CN104498731A - Oxygen-enriched side-blown low-temperature alkaline sulfur-fixing smelting method and oxygen-enriched side-blown low-temperature alkaline sulfur-fixing smelting equipment - Google Patents
Oxygen-enriched side-blown low-temperature alkaline sulfur-fixing smelting method and oxygen-enriched side-blown low-temperature alkaline sulfur-fixing smelting equipment Download PDFInfo
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Abstract
The invention relates to an oxygen-enriched side-blown low-temperature alkaline sulfur-fixing smelting method and oxygen-enriched side-blown low-temperature alkaline sulfur-fixing smelting equipment, belonging to the technical field of non-ferrous metallurgy. The method comprises the following steps: mixing and pelletizing a lead-containing material, sodium carbonate and coal granules; uniformly feeding the components to a side-blown converter by virtue of conveying equipment; introducing oxygen-enriched air for low-temperature alkaline smelting to produce three products, namely wet lead or noble lead, smelting slag and smoke; introducing noble metals such as gold, silver and the like into the wet lead which is discharged from a siphon mouth; discharging the smelting slag from a slag tap; after water logging of the smelting slag, crystallizing the filtrate in steps to obtain sodium carbonate and sodium sulphide products; after dedusting the smoke, returning soot to raw materials; and after exhaust gas is absorbed by an alkaline liquid, directly discharging the exhaust gas. According to the technical scheme, the method and the equipment have the advantages of low energy consumption, low cost, environmental friendliness and the like and have remarkable economical and social benefits..
Description
Technical field
The present invention relates to the method and apparatus of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali; Belong to technical field of non-ferrous metallurgy.
Technical background
China is the country that lead resource is abundant in the world, occupies second place of the world, and not only distribution is wide, and type is many, and Resources Prospect is good.But, along with large-scale development in recent years, in China's lead resource, high-grade ore reduces year by year, compare with international lead resource, large ore deposit is few, middle-low grade resource accounts for more than 50%, what developed finds out that resource reserve accounts for nearly 55%, and can find out that the proportion of resource reserve is lower for design and planning utilization, the reserves do not utilized concentrate on construction condition and the bad mining area of resources supplIes mostly.From 2000, China became importer from Qian Xin raw material net exporter.
Domestic lead consumes mainly lead storage battery, and in national plumbous consumption structure, lead acid cell consumption is plumbous accounts for 78% of overall consumption.Therefore, from waste lead storage battery, the plumbous main path becoming secondary lead and reclaim is reclaimed.Secondary lead accounts for 40% of International Lead ultimate production, but the secondary lead of 90% is from scrap battery.
The melting technologies such as reverberatory furnace, blast furnace and cupola furnace that in current most of secondary lead enterprises of China technique, main employing is traditional, grid is mixing together with plumbous mud, substantially without pretreatment technology; Some small businesss, self-employed worker even adopt original earth kiln soil stove to smelt; Also exist that number of the enterprise is many, small scale, power consumption is high, seriously polluted, industrial technology falls behind, metal recovery rate and the problem such as to make a low multiple use.Mainly: lead recovery is low, domestic most factory rate of recovery is generally 80% ~ 85% (external common level 95%); Severe environmental pollution, due to backward in technique, the lead steam discharged in fusion process, lead dust, sulfurous gas severe overweight, tens times that are up to state standards.
Patent CN 102965510 A (the solid sulfur melting bath melting method of reduction of the leaded secondary material of low-sulfur and Fu Tie solid waste of heavy metal and equipment) carries out oxygen enriched molten bath melting, sulphur is with the form output of iron sulfonium, elimination low-concentration sulfur dioxide pollutes, achieve the melting continuously of the leaded secondary material of low-sulfur, there is eco-friendly advantage.But fusion process is pyroreaction, energy consumption is comparatively large, and in flue gas, Dust Capacity is large, and iron sulfonium productive rate is large, reclaims relieving haperacidity again after iron sulfonium, cost of investment and production cost larger.
