CN110343878B - Energy-saving and environment-friendly production method of nickel-iron alloy - Google Patents
Energy-saving and environment-friendly production method of nickel-iron alloy Download PDFInfo
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22C1/023—Alloys based on nickel
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Abstract
An energy-saving and environment-friendly production method of a nickel-iron alloy belongs to the field of pyrometallurgy and is characterized in that: the method comprises the steps of uniformly mixing a mixture of stainless steel sludge, stainless steel acid slag, stainless steel oxide skin, stainless steel grinding wheel ash and returned dust with pulverized coal according to a certain proportion, then granulating, drying and sintering in a rotary kiln, conveying a sintering material by a closed shaftless screw conveyor, smelting by a fully-closed ore-smelting electric furnace to obtain a nickel-iron alloy and molten slag, wherein the nickel-iron alloy is used as a raw material for producing the stainless steel, the molten slag is quenched by water to be used as a building material raw material, and smelting smoke is subjected to cyclone dust collection, cloth bag dust collection, alkali liquor washing and demisting by an electric demister and then is discharged through. The fuel required by the rotary kiln drying and sintering is hot coal gas generated by smelting in an ore-smelting electric furnace, and the rotary kiln sintering material enters the totally-enclosed ore-smelting electric furnace to be smelted in a hot state. The smelting method has the advantages of full energy utilization, standard emission of flue gas, less fixed investment, small occupied area, low production and operation cost and obvious social, economic and environmental benefits.
Description
Technical Field
The invention belongs to the field of pyrometallurgy, and particularly relates to an energy-saving and environment-friendly method for producing a nickel-iron alloy.
Background
With the development of social economy, the living standard of people is improved, the consumption of stainless steel is greatly increased, and the production and processing industries of the stainless steel are rapidly developed. In 2018, the yield of stainless steel crude steel in China reaches 2670.68 ten thousand tons, wherein 1282.07 thousand tons of 300 series (Cr-Ni steel) are used. In the stainless steel processing industry, the produced stainless steel sludge and stainless steel acid sludge are about 3% -5% of the stainless steel yield, the sludge contains valuable metal elements such as Ni, Cr, Fe and the like, the content of Ni and Cr is about 2 times of that of laterite-nickel ore, and CaF is contained2、CaO、SiO2、CaSO4And the like, belonging to dangerous waste. In addition, stainless steel oxide skin and stainless steel grinding wheel ash which account for about 1% of the stainless steel processing output are generated, and the method belongs to general solid wastes.
With the increasing exhaustion of resources and the continuous improvement of environmental protection requirements, the rational utilization of the stainless steel sludge, the stainless steel acid sludge, the stainless steel oxide skin and the stainless steel grinding wheel ash is related to the healthy development of stainless steel enterprises in China. The stainless steel sludge is utilized by a pyrogenic process and a wet process. The wet process has complex flow and more devices, generates a large amount of waste water and waste residues, is very easy to generate secondary pollution, and can not finally solve the problem of harm of the waste residues to the environment. The pyrogenic process is suitable for large-scale continuous production to obtain a nickel-iron alloy product, the produced water quenching slag can be used as a building material raw material, waste gas containing sulfur dioxide, hydrogen chloride and hydrogen fluoride can be discharged after being absorbed and purified by alkali liquor, and the waste water can be recycled without waste water discharge. At present, the fire method technology is gradually applied to the stainless steel sludge treatment process. The fire method technology currently and generally adopts the following steps: stainless steel sludge (or mixed with laterite-nickel ore according to a certain proportion) is dried in a rotary kiln, then added with a carbonaceous reducing agent and limestone and roasted in a rotary kiln, and finally smelted in an ore-smelting electric furnace to obtain the ferronickel alloy. The process has high nickel and iron recovery rate, but has long process flow and large fixed investment. In the aspect of energy saving and consumption reduction, the water content of the stainless steel sludge is as high as about 60 percent, and a large amount of fuel is consumed for removing the water. In the prior art, coal gas generated by smelting of the ore-smelting electric furnace is not effectively utilized, cold-state feeding is adopted in the ore-smelting electric furnace, and the problem of hot-state feeding is still not well solved, so that the energy consumption is high.
