.%
Example 1
Pelletizing by using vanadium titano-magnetite as a raw material, wherein the water content of the raw material is 5.0 wt%, adding a binder accounting for 3.0 wt% of the vanadium titano-magnetite powder to keep the water content at 8.0 wt% during pelletizing, fully mixing uniformly, sieving the mixture to below 1mm, and pelletizing by using a disc pelletizer, wherein the pelletizing time is 10-12 min, and the pellet size is 10-12 mm. The obtained iron ore green pellets are detected to have the falling strength of 3.5 times/(0.5 m) and the compressive strength of 13.7N/pellet.
Comparative example 1
Pelletizing by taking vanadium titano-magnetite as a raw material, wherein the water content of the raw material is 5.0 wt%, adding water accounting for 3.0 wt% of the vanadium titano-magnetite powder to keep the water content at 8.0 wt% during pelletizing, adding bentonite binder accounting for 1.0 wt% of the iron ore powder, fully and uniformly mixing, sieving the material to below 1mm, and pelletizing by adopting a disc pelletizer, wherein the pelletizing time is 10-12 min, and the pellet size is 10-12 mm. The obtained iron ore green pellets are detected to have the falling strength of 2.3 times/(0.5 m) and the compressive strength of 11.7N/pellet.
Comparative example 2
Pelletizing by taking vanadium titano-magnetite as a raw material, wherein the water content of the raw material is 5.0 wt%, adding water accounting for 3.0 wt% of the vanadium titano-magnetite powder to keep the water content at 8.0 wt% during pelletizing, adding bentonite binder accounting for 1.5 wt% of the iron ore powder, fully and uniformly mixing, sieving the material to below 1mm, and pelletizing by adopting a disc pelletizer, wherein the pelletizing time is 10-12 min, and the pellet size is 10-12 mm. The obtained iron ore green pellets are detected to have the falling strength of 3.3 times/(0.5 m) and the compressive strength of 13.2N/pellet.
Comparing the green pellet index data of example 1 with that of comparative examples 1-2, in order to meet the minimum requirement that the drop strength of the iron ore green pellets is higher than 3.0 times/(0.5 m), the minimum addition amount of the bentonite binder needs to be more than 1.5%. In example 1, when 3.0 wt% of a binder prepared from low-rank brown coal was added (i.e., the amount of humic acid added was 0.45 wt%), both the green pellet falling strength and compressive strength were higher than those of the green pellets when 1.5 wt% of a bentonite binder was added. The prepared binder has good binding performance and small dosage, and can improve the balling performance of the iron ore difficult to be pelletized.
Example 2
The vanadium titano-magnetite is subjected to 3 times of pretreatment by a high pressure roller and then is pelletized, water accounting for 1.0 wt% of the mass of the vanadium titano-magnetite and 2.0 wt% of binder slurry are added into iron ore powder to keep the water at 8.0 wt% during pelletizing, the materials are thoroughly and uniformly mixed, the materials are sieved to below 1mm, and pelletizing is carried out by a disc pelletizer, wherein the pelletizing time is 10-12 min, and the pellet size is 10-12 mm. The obtained iron ore green pellets are detected to have the falling strength of 8.6 times/(0.5 m) and the compressive strength of 21.3N/pellet.
Comparative example 3
The vanadium titano-magnetite is subjected to 3 times of pretreatment by a high pressure roller and then is pelletized, water accounting for 3.0 wt% of the iron ore powder is added into the iron ore powder to keep the water accounting for 8.0 wt% of the iron ore powder during pelletizing, then bentonite binder accounting for 1.5 wt% of the iron ore powder is added into the iron ore powder, the materials are fully and uniformly mixed, the materials are sieved to be below 1mm, and a disc pelletizer is adopted for pelletizing, wherein the pelletizing time is 10-12 min, and the pellet size is 10-12 mm. The obtained iron ore green pellets are detected to have the falling strength of 5.7 times/(0.5 m) and the compressive strength of 18.4N/pellet.
Comparing the green ball index data in example 2 with that in comparative example 3, when the vanadium titano-magnetite raw material was pretreated by high-pressure roll milling and 2 wt% of the binder prepared from low-rank brown coal was added (i.e., the amount of humic acid component added was 0.3%), the green ball drop strength and compressive strength reached 8.6 times/(0.5 m) and 21.3N/piece, respectively, and the drop strength was 5.7 times/(0.5 m) and 18.4N/piece at a level far higher than 1.5 wt% of the bentonite. The prepared binder has good bonding performance, and can obviously improve the balling performance of the iron ore resources difficult to be ballized; the dosage is less, and the production cost of the iron ore pellets is reduced.
Further comparing the main chemical components of the finished pellets of different binders in table 2, the iron grade of the finished oxidized pellets produced by the binder prepared by the invention is 54.65%, which is 1% higher than that of the finished oxidized pellets produced by bentonite binder. According to the blast furnace production practice, the iron grade in finished pellets fed into the furnace is improved by 1%, the blast furnace coke ratio is reduced by 2%, the ironmaking yield is improved by 3%, and the blast furnace slag amount is reduced by 20kg/t, so that the ironmaking production cost can be greatly reduced by adopting the binder prepared by the invention.