Due to above various reasons, above oxygen enriched molten bath smelting technique does not all obtain industrial utilization, and existing secondary lead resource still adopts original blast furnace high melt technology, therefore needs a kind of practical technology of exploitation badly.
Current technology utilizes side-blown converter to carry out the solid sulphur melting of oxygen-enriched side-blowing, and the material of process mainly divides two classes, and a class is the primary ore after roasting, and a class is secondary lead material; During process regeneration feed, general employing carries out solid sulphur with irony, generates iron sulfonium, carries out roasting relieving haperacidity after the fragmentation of iron sulfonium.But no matter adopt any material, its smelting temperature is generally at about 1200 DEG C, and therefore energy consumption is high.When adopting the primary ore after roasting as raw material, need provide supporting acid making system, but acid making system investment is large, Product recycling profit is low; Cause it cannot realize the production of large-scale less energy-consumption, high benefit.Adopt secondary lead material, take irony as sulphur-fixing agent when smelting, because smelting temperature original text, sulphur exist with the sulphate form of low value, also cause it cannot realize the production of large-scale less energy-consumption, high benefit.
Summary of the invention
The high pollution existed for existing secondary lead resource blast furnace volatile smelting technology, high energy consumption and existing oxygen enriched molten bath smelting technique cannot the deficiencies of industrialization conscientiously, and the present invention aims to provide the method and apparatus that a kind of oxygen-enriched side-blowing low-temperature alkali consolidates sulphur melting.
The method of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, comprises the steps:
Step one
Add water after lead-containing material, reductive agent, sodium carbonate being mixed granulation, obtains smelting particle for subsequent use; The mass ratio of described sodium carbonate and lead-containing material is 0.4-5:1; The consumption of reductive agent be by the plumbous Restore All in lead-containing material be the theoretical amount of simple substance lead 1.5-3 doubly;
Step 2
Step one gained is smelted particle for subsequent use, to add continuously in oxygen-enriched side-blowing smelting furnace and to pass into oxygen rich gas, at 800 ~ 1000 DEG C, carrying out retailoring, obtain lead bullion or precious metals containing lead, smelting slag, flue gas.
The method of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, described lead-containing material is selected from the mixture of secondary lead raw material or secondary lead raw material and lead ore powder, and described secondary lead raw material is selected from least one in scrap battery clay and screen, sulfuric acid lead skim, plumbous oxide cigarette ash, matte slag.
The method of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, described lead ore powder is selected from least one in lead sulfide breeze, lead chloride ground-slag, lead fume dirt.
The method of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, the granularity≤5mm of described lead-containing material.
The method of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, described reductive agent is solid reductant, and described solid reductant is selected from least one in coke, gac, reduction coal; Granularity≤the 10mm of described solid reductant.
The method of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, in described lead-containing material, plumbous mass percentage is 30-90%.
The method of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, O in described oxygen rich gas
2volumetric concentration is 30% ~ 90%, and it is 0.1MPa ~ 1.6MPa that oxygen rich gas sends into pressure, O in oxygen rich gas
2flow with the pass smelting particulate charge amount for subsequent use is: (180Nm
3~ 420Nm
3)/(t smelts particle for subsequent use).
The method of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, described oxygen rich gas is made up of oxygen and nitrogen.
The method of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, the granularity of smelting particle for subsequent use is 3mm ~ 25mm; The mass percentage smelting water in particle for subsequent use is 7% ~ 15%.
The method of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, the sulphur contained in secondary lead raw material and/or lead ore powder enters in smelting slag with the form of sodium sulphite, and smelting slag recycles sodium carbonate in smelting slag and sodium sulphite through water logging; Described water logging is: be added to the water by smelting slag by liquid-solid mass ratio 3-6:1, until filter after the complete loose pulverizing of slag, filtrate, through fractional crystallization, obtains sodium carbonate and sodium sulphite product respectively; During water logging, control temperature is 20-90 DEG C.