Disclosure of Invention
The invention aims to solve the main technical problems that: by optimizing the process flow and the equipment configuration, high-temperature coal gas generated by smelting in the ore-smelting electric furnace is directly used as fuel required by drying and sintering in a rotary kiln, and the sintering material enters the ore-smelting electric furnace in a hot state for reduction smelting, so that the production flow is short, the fixed investment and the energy consumption are reduced, the energy conservation and the environmental protection of the production of the nickel-iron alloy are realized, and the cost is reduced.
The invention is realized by the following modes:
1. mixing and granulating: the method comprises the following steps of preliminarily mixing a mixture of stainless steel sludge, stainless steel acid sludge, stainless steel oxide skin and stainless steel grinding wheel ash and returned dust with coal powder according to the ratio of 1: 0.10-0.25, conveying the mixture to an upper storage bin by a grab bucket traveling crane, conveying the mixture to a double-shaft mixer by a belt for stirring and mixing, feeding the mixture into a roller granulator, and controlling the roller granulator to spray granulating water for uniform granulation.
2. Drying and sintering in a rotary kiln: the aggregate is conveyed to a discharge bin at the tail of a rotary kiln by a belt, enters the rotary kiln from the discharge bin, moves towards the kiln head by the horizontal inclination angle and the rotation of the rotary kiln, is in reverse contact with high-temperature flue gas, the temperature of the aggregate is continuously raised, free water and crystal water in the aggregate are removed, hydroxide is decomposed to generate oxide, partial oxide is reduced, the sintered aggregate enters the kiln head bin after coming out of the kiln head, a speed-adjustable closed shaftless spiral conveyor is arranged at the lower part of the kiln head bin, and the sintered aggregate is conveyed to a discharge port of a fully-closed ore-smelting electric furnace in a hot state. The fuel used for drying and sintering the rotary kiln is hot coal gas generated by a totally enclosed ore-smelting electric furnace, and excess air is supplemented to ensure that the temperature of the flue gas after the hot coal gas is combusted in the kiln head is 600-1000 ℃ and the temperature of the flue gas at the kiln tail is 180-130 ℃.
3. Supplement of carbonaceous reducing agent and limestone flux: under the general condition, the calcium content in the stainless steel sludge can meet the requirement of being used as a flux, and under the special condition that the calcium flux is insufficient, lime is added during the batching or limestone is added from a discharge bin at the tail of a rotary kiln; the coke replenishing process includes setting coke bin over the screw conveyer, feeding material to the screw conveyer via the star feeding valve in the lower part of the coke bin, and increasing the screw pitch or the width of the screw sheet to increase the conveying amount of the screw conveyer.
4. Smelting in an ore-smelting electric furnace: the method adopts a totally enclosed ore-smelting electric furnace for smelting, a feed inlet is arranged in the middle of a furnace top cover, three gas outlets are arranged on the furnace top cover, the other ends of the gas pipes are converged together and then extend into a kiln head, and the gas outlets of the ore-smelting electric furnace are positioned on the other side of a self-baking electrode relative to the position of the feed inlet, so that the dust content of gas can be reduced. The temperature of the sintering material is about 650 ℃, because the sintering material is fed in a thermal state, the gas temperature of the totally enclosed ore-smelting electric furnace reaches above 800 ℃, therefore, the sintering material is reduced by the gas without power consumption for preheating after entering the furnace, thereby improving the yield of the electric furnace and saving electricity by about 25% per ton of products. Because the temperature of the coal gas is higher than the ignition point of the coal gas, the coal gas can be combusted when meeting air, and therefore, the coal gas is relatively safe. Because the gas temperature is high, the outer wall of the gas pipe is provided with an air jacket, normal temperature air is blown in by a fan, the air is preheated while the gas pipe is cooled and protected, and the preheated air is used as combustion-supporting gas for gas combustion.
