CN113174455B - Comprehensive utilization method for smelting reduction of high-iron red mud by side-top combined blowing - Google Patents
Comprehensive utilization method for smelting reduction of high-iron red mud by side-top combined blowing Download PDFInfo
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- CN113174455B CN113174455B CN202110467970.2A CN202110467970A CN113174455B CN 113174455 B CN113174455 B CN 113174455B CN 202110467970 A CN202110467970 A CN 202110467970A CN 113174455 B CN113174455 B CN 113174455B
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B11/00—Making pig-iron other than in blast furnaces
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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Abstract
A comprehensive utilization method for smelting reduction of high-iron red mud by side-top combined blowing mainly comprises the following steps: mixing the high-iron red mud with a reducing agent, a slagging constituent and fluorite; adding the mixed raw materials into a smelting pool of a reduction furnace, carrying out reduction reaction, blowing mixed gas of reducing gas and oxygen at the side part in the reduction process, and blowing oxygen-enriched air and fuel gas at the top part; low-sulfur low-phosphorus pig iron and reducing slag are obtained through side-top combined blowing, melting and reducing, and the hot reducing slag is used for preparing rock wool products or cement clinker through direct water quenching after the procedures of tempering, centrifuging and wire drawing. By utilizing the side-top composite blowing melting reduction method, the high-iron red mud can be continuously reduced, the low-residue high-quality pig iron product can be directly obtained, the reduction rate of iron can reach more than 95 percent, and the yield of sodium oxide recovered in a flue gas form can reach more than 70 percent.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of Bayer process red mud, and particularly relates to a comprehensive utilization method of side-top composite blowing melting reduced high-iron red mud.
Background
With the rapid development of the steel industry and the aluminum industry in China, iron and aluminum ore resources are increasingly tense, and more than 50 percent of alumina and more than 40 percent of electrolytic aluminum in the world are produced by China with the bauxite reserves less than 3 percent of the world. The iron ore resource and bauxite in China depend on the outside by more than 60%. So that the production cost of the steel industry and the aluminum industry in China is greatly increased. Meanwhile, a large amount of low-quality iron and bauxite resources in China are not effectively and comprehensively utilized, the idle high-iron bauxite resources are more than 15 hundred million t, and in addition, the global red mud inventory is estimated to exceed 27 hundred million t and is increasing at a speed of 1.2 hundred million t. Therefore, the comprehensive utilization technology of the high-iron red mud has important strategic significance on the safe supply of iron and aluminum resources in China.
Although the existing comprehensive utilization method of the high-iron red mud can realize the utilization of iron/aluminum and other multi-components in the red mud, the problems that pig iron products cannot be directly obtained, or auxiliary means such as iron bath and the like are required in the pig iron reduction process, and the red mud cannot be massively consumed exist are more.
Disclosure of Invention
The invention provides a method for reducing high-iron red mud by side-top combined blowing fusion to obtain a low-residue high-quality pig iron product, aiming at the defects of the existing high-iron Bayer process red mud utilization technology.
The technical scheme of the invention comprises the following steps:
(1) High-iron red mud (red mud produced from gibbsite ore and diaspore ore) is used as a raw material and is mixed with a reducing agent, a slagging agent and fluorite. Wherein the reducing agent is one or a mixture of several of pulverized coal, coke or waste cathode carbon blocks mixed in any proportion, and the molar ratio of carbon in the reducing agent to ferric oxide in the high-iron red mud is (1.5-6) to 1; the slagging agent is a calcium source and is a mixture of one or more of limestone, hydrated lime or carbide slag mixed in any proportion, and the mass ratio of calcium oxide in the calcium source to the sum of silicon oxide and aluminum oxide in the high-iron red mud is (0.8-1.5): 1; the addition amount of fluorite is 8-15% of the amount of calcium oxide.
(2) And adding the mixed raw materials into a smelting pool of a reducing furnace for reduction reaction. The reduction reaction temperature is 1450-1700 ℃, and the reaction time is 20-140 min. The addition modes of the mixture comprise the following two modes: adding the mixture into a reduction furnace vortex area through a vortex feed inlet, and rolling the mixture into the interior of a molten pool under the action of the molten pool vortex; or oxygen-enriched air and reducing gas are used as carrier gas to blow the mixture into a reduction furnace molten pool by a side-blowing spray gun.
