CN109385521B - Production process for lead-antimony mixed ore oxygen-enriched molten pool low-temperature oxidation smelting - Google Patents
Production process for lead-antimony mixed ore oxygen-enriched molten pool low-temperature oxidation smelting 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
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- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
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- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- C22B11/02—Obtaining noble metals by dry processes
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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Abstract
The invention discloses a production process for lead-antimony mixed ore oxygen-enriched molten pool low-temperature oxidation smelting, belonging to the field of non-ferrous metal smelting. The process comprises the following steps of 1) batching: uniformly mixing the raw materials and the auxiliary materials according to the mass ratio to obtain a mixture; 2) and (3) granulating: preparing the mixture into spherical particles; 3) oxidizing and smelting: feeding the prepared spherulites into an oxygen-enriched oxidation furnace for low-temperature oxidation smelting, producing liquid oxidation slag after smelting, and feeding the liquid oxidation slag into reduction smelting through a chute; high concentration SO produced after smelting2Cooling and dust collecting the flue gas, and then sending the flue gas to prepare acid. The invention comprises the following steps: 1) aiming at the problem that the existing oxidation smelting production process of jamesonite produces low-concentration SO2The SO in the smoke after smelting is effectively improved by adopting oxygen-enriched molten pool smelting after the emission reaches the standard after environmental protection treatment2The concentration meets the requirement of configuring a conventional acid making system, the pollution is reduced, and the recovery rate is improved; 2) the low-temperature oxygen-enriched oxidation process is adopted, so that the smoke dust rate is greatly reduced, and the smoke dust quality is improved.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a non-ferrous metal smelting process, in particular to a production process for lead-antimony mixed ore oxygen-enriched melting bath low-temperature oxidation smelting.
[ background of the invention ]
For the treatment of jamesonite, the smelting process flow adopted at present is as follows: antimony-lead concentrate → fluidized bed roasting → sintering of sintering disk → reduction of blast furnace → crude antimony-lead alloy. The process flow comprises the following steps: roasting the brittle sulfur antimony lead concentrate in a fluidized bed furnace for desulfurization, mixing the calcine with the brittle sulfur antimony lead concentrate, the return material, the quartz sand, the limestone powder and the anthracite for blending, sintering by using a sintering disc, and then reducing and smelting the sintered block in a blast furnace to produce the antimony lead alloy. However, the defects and shortcomings of the traditional smelting process are mainly as follows:
(1) low concentration SO is produced at each part of roasting, sintering machine and blast furnace2The flue gas can not be provided with a conventional acid making device to produce sulfuric acid, and the flue gas is subjected to desulfurization treatment and then is discharged after reaching the standard.
(2) The process flow is long, the number of intermediate links is large, the requirement of material returning proportion in the sintering process is large, and the process is circulated and reciprocated, so that the production efficiency is low, the number of intermediate products is large, and the metal recovery rate is low.
(3) Compared with oxygen enrichment and high-temperature strengthening smelting, the method has larger differences in the aspects of production efficiency, unit product production cost, investment yield and the like.
(4) The energy consumption is high. The chemical reaction dispersion and the heat utilization of sulfur in the raw materials are low, the comprehensive energy consumption of the refined antimony unit product reaches 2400-2500 kgce/t, and meanwhile, the flue gas is dispersed and has low temperature, and a waste heat boiler cannot be arranged to recover the flue gas waste heat.
(5) The sintering machine and other smelting production sites have high environmental pollution control difficulty and poor working conditions.
(6) The production automation degree is lower.
(7) Blast furnace reduction requires metallurgical coke and cannot use coal directly.
[ summary of the invention ]
In order to solve the problems, the invention aims to provide a production process for oxygen-rich molten pool low-temperature oxidation smelting of lead-antimony mixed ore, which comprises the following steps: 1) aiming at the problems that the existing oxidation smelting production process of jamesonite produces low-concentration SO more or less2The SO in the smoke after smelting is effectively improved by adopting oxygen-enriched molten pool smelting after the emission reaches the standard after environmental protection treatment2The concentration meets the requirement of configuring a conventional acid making system, the pollution is reduced, and the recovery rate is improved; 2) the low-temperature oxygen-enriched oxidation process is adopted, so that the smoke dust rate is greatly reduced, and the smoke dust quality is improved.