In an ore-smelting electric furnace, arc discharge heating is utilized to generate high temperature of 1500-1600 ℃, at the temperature, metal oxides of nickel, chromium and iron are reduced by carbon to generate alloy and sink, while silicon, magnesium and calcium do not reach the temperature at which reduction reaction occurs, only slag is generated, the slag floats upwards due to smaller density than the alloy, the alloy and the slag are separated, and slag and the alloy are discharged intermittently. After the nickel-iron alloy is discharged, the cast ingot is formed into blocks to be sold as products. The slag is water quenched to be used as building material.
5. Flue gas treatment: in an ore-smelting electric furnace, under the condition that the temperature is higher than 1000 ℃ and carbon is excessive, carbon is reduced to metal to generate carbon monoxide gas, the carbon monoxide gas is led out through a gas pipe and enters a kiln head of a rotary kiln, the carbon dioxide gas is combusted in the kiln head when meeting combustion air and generates heat, high-temperature flue gas is used for drying, sintering and granulating the mixture, meanwhile, the temperature of the flue gas is reduced to 180-130 ℃, the flue gas is sent to a purification tower by an induced draft fan for alkali liquor washing after being collected by a cyclone dust collector and a cloth bag dust collector, the mixture is discharged through a chimney after being treated by an electric demister to reach the standard, and the collected smoke dust is returned to be.
The invention has the beneficial effects that:
the method has the advantages of short production process flow, low fixed investment, full utilization of sensible heat and latent heat of the flue gas, low energy consumption, high metal recovery rate, thorough environment-friendly treatment of the flue gas, low smelting production cost and remarkable social, economic and environment-friendly benefits. The invention is not limited to the production of 300 series (Cr-Ni steel) stainless steel, the production of ferronickel alloy products by waste materials and sludge generated in the processing industry, and is also suitable for the production of other products by reduction smelting in an ore-smelting electric furnace. The technical indexes of the traditional smelting method and the invention are compared (see table 1).
TABLE 1 comparison of the technical indices of the conventional smelting process and the present invention
| Item | Rotary kiln drying-rotary kiln roasting-ore smelting method by electric furnace | The invention |
| Fixed investment | 100％ | 87％ |
| Floor area | 100％ | 80％ |
| Coal consumption | 100％ | 75％ |
| Electricity consumption | 100％ | 81％ |
| Labor productivity | 100％ | 120％ |
| Production cost | 100％ | 85％ |
Drawings
FIG. 1 is a process flow chart of the energy-saving and environment-friendly ferronickel alloy production method
FIG. 2 is a connection diagram of the production method and equipment of the ferronickel alloy with energy saving and environmental protection
Labeled as: 1-double-shaft stirrer, 2-roller granulator, 3-rotary kiln, 4-sealed shaftless screw conveyor, 5-coke bin, 6-totally enclosed ore-smelting electric furnace, 7-ingot casting machine, 8-water quenching slag pool, 9-cyclone dust collector, 10-cloth bag dust collector, 11-induced draft fan, 12-purification tower, 13-electric demister and 14-chimney.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention.
The dry-based components of the mixture of stainless steel sludge, stainless steel acid sludge, stainless steel oxide skin and stainless steel grinding wheel ash (see table 2).
TABLE 2 Dry composition of mixture of stainless sludge, acid sludge, scale and mortar (%)
| Item | Nickel (II) | Iron | Chromium (III) | Calcium carbonate | Sulfur | Fluorine | Moisture content |
| Industrial analysis | 3.9 | 18.7 | 2.1 | 17.6 | 1.3 | 1.5 | 51 |
Pulverized coal composition (see table 3).
TABLE 3 pulverized coal composition (%)
Example 1
As shown in fig. 1 and 2, the invention relates to an energy-saving and environment-friendly method for producing a nickel-iron alloy, which comprises the following steps:
1. mixing and granulating: the method comprises the following steps of preliminarily mixing and homogenizing a mixture of stainless steel sludge, stainless steel acid sludge, stainless steel oxide skin and stainless steel grinding wheel ash and return dust and pulverized coal in a ratio of 1: 0.16, conveying the mixture to an upper storage bin by a grab bucket crane, conveying the mixture to a double-shaft stirrer 1 by a belt to stir and mix the mixture, feeding the mixture into a roller granulator 2, and controlling the roller granulator 2 to spray granulating water to uniformly granulate.