The main reactions of the reduction process are as follows:
3H 2 +Fe 2 O 3 ＝3H 2 O+2Fe
3C+Fe 2 O 3 ＝3CO+2Fe
3CO+Fe 2 O 3 ＝3CO 2 +2Fe
CH 4 +Fe 2 O 3 ＝CO 2 +2H 2 O+2Fe
sodium oxide in the high-iron red mud is volatilized at high temperature in the reduction process and enters reduction flue gas for enrichment and recovery.
Blowing mixed gas of reducing gas and oxygen at the side part in the reduction process, wherein the reducing gas is one or more of hydrogen, carbon monoxide or natural gas mixed in any proportion, and the mixing proportion of the reducing gas and the oxygen is CO and H in the mixed gas 2 Or (CO + H) 2 ) And O 2 The molar ratio of (0.2-1.8): 1, or CH in natural gas 4 And O 2 The molar ratio of (1-2) to (1). Oxygen-enriched air and fuel gas are blown at the top of the reduction process.
(3) Low-sulfur low-phosphorus pig iron and reducing slag (namely molten slag) are obtained through side-top combined blowing, melting and reducing, and the hot reducing slag is used for preparing rock wool products or cement clinker through direct water quenching after the working procedures of tempering, centrifuging and wire drawing. The low-sulfur and low-phosphorus concrete meets the requirements of the contents of sulfur less than 0.05 percent, phosphorus less than 0.05 percent, sulfur (less than or equal to 0.07 percent) and phosphorus (less than 0.1 percent) which are lower than L03 in high-quality steelmaking pig iron.
The invention has the characteristics and beneficial effects that:
(1) The method can realize the continuous reduction of the high-iron red mud, and directly obtain low-residue high-quality pig iron products; the reduction rate of iron in the high-iron red mud reaches over 95 percent by adopting the method, and the yield of the sodium oxide recovered in the form of flue gas reaches over 70 percent. CO generated by melting reduction is fully combusted, the temperature of a molten pool is raised and heated, the heat balance in the furnace is ensured, the full utilization of energy is realized, and the comprehensive energy consumption is reduced.
(2) By adopting vortex melting reduction, the reaction materials can be quickly sucked and added, the dispersion of the materials is strengthened, and the reduction efficiency is accelerated.
(3) The reduced slag can be used for preparing rock wool and other products or can be used as a cement raw material by water quenching after quenching and tempering, so that high-value utilization of multiple components in the high-iron red mud is realized.
Drawings
FIG. 1 is a side-top combined-blown bath reduction furnace used in the method of the present invention; wherein 1-raw material inlet, 2-vortex zone, 3,4,5,6, 7-top blowing spray gun, 8-tail gas discharge outlet, 9-slag outlet, 10-iron outlet, 11,12,13,14, 15-side blowing spray gun.
Detailed Description
The structure of the side-top combined-blown molten pool reduction furnace used in examples 1 to 3 of the present invention is shown in FIG. 1.
The high-iron red mud adopted by the embodiment of the invention comprises the following main components: fe 2 O 3 41.63％，Al 2 O 3 17.25％，SiO 2 10.20％，TiO 2 8.50％，Na 2 O6.50%, caO1.61% and others.
The reducing agent adopted for the pulverized coal comprises the following main components: 69.17% of fixed carbon, 11.13% of ash and 19.42% of volatile components.
The main components of the reducing agent coke are as follows: 84.5 percent of fixed carbon, 12.1 percent of ash and 2.3 percent of volatile matter.
The adopted reducing agent cathode carbon block mainly comprises the following components: 52.1% of fixed carbon, 37.2% of ash and 9.1% of volatile components.
The lime contains 80% of available CaO and the rest is SiO 2 And other materials.
CaF of fluorite 2 The content is 86 percent, and the rest is Al 2 O 3 、SiO 2 And other materials.
The production content of the invention is not limited to the adoption of the raw materials, for example, the reducing agent can also be replaced by coal powder, and the consumption of fluorite is reduced; the lime can also be replaced by calcium carbonate or calcium carbide smelting waste residue.
Example 1
A comprehensive utilization method for smelting reduction of high-iron red mud by side-top combined blowing comprises the following steps:
(1) Mixing the high-iron red mud with a reducing agent, limestone and fluorite, wherein the reducing agent is pulverized coal, and the molar ratio of carbon in the reducing agent to iron oxide in the high-iron red mud is 1.5; the ratio of the calcium oxide in the added limestone to the sum of the mass of the silicon oxide and the mass of the aluminum oxide in the high-iron red mud is 1.5; the amount of fluorite added is 8% of the amount of calcium oxide in the calcium source.