The equipment of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, comprise be positioned at side-blown bottom of furnace body laying fireproof bricks cupola well (9), be positioned at the copper water jacket (10) in the middle part of body of heater and be positioned at the molten steel cover (11) of upper of furnace body, main charging opening (3a), auxiliary charging opening (3b), smoke outlet (4), slag escape orifice (7), metal escape orifice (8), main air port (2), overfiren air port (6), tertiary air orifice (5); Described main air port (2) arranges the bottom of copper water jacket (10), and described overfiren air port (6) is arranged on the top of molten steel cover (11); Described tertiary air orifice (5) is arranged on the top of molten steel cover; Described slag escape orifice (7) is arranged on main air port (2) below.
The equipment of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention, described main air port (2) is 0.4-0.7:1 to the vertical range of cupola well (9) bottom and the high ratio of stove;
Described overfiren air port (6) is 0.5-0.9:1 to the vertical range of cupola well (9) bottom and the high ratio of stove;
Described tertiary air orifice (5) is 0.7-1:1 to the vertical range of cupola well (9) bottom and the high ratio of stove.
When the equipment of the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali of the present invention is for smelting lead-containing material, in stove, pass into oxygen rich gas by main air port (2), overfiren air port (6), tertiary air orifice (5); During smelting, the aspirated pressure of main air port (2) is 0.2MPa ~ 2Mpa, main air port (2) send into O in oxygen rich gas
2flow with refine particulate charge amount for subsequent use and meet 50Nm
3~ 150Nm
3)/(t smelts particle for subsequent use); The aspirated pressure of overfiren air port (6) is 0.1MPa ~ 0.4Mpa, overfiren air port (6) send into O in oxygen rich gas
2flow with refine the satisfied (20Nm of particulate charge amount for subsequent use
3~ 120Nm
3)/(t smelts particle for subsequent use); The aspirated pressure of tertiary air orifice (5) is 0.1MPa ~ 0.4Mpa, tertiary air orifice (5) send into O in oxygen rich gas
2flow with refine the satisfied (5Nm of particulate charge amount for subsequent use
3~ 80Nm
3)/(t smelts particle for subsequent use).
Beneficial effect
Sodium carbonate, secondary lead material and reductive agent are first prepared burden by the present invention, compound after preparing is joined in side-blown converter, blast oxygen enrichment and carry out melting, fusion process oxygen enrichment directly blasts slag blanket, oxygen and the coal grain direct reaction falling into slag blanket, greatly accelerate speed of response, each component generation redox reaction in lead-containing material, precipitation liquid is plumbous, the metallic lead that reaction generates sinks to the bottommost in molten bath because density is comparatively large, finally released by siphon port, slag blanket floats on molten bath topmost, and the smelting slag below air port stirs little.
Advantage of the present invention is as follows:
1. the present invention is owing to taking the method for caustic fusion, achieves a plumbous step retailoring under low temperature, low stain condition, whole smelting process simply, is easily controlled.Simultaneously can also the sodium sulphite of output high level.
2. in the present invention, sulphur is fixed with the form of sodium sulphite, output high level vulcanizate, when processing the secondary lead raw material containing the precious metal such as gold and silver, can the precious metal such as synthetical recovery gold and silver, and good in economic efficiency.
3. utilize side-blown converter to carry out low smelting heat under excess oxygen, energy consumption is low, and reducing atmosphere controls good.
Accompanying drawing explanation
Fig. 1 is the front view of side-blown converter of the present invention;
Fig. 2 is the side-view of side-blown converter of the present invention.
In the drawings
1-molten bath district; 2-main air port; 3-charging opening; 4-smoke outlet; 5-tertiary air orifice; 6-overfiren air port; 7-slag escape orifice; 8-metal escape orifice; 9-cupola well; 10-copper water jacket; 11-molten steel cover.