2. Drying and sintering in a rotary kiln: the aggregate is conveyed to a kiln tail discharging bin of a rotary kiln 3 by a belt, enters the rotary kiln 3 from the discharging bin, moves towards the kiln head by the horizontal inclination angle and the rotation of the rotary kiln 3, is in reverse contact with high-temperature flue gas, the temperature of the aggregate is continuously raised, free water and crystal water in the aggregate are removed, hydroxide is decomposed to generate oxide, partial oxide is reduced, sintered materials come out from the kiln head and enter the kiln head discharging bin, a speed-adjustable closed shaftless spiral conveyor 4 is arranged at the lower part of the kiln head discharging bin, and the sintered materials are conveyed to a discharging port of a fully-closed ore-smelting electric furnace 6 in a hot state. The fuel used by the rotary kiln 3 is hot coal gas generated by a totally enclosed ore-smelting electric furnace 6, and excess air is supplemented to ensure that the temperature of flue gas after the hot coal gas is combusted in a kiln head is controlled to be 700-800 ℃ and the temperature of the flue gas at a kiln tail is 180-130 ℃.
3. Smelting in an ore-smelting electric furnace: the sintering material is fed into the furnace at the temperature of about 650 ℃, and is heated by arc discharge in a totally enclosed ore-smelting electric furnace 6 to generate the high temperature of 1500-1600 ℃, at the temperature, metal oxides of nickel, chromium and iron are reduced by carbon to generate alloy and sink, while silicon, magnesium and calcium do not reach the temperature for generating reduction reaction, only slag is generated, and the slag floats up because the density is smaller than that of the alloy, so that the nickel, the chromium and the iron are separated, and the slag is discharged intermittently. The ferronickel alloy is discharged and cast into blocks by an ingot casting machine 7 to be sold as products, the slag is made into building material raw materials after water quenching treatment, and the recovery rates of nickel, chromium and iron are respectively 94.5%, 91.3% and 80.6%.
4. Flue gas treatment: the flue gas from the tail of the rotary kiln is sent to a purification tower 12 by an induced draft fan 11 after being collected by a cyclone dust collector 9 and a bag dust collector 10, is treated by an electric demister 13 to reach the standard and is discharged by a chimney 14, and the collected flue gas returns to the batching.
Example 2
1. Mixing and granulating: the method comprises the following steps of preliminarily mixing and homogenizing the mixture of stainless steel sludge, stainless steel acid sludge, stainless steel oxide skin and stainless steel grinding wheel ash and the returned dust and coal powder according to the ratio of 1: 0.11, conveying the mixture to an upper storage bin by a grab bucket crane, conveying the mixture to a double-shaft mixer 1 by a belt for mixing, feeding the mixture into a roller granulator 2, and controlling the roller granulator 2 to spray granulating water for uniform granulation.
2. Drying and sintering in a rotary kiln: the aggregate is conveyed to a kiln tail discharging bin of a rotary kiln 3 by a belt, enters the rotary kiln 3 from the discharging bin, moves towards the kiln head by the horizontal inclination angle and the rotation of the rotary kiln 3, is in reverse contact with high-temperature flue gas, the temperature of the aggregate is continuously raised, free water and crystal water in the aggregate are removed, hydroxide is decomposed to generate oxide, partial oxide is reduced, sintered materials come out from the kiln head and enter the kiln head bin, a speed-adjustable closed shaftless spiral conveyor 4 is arranged at the lower part of the kiln head bin, and the sintered materials are conveyed to a discharging port of a fully-closed ore-smelting electric furnace 6 in a hot state. The fuel used by the rotary kiln 3 is hot coal gas generated by a totally enclosed ore-smelting electric furnace 6, and excess air is supplemented to ensure that the temperature of flue gas after the hot coal gas is combusted in a kiln head is controlled to be 700-800 ℃ and the temperature of the flue gas at a kiln tail is 180-130 ℃.
3. Supplement of carbonaceous reducing agent: coke is put into a coke bin 5 and fed onto the closed shaftless screw conveyor 4 through a star-shaped feeding valve at the lower part of the bin, and the feeding amount of the coke is 5 percent of that of sintered materials.