(2) And adding the mixture into a reduction furnace vortex area from a vortex feed inlet, and rolling the mixture into a molten pool under the action of the molten pool vortex to perform reduction reaction. The reduction reaction temperature is 1650 ℃, and the reduction reaction time is 20min. CO and O in the reduction process 2 The mixed gas of CO and O is introduced from the side part of the reduction furnace 2 The molar ratio is 0.2.
(3) Low-sulfur low-phosphorus pig iron and molten slag are obtained through side-top combined blowing melting reduction, and the hot reduced slag is used for preparing rock wool products after the working procedures of tempering, centrifuging and wire drawing. In this example, the reduction rate of iron in the high-iron red mud was 96.5%, and the yield of sodium oxide recovered as flue gas was 85%.
Example 2
A comprehensive utilization method for smelting reduction of high-iron red mud by side-top combined blowing comprises the following steps:
(1) Mixing the high-iron red mud with a reducing agent, limestone and fluorite, wherein the reducing agent is a waste cathode carbon block, and the molar ratio of carbon in the reducing agent to iron oxide in the high-iron red mud is 6.5; the ratio of the calcium oxide in the added limestone to the sum of the mass of the silicon oxide and the mass of the aluminum oxide in the high-iron red mud is 0.8; the amount of fluorite added is 15% of the amount of calcium oxide.
(2) And adding the mixture into a vortex area of the reduction furnace from a vortex feed inlet, and rolling the mixture into the molten pool under the action of the vortex of the molten pool to perform reduction reaction. The reduction reaction temperature is 1450 ℃, and the reduction reaction time is 140min. CO and O in the reduction process 2 The mixed gas of CO and O is introduced from the side part of the reduction furnace 2 The molar ratio is 1.8.
(3) Low-sulfur low-phosphorus pig iron and molten slag are obtained through side-top combined blowing, melting and reducing, and the hot reduced slag is used for preparing rock wool products after the working procedures of tempering, centrifuging and wire drawing. In this example, the reduction rate of iron in the high-iron red mud was 95.0%, and the yield of sodium oxide recovered as flue gas was 71%.
Example 3
A comprehensive utilization method for smelting reduction of high-iron red mud by side-top combined blowing comprises the following steps:
(1) Mixing the high-iron red mud with a reducing agent, limestone and fluorite, wherein the reducing agent is a waste cathode carbon block, and the molar ratio of carbon in the reducing agent to iron oxide in the high-iron red mud is 4; the ratio of the calcium oxide in the added limestone to the sum of the mass of the silicon oxide and the mass of the aluminum oxide in the high-iron red mud is 1; the amount of fluorite added is 10% of the amount of calcium oxide.
(2) And adding the mixture into a reduction furnace vortex area from a vortex feed inlet, and rolling the mixture into a molten pool under the action of the molten pool vortex to perform reduction reaction. The reduction reaction temperature is 1500 ℃, and the reduction reaction time is 60min. CO and O in the reduction process 2 The mixed gas is introduced from the side part of the reduction furnace, and CO and O are introduced 2 The molar ratio is 1.
(3) Low-sulfur low-phosphorus pig iron and molten slag are obtained through side-top combined blowing, melting and reducing, and the hot reduced slag is used for preparing rock wool products after the working procedures of tempering, centrifuging and wire drawing. In this example, the reduction rate of iron in the high-iron red mud was 95.8%, and the yield of sodium oxide recovered as flue gas was 78%.
Claims (2)
1. A comprehensive utilization method for smelting reduction of high-iron red mud by side-top combined blowing is characterized by comprising the following steps:
(1) Mixing the high-iron red mud with a reducing agent, a slagging constituent and fluorite; the reducing agent is one or a mixture of several of pulverized coal, coke or waste cathode carbon blocks mixed in any proportion; the slagging agent is a calcium source and is one or a mixture of more of limestone, hydrated lime or carbide slag in any proportion; the molar ratio of carbon in the reducing agent to iron oxide in the high-iron red mud is (1.5-6) to 1; the ratio of the mass sum of the calcium oxide in the slagging constituent and the mass sum of the silicon oxide and the aluminum oxide in the high-iron red mud is (0.8-1.5): 1; the addition amount of fluorite is 8-15% of the amount of calcium oxide;
(2) Adding the mixed raw materials into a smelting pool of a reducing furnace for reduction reaction; the reduction reaction temperature is 1450 to 1700 ℃, and the reaction time is 20 to 140min; the reduction furnace adopts a side-top composite blowing molten pool reduction furnace; the top of the reduction furnace is provided with 5 top-blowing spray guns, one side of the reduction furnace is provided with 5 side-blowing spray guns, and the tail of the reduction furnace is provided with a slag outlet and an iron outlet;
in the reduction process, the side part is sprayed with mixed gas of reducing gas and oxygen, and the top part is sprayed with oxygen-enriched air and fuel gas; wherein the reducing gas is one or more of hydrogen, carbon monoxide or natural gas mixed gas in any proportion, and the mixing proportion of the reducing gas and the oxygen is CO and H in the reducing gas 2 Or (CO + H) 2 ) And O 2 The molar ratio is (0.2 to 1.8): 1, or CH in natural gas 4 And O 2 The molar ratio of (1 to 2) to (1);
(3) The low-sulfur low-phosphorus pig iron and the reducing slag are obtained through side-top combined blowing melting reduction, the thermal reducing slag is used for preparing rock wool products or directly water-quenching cement clinker after the processes of tempering, centrifuging and wire drawing, the reduction rate of iron in the high-iron red mud reaches over 95 percent, and the yield of sodium oxide recovered in a flue gas mode reaches over 70 percent.