TABLE 2 Main chemical composition/wt% of finished oxidized pellets
Claims (8)
1. A method for preparing an oxidized pellet binder from low-rank coal is characterized by comprising the following steps: crushing low-rank coal, performing oxidation fermentation, adding solid caustic soda and water to adjust slurry, and heating and stirring to obtain an oxidized pellet binder; the addition amount of the solid caustic soda accounts for 20-30% of the mass of the low-rank coal; the addition amount of water is 2-5 times of the mass of the low-rank coal; the temperature of the oxidative fermentation is 80-200 ℃, the time is 2-10 hours, and after the oxidative fermentation is finished, the low-rank coal is further ground until the content of particles with the particle size of less than 0.1mm reaches more than 70%.
2. The method for manufacturing the oxidized pellet binder from the low-rank coal as claimed in claim 1, wherein the method comprises the following steps: the content of humic acid in the low-rank coal is not less than 25wt%, and the low-rank coal is crushed until the granularity is less than 10 mm.
3. The method for manufacturing the oxidized pellet binder from the low-rank coal as claimed in claim 2, wherein the method comprises the following steps: the content of humic acid in the low-rank coal is not less than 30 wt%.
4. The method for manufacturing the oxidized pellet binder from the low-rank coal as claimed in claim 1, wherein the method comprises the following steps: the heating and stirring temperature is 50-100 ℃, and the time is 1-5 h.
5. The oxidized pellet binder of any of claims 1-4 produced by the method of producing oxidized pellet binder from low rank coal.
6. The use of the oxidized pellet binder of claim 5, wherein: adding the iron ore powder into the mixture for pelletizing to obtain the iron ore green pellets for the oxidized pellets.
7. Use of an oxidized pellet binder as claimed in claim 6, characterized in that: the iron ore powder is firstly subjected to wet grinding or high-pressure roller grinding treatment and then is subjected to pelletizing.
8. Use of an oxidized pellet binder as claimed in claim 6, characterized in that: the addition amount of the oxidized pellet binder accounts for 1-4% of the mass of the iron ore powder, and the humic acid amount in the oxidized pellet binder accounts for 0.2-0.5% of the mass of the iron ore powder.
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| CN202010235639.3A CN111254278B (en) | 2020-03-30 | 2020-03-30 | Oxidized pellet binder prepared from low-rank coal and preparation method and application thereof |
| PCT/CN2021/083574 WO2021197258A1 (en) | 2020-03-30 | 2021-03-29 | Oxidized pellet binding agent made from low-rank coal, preparation method for same, and applications thereof |
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| CN111254278B (en) * | 2020-03-30 | 2021-08-27 | 中南大学 | Oxidized pellet binder prepared from low-rank coal and preparation method and application thereof |
| CN113388734B (en) * | 2021-02-26 | 2024-01-05 | 安徽工业大学 | Method for treating waste catalyst by strengthening pellet cohesiveness |
| CN113182079B (en) * | 2021-04-28 | 2022-11-29 | 郑州大学 | Method for producing mineralized metallurgical medicament by using low-rank coal for quality improvement, mineralized metallurgical medicament and application |
| CN114854984B (en) * | 2022-04-13 | 2023-08-29 | 昆明理工大学 | Preparation method and application method of composite binder for producing oxidized pellets |
| CN114774678B (en) * | 2022-05-31 | 2023-07-14 | 本钢板材股份有限公司 | Method for producing fluxed pellets from high-silicon mineral powder |
| CN115198088B (en) * | 2022-06-07 | 2023-11-14 | 首钢京唐钢铁联合有限责任公司 | Pellet produced by adding blast furnace environment dust and preparation method thereof |
| CN114959151B (en) * | 2022-06-16 | 2023-06-23 | 浙江工贸职业技术学院 | Vanadium-titanium ore and iron-containing dust coupling reduction process |
| CN115323169B (en) * | 2022-08-02 | 2023-11-14 | 首钢京唐钢铁联合有限责任公司 | Pellet ore and preparation method thereof |
| CN116287680A (en) * | 2023-04-23 | 2023-06-23 | 中天钢铁集团(南通)有限公司 | Specularite pellet production method |
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| US6342089B1 (en) * | 1997-09-02 | 2002-01-29 | Mcgaa John R. | Direct reduced iron pellets |
| CN100360691C (en) * | 2006-03-14 | 2008-01-09 | 淄博宜龙化工有限公司 | Pelletizing binder with starch and humus acid and production thereof |
| CN101570821B (en) * | 2009-06-15 | 2010-12-08 | 中南大学 | Sintering method of high proportion specularite concentrate |
| CN104178626B (en) * | 2014-08-28 | 2016-06-15 | 中南大学 | A kind of method improving iron ore concentrate green pellet strength |
| CN111254278B (en) * | 2020-03-30 | 2021-08-27 | 中南大学 | Oxidized pellet binder prepared from low-rank coal and preparation method and application thereof |
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| Effects of metal cations on the fulvic acid (FA) adsorption onto natural iron oxide in iron ore pelletizing process;Youlian Zhou et.al;《Powder Technology》;20160816;第302卷;第90-99页 * |
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Application publication date: 20200609 Assignee: Panzhihua Gangcheng Group Co.,Ltd. Assignor: CENTRAL SOUTH University Contract record no.: X2022980025911 Denomination of invention: A kind of oxidized pellet binder made of low rank coal and its preparation method and application Granted publication date: 20210827 License type: Exclusive License Record date: 20221212 |
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