4. Smelting in an ore-smelting electric furnace: the sintering material is fed into the furnace at the temperature of about 650 ℃, and is heated by arc discharge in a totally enclosed ore-smelting electric furnace 6 to generate the high temperature of 1500-1600 ℃, at the temperature, metal oxides of nickel, chromium and iron are reduced by carbon to generate alloy and sink, while silicon, magnesium and calcium do not reach the temperature for generating reduction reaction, only slag is generated, and the slag floats up because the density is smaller than that of the alloy, so that the nickel, the chromium and the iron are separated, and the slag is discharged intermittently. The ferronickel alloy is discharged and cast into blocks by an ingot casting machine 7 to be sold as products, the slag is made into building material raw materials after water quenching treatment, and the recovery rates of nickel, chromium and iron are respectively 95.0%, 91.7% and 81.9%.
5. Flue gas treatment: the flue gas from the tail of the rotary kiln is sent to a purification tower 12 by an induced draft fan 11 after being collected by a cyclone dust collector 9 and a bag dust collector 10, is treated by an electric demister 13 to reach the standard and is discharged by a chimney 14, and the collected flue gas returns to the batching.
Claims (4)
1. An energy-saving and environment-friendly production method of a nickel-iron alloy belongs to the field of pyrometallurgy and is characterized in that: uniformly mixing a mixture of stainless steel sludge, stainless steel acid slag, stainless steel oxide skin, stainless steel grinding wheel ash and returned dust with pulverized coal according to a certain proportion, then granulating, drying and sintering in a rotary kiln, smelting in an ore-smelting electric furnace to obtain ferronickel alloy and molten slag, and discharging smelted flue gas through a chimney after cyclone dust collection, cloth bag dust collection, alkali liquor washing and demisting by an electric demister; the rotary kiln is characterized in that a storage bin is arranged at the outlet end of the rotary kiln, a closed shaftless spiral conveyor is arranged at the lower part of the storage bin, a coke storage bin is arranged above the closed shaftless spiral conveyor, the closed shaftless spiral conveyor is fed through a star-shaped feeding valve at the lower part of the storage bin, the conveying capacity at the rear end of the closed shaftless spiral conveyor is increased by increasing the screw pitch or the width of a spiral sheet, an air jacket is arranged on the outer wall of the closed shaftless spiral conveyor, normal-temperature air is blown in through a fan, and the air is preheated and then used as combustion-; the ore-smelting electric furnace is a totally enclosed ore-smelting electric furnace, a charging hole is arranged in the middle of a furnace top cover, hot feeding is adopted, three coal gas outlets are arranged on the furnace top cover, the other ends of the coal gas pipes are converged together and then extend into a kiln head, the coal gas outlets of the ore-smelting electric furnace are arranged on the other side of the self-baking electrode relative to the position of the charging hole, an air jacket is arranged on the outer wall of each coal gas pipe, normal temperature air is blown in by a fan, and the air is preheated and then used as combustion-supporting gas for coal gas combustion.
2. The energy-saving and environment-friendly ferronickel alloy production method according to claim 1, characterized in that: the mixture of the stainless steel sludge, the stainless steel acid sludge, the stainless steel oxide skin, the stainless steel grinding wheel ash and the return dust and the pulverized coal are mixed according to a certain proportion as follows: 1: 0.10-0.25.
3. The energy-saving and environment-friendly ferronickel alloy production method according to claim 1, characterized in that: the granulation is one of roller granulator granulation, disc granulator granulation and briquetting machine granulation.
4. The energy-saving and environment-friendly ferronickel alloy production method according to claim 1, characterized in that: the fuel used for drying and sintering the rotary kiln is hot coal gas generated by an ore-smelting electric furnace, and excess air is supplemented to ensure that the temperature of the hot coal gas is 600-1000 ℃ after the hot coal gas is combusted in the kiln head and the temperature of the kiln tail flue gas is 180-130 ℃.
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| JP5975093B2 (en) * | 2014-12-24 | 2016-08-23 | 住友金属鉱山株式会社 | Nickel oxide ore smelting method |
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