2. The comprehensive utilization method of the red mud produced by the lateral-top combined blowing-melting reduction of the high-iron material according to claim 1, wherein in the step (2), the mixture is added in the following two ways: adding the mixture into a reduction furnace vortex area through a vortex feed inlet, and rolling the mixture into the interior of a molten pool under the action of the molten pool vortex; or oxygen-enriched air and reducing gas are used as carrier gas to blow the mixture into a reduction furnace molten pool by a side-blowing spray gun.
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| CN202110467970.2A CN113174455B (en) | 2021-04-28 | 2021-04-28 | Comprehensive utilization method for smelting reduction of high-iron red mud by side-top combined blowing |
| PCT/CN2021/096803 WO2022227185A1 (en) | 2021-04-28 | 2021-05-28 | Comprehensive utilization method for side-top composite injection smelting reduction of high-iron red mud |
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| US3525604A (en) * | 1966-10-21 | 1970-08-25 | Edward M Van Dornick | Process for refining pelletized metalliferous materials |
| CN101705360B (en) * | 2009-11-26 | 2011-07-20 | 阳谷祥光铜业有限公司 | Copper-smelting thermal slag iron-extracting process and device |
| IT1402152B1 (en) * | 2010-10-08 | 2013-08-28 | Ecotec Gestione Impianti S R L | PROCEDURE AND REACTOR FOR THE TRANSFORMATION INTO THE PLASMA STATE OF PULVERULATED BY-PRODUCTS, FROM THE PROCESSING OF THE BAUXITE, IN AN INERT AND COMPACT RESIDUE, CONTAINING PRODUCTS OF INDUSTRIAL INTEREST. |
| CN102816880B (en) * | 2012-08-17 | 2014-04-02 | 东北大学 | Ironmaking and aluminum extraction comprehensive utilization method of high-iron red mud |
| CN108676942A (en) * | 2018-05-18 | 2018-10-19 | 廖辉明 | The materials such as a kind of iron content and/or zinc lead bronze tin cooperate with processing recovery method with molten steel slag |
| CN109970368A (en) * | 2019-04-11 | 2019-07-05 | 东北大学 | A kind of method that the melting and reducing dealkalize of iron red mud vortex mentions the direct cement of iron |
| CN110055365A (en) * | 2019-04-11 | 2019-07-26 | 东北大学 | A kind of method that calcification-carbonization iron red mud recycles iron and tailings cement |
| CN109913655A (en) * | 2019-04-11 | 2019-06-21 | 东北大学 | A kind of method that red mud recycles sodium, iron and titanium while the direct cement of liquid slag |
| CN110066923A (en) * | 2019-04-11 | 2019-07-30 | 东北大学 | Red mud synthetical recovery low-melting-point metal, iron, vanadium and the method for melting slag cement |
| CN110172539A (en) * | 2019-06-19 | 2019-08-27 | 上海科麟沃环境科技有限公司 | Iron content red mud recovery method, rock wool preparation method and corresponding rock wool |
| CN111394534B (en) * | 2020-02-21 | 2021-05-18 | 东北大学 | Method for continuous smelting reduction iron making |
| CN111485043A (en) * | 2020-06-01 | 2020-08-04 | 上海驰春节能科技有限公司 | Dephosphorization process and device for liquid steel slag |
| CN112442565A (en) * | 2020-11-24 | 2021-03-05 | 东北大学 | High-iron red mud reduction iron extraction process |
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