Embodiment
Embodiment 1:
Cupola well is of a size of 1600 × 2500mm, hearth area is 4m in design
2side-blown converter, stove both sides respectively arrange 3 main air ports, by slag escape orifice with put metallic antimony mouth Position Design and guarantee the slag blanket degree of depth in 1200mm, metallic antimony layer depth at 500mm, on melt liquid level, stove both sides, 1500mm place respectively arrange 3 overfiren air ports, above overfiren air port, stove both sides, 1000mm place respectively arrange 2 tertiary air orifices, arrange φ 300mm charging opening one, smoke outlet is of a size of 400 × 400mm.
Test in above-mentioned side-blown converter.
Get the raw materials ready:
Get the scrap battery clay of leaded 68.76% to mix with the broken grid of leaded 93.12%, mixture leaded 76.31%; Sodium carbonate add-on is 40% of relative lead materials quality, add that coal grain amount is relative lead materials quality 10%, and it is 8% that above-mentioned material is added water to material moisture in drum pelletizer, makes particle diameter for subsequent use at the spherolite of 5mm ~ 18mm.
Melting:
Join in above-mentioned side-blown converter by above-mentioned spherolite material with the feed rate of 10t/h, smelting temperature controls between 800 ~ 900 DEG C, O in the oxygen-rich air that main air port blasts
2concentration is 50%, and all the other are N
2, oxygen-rich air pressure is 0.8MPa, and oxygen-rich air flow is 3000Nm
3/ h; O in secondary air and tertiary air
2concentration is all 50%, and all the other are N
2, pressure-controlling is at 0.2MPa, and secondary air flow is 500Nm
3/ h, tertiary air flow is 300Nm
3/ h.Lead recovery 94.31%, lead bullion leaded 98.74%.Get slag 50kg 150L water to soak at normal temperatures, substep reclaims sodium carbonate and sodium sulphite, and substep condensing crystal obtains sodium sulphite product 10kg, and sulfur-fixing rate is more than 90%.
Embodiment 2:
Smelting furnace is identical with embodiment 1.
Get the raw materials ready:
Get the scrap battery clay of leaded 68.76% and the sulphide ores original ore powder of leaded 20.14%, Au 4g/t mixes, compound leaded 50.12%; Sodium carbonate add-on is 40% of relative lead materials quality, add that coal grain amount is relative lead materials quality 10%, and it is 8% that above-mentioned material is added water to material moisture in drum pelletizer, makes particle diameter for subsequent use at the spherolite of 5mm ~ 18mm.
Melting:
Join in above-mentioned side-blown converter by above-mentioned spherolite material with the feed rate of 10t/h, smelting temperature controls between 800 ~ 900 DEG C, O in the oxygen-rich air that main air port blasts
2concentration is 50%, and all the other are N
2, oxygen-rich air pressure is 0.8MPa, and oxygen-rich air flow is 3000Nm
3/ h; O in secondary air and tertiary air
2concentration is all 50%, and all the other are N
2, pressure-controlling is at 0.2MPa, and secondary air flow is 500Nm
3/ h, tertiary air flow is 300Nm
3/ h.Lead recovery 93.11%, lead bullion leaded 99.12%, containing Au 8.2g/t in lead bullion, golden direct yield 97.67%.Get slag 50kg 150L water to soak at normal temperatures, substep reclaims sodium carbonate and sodium sulphite, and substep condensing crystal obtains sodium sulphite product 18kg, and sulfur-fixing rate is more than 90%.
Claims (9)
1. a method for the solid sulphur melting of oxygen-enriched side-blowing low-temperature alkali, is characterized in that, comprise the steps:
Step one
Add water after lead-containing material, reductive agent, sodium carbonate being mixed granulation, obtains smelting particle for subsequent use; The mass ratio of described sodium carbonate and lead-containing material is 0.4-5:1; The consumption of reductive agent be by the plumbous Restore All in lead-containing material be the theoretical amount of simple substance lead 1.5-3 doubly;
Step 2
Step one gained is smelted particle for subsequent use, to add continuously in oxygen-enriched side-blowing smelting furnace and to pass into oxygen rich gas, at 800 ~ 1000 DEG C, carrying out retailoring, obtain lead bullion or precious metals containing lead, smelting slag, flue gas.
2. the method for the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali according to claim 1, is characterized in that:
Described lead-containing material is selected from the mixture of secondary lead raw material or secondary lead raw material and lead ore powder, and described secondary lead raw material is selected from least one in scrap battery clay and screen, sulfuric acid lead skim, plumbous oxide cigarette ash, matte slag; Described lead ore powder is selected from least one in lead sulfide breeze, lead chloride ground-slag, lead fume dirt;
In described lead-containing material, plumbous mass percentage is 30-90%.
3. the method for the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali according to claim 1, is characterized in that:
Granularity≤the 5mm of described lead-containing material;
Described reductive agent is solid reductant, and described solid reductant is selected from least one in coke, gac, reduction coal; Granularity≤the 10mm of described solid reductant.
4. the method for the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali according to claim 1, is characterized in that: O in described oxygen rich gas
2volumetric concentration is 30% ~ 90%, and it is 0.1MPa ~ 1.6MPa that oxygen rich gas sends into pressure, O in oxygen rich gas
2flow with the pass smelting particulate charge amount for subsequent use is: (180Nm
3~ 420Nm
3)/(t smelts particle for subsequent use).
5. the method for the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali according to claim 1, is characterized in that: the granularity of smelting particle for subsequent use is 3mm ~ 25mm; The mass percentage smelting water in particle for subsequent use is 7% ~ 15%.
6. the method for the solid sulphur melting of a kind of oxygen-enriched side-blowing low-temperature alkali according to claim 1, it is characterized in that: the sulphur contained in secondary lead raw material and/or lead ore powder enters in smelting slag with the form of sodium sulphite, smelting slag recycles sodium carbonate in smelting slag and sodium sulphite through water logging; Described water logging is: be added to the water by smelting slag by liquid-solid mass ratio 3-6:1, until filter after the complete loose pulverizing of slag, filtrate, through fractional crystallization, obtains sodium carbonate and sodium sulphite product respectively; During water logging, control temperature is 20-90 DEG C.
7. oxygen-enriched side-blowing smelting furnace as claimed in claim 1, is characterized in that: described oxygen-enriched side-blowing smelting furnace comprise be positioned at side-blown bottom of furnace body cupola well (9), be positioned at the copper water jacket (10) in the middle part of body of heater and be positioned at the molten steel cover (11) of upper of furnace body, main charging opening (3a), auxiliary charging opening (3b), smoke outlet (4), slag escape orifice (7), metal escape orifice (8), main air port (2), overfiren air port (6), tertiary air orifice (5); Described main air port (2) arranges the bottom of copper water jacket (10), and described overfiren air port (6) is arranged on the top of molten steel cover (11); Described tertiary air orifice (5) is arranged on the top of molten steel cover; Described slag escape orifice (7) is arranged on main air port (2) below.
8. oxygen-enriched side-blowing smelting furnace according to claim 7, is characterized in that:
Described main air port (2) is 0.4-0.7:1 to the vertical range of cupola well (9) bottom and the high ratio of stove;
Described overfiren air port (6) is 0.5-0.9:1 to the vertical range of cupola well (9) bottom and the high ratio of stove;
Described tertiary air orifice (5) is 0.7-1:1 to the vertical range of cupola well (9) bottom and the high ratio of stove.
9. oxygen-enriched side-blowing smelting furnace according to claim 7, is characterized in that: during for smelting lead-containing material, passes into oxygen rich gas by main air port (2), overfiren air port (6), tertiary air orifice (5) in stove; During smelting, the aspirated pressure of main air port (2) is 0.2MPa ~ 2Mpa, main air port (2) send into O in oxygen rich gas
2flow with refine particulate charge amount for subsequent use and meet 50Nm
3~ 150Nm
3)/(t smelts particle for subsequent use); The aspirated pressure of overfiren air port (6) is 0.1MPa ~ 0.4Mpa, overfiren air port (6) send into O in oxygen rich gas
2flow with refine the satisfied (20Nm of particulate charge amount for subsequent use
3~ 120Nm
3)/(t smelts particle for subsequent use); The aspirated pressure of tertiary air orifice (5) is 0.1MPa ~ 0.4Mpa, tertiary air orifice (5) send into O in oxygen rich gas
2flow with refine the satisfied (5Nm of particulate charge amount for subsequent use
3~ 80Nm
3)/(t smelts particle for subsequent use).
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|---|---|---|---|
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| CN201410734457.5A CN104498731B (en) | 2014-12-04 | 2014-12-04 | A kind of method and apparatus of the solid sulfur melting of oxygen-enriched side-blowing low-temperature alkali |
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| CN104846214A (en) * | 2015-04-21 | 2015-08-19 | 云南驰宏锌锗股份有限公司 | Method for processing heavy metal-containing gypsum residue by oxygen-rich top-blown lead smelting furnace |
| CN104862483A (en) * | 2015-05-13 | 2015-08-26 | 杨华锋 | Method for disposing secondary lead materials by high oxygen-enriched side-blown bath smelting combination acid-making system |
| CN104894379A (en) * | 2015-05-11 | 2015-09-09 | 池州西恩新材料科技有限公司 | Method for carrying out reduction treatment on solid waste containing heavy metal through oxygen-enriched side blown converter |
| CN106086459A (en) * | 2016-08-30 | 2016-11-09 | 安阳市岷山有色金属有限责任公司 | A kind of oxygen bottom-blowing direct-reduction lead smelting process |
| CN106498164A (en) * | 2016-10-19 | 2017-03-15 | 湖南中大联合创新科技发展有限公司 | A kind of process for processing non-ferrous metal material using energy saving and environment friendly oxygen-enriched air smelting stove |
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| CN108350523A (en) * | 2015-10-16 | 2018-07-31 | 弗朗西斯科·哈维尔·卡德纳斯·阿尔比托 | Method for extracting metals from metal-bearing sulfide ore concentrates by direct reduction and regeneration and recovery of reducing agent iron and fluxing agent sodium carbonate |
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| CN104846214A (en) * | 2015-04-21 | 2015-08-19 | 云南驰宏锌锗股份有限公司 | Method for processing heavy metal-containing gypsum residue by oxygen-rich top-blown lead smelting furnace |
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| CN104894379A (en) * | 2015-05-11 | 2015-09-09 | 池州西恩新材料科技有限公司 | Method for carrying out reduction treatment on solid waste containing heavy metal through oxygen-enriched side blown converter |
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| CN108350523A (en) * | 2015-10-16 | 2018-07-31 | 弗朗西斯科·哈维尔·卡德纳斯·阿尔比托 | Method for extracting metals from metal-bearing sulfide ore concentrates by direct reduction and regeneration and recovery of reducing agent iron and fluxing agent sodium carbonate |
| CN106086459A (en) * | 2016-08-30 | 2016-11-09 | 安阳市岷山有色金属有限责任公司 | A kind of oxygen bottom-blowing direct-reduction lead smelting process |
| CN106498164A (en) * | 2016-10-19 | 2017-03-15 | 湖南中大联合创新科技发展有限公司 | A kind of process for processing non-ferrous metal material using energy saving and environment friendly oxygen-enriched air smelting stove |
| CN108239705A (en) * | 2018-01-31 | 2018-07-03 | 河南豫光金铅股份有限公司 | A kind of zinc leaching residue processing dual chamber Double bottom side-blown converter and its processing method |
| CN108239705B (en) * | 2018-01-31 | 2019-09-06 | 河南豫光金铅股份有限公司 | A kind of zinc leaching residue processing dual chamber Double bottom side-blown converter and its processing method |
| CN110295285A (en) * | 2019-08-02 | 2019-10-01 | 四川正祥环保技术有限公司 | A method of zinc is recycled from oxygen-enriched solid sulphur reduction melting clinker |
| CN110295285B (en) * | 2019-08-02 | 2021-04-16 | 四川正祥环保技术有限公司 | Method for recovering zinc from oxygen-enriched solid sulfur reduction smelting slag |
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