The technical scheme for realizing the purpose of the invention is as follows:
a production process for lead-antimony mixed ore oxygen-enriched molten pool low-temperature oxidation smelting comprises the following steps:
(1) preparing materials: uniformly mixing raw materials and auxiliary materials comprising lead-antimony mixed ore, quartz sand and limestone according to a mass ratio to obtain a mixture; wherein, the lead-antimony mixed ore is used as a raw material, and quartz sand and limestone are used as auxiliary materials;
(2) and (3) granulating: preparing the mixture into spherulites with the particle size of 12-20 mm, wherein the water content of the spherulites is 5-10%;
(3) oxidizing and smelting: feeding the prepared spherulites into an oxygen-enriched oxidation furnace for oxidation smelting, and carrying out periodic operation according to feeding, heating and slag discharging; firstly, desulfurizing and dearsenizing a mixture by adopting a low-temperature oxygen-enriched oxidation process, controlling the temperature of a flue gas outlet at the top of a furnace to be 750-850 ℃, and performing feeding operation according to the oxygen-material ratio, the feeding speed and the micro-negative pressure of the flue gas outlet at the top of the furnace, which are determined by the components of the raw materials and the furnace condition; secondly, stopping feeding after feeding of each furnace is finished, and adding the smokeless coal particles to heat the oxygen-enriched oxidation furnace; and then, after the temperature of the flue gas outlet at the top of the furnace rises to 850-950 ℃, stopping adding the smokeless coal particles, carrying out slag discharging operation, and enabling the produced liquid lead-antimony oxide slag to enter reduction smelting through a chute.
Further, the method also comprises the step (4) of recovering the dust-containing flue gas: the dust-containing smoke gas produced by the oxygen-enriched oxidation furnace is sent to a sulfuric acid workshop for acid production after waste heat recovery by a waste heat boiler, dust collection by an electric dust collector, quenching dearsenification and cloth bag dust collection, the smoke dust produced by the waste heat boiler returns to smelting, and the smoke dust produced by the electric dust collector is sent to a reverberatory furnace for producing No. 2 antimony.
Further, the lead-antimony mixed ore is a lead-antimony mixed ore containing 15% by mass or more of lead and 10% by mass or more of antimony, as represented by jamesonite.
Further, the mass ratio of the lead-antimony mixed ore to the quartz sand to the limestone is 100: 3-10: 3-5.
Furthermore, the blowing-in mode of the oxygen-enriched air in the oxygen-enriched oxidation furnace adopts a bottom blowing mode.
Further, the oxygen/material ratio in the step (3) is 200-240Nm3The charging speed is 12-14t/h, the micro negative pressure of a smoke outlet at the top of the furnace is-0.1 to-50 Pa, the charging time is 70-80min, and the heating time is 20-30 min.
Further, SO in the dust-containing flue gas produced in the oxygen-enriched oxidation furnace2The concentration of the gas is more than 10%.
Furthermore, the smoke rate produced by the oxygen-enriched oxidation furnace is less than 10%.
Further, the whole process of the production process is controlled by adopting a DCS control system.
By adopting the technical scheme, the invention has the beneficial effects that:
(1) the adaptability to raw materials is strong: the invention can directly treat the medium-low grade lead-antimony mixed ore which is represented by brittle sulfur lead-antimony ore and has lead content of more than 15% and antimony content of more than 10% and is difficult to treat in the prior art.
(2) And (3) environmental protection: firstly, the smelting process is carried out in a closed oxygen-enriched oxidation furnace, the micro-negative pressure operation of a flue gas outlet of the oxygen-enriched oxidation furnace can be stably controlled in the production, and SO is avoided2The smoke escapes; ② SO produced by oxygen-enriched oxidation furnace2The smoke concentration is up to more than 10 percent, the requirement of configuring a conventional acid making system can be completely met, and the tail gas after acid making reaches the standard and is discharged; thirdly, the concentrate and the auxiliary materials are directly fed into the furnace after being proportioned and granulated, and sintering and powder returning operation are not needed; and fourthly, the direct oxidation smelting is carried out only by adopting an oxygen-enriched oxidation furnace, the operation environment in front of the furnace is excellent, and the problem of serious pollution of production sites of sintering machines and blast furnaces prepared by the traditional process is solved. Fifthly, oxygen-enriched oxidation molten pool smelting is adopted to replace air blasting of a sintering machine-a blower, the smoke discharge amount is obviously reduced, and meanwhile, the smoke dust rate carried in the smoke evacuation process is reduced, and the smoke dust amount is reduced by about 2/3. In addition, the flue gas is also subjected to dust collection and arsenic removal treatment, so that the pollution of the tail gas discharged by the invention is greatly reduced, and the emission standard is reached.
(3) The energy consumption is low: firstly, oxidizing the brittle sulfur antimony lead concentrate by using an oxygen-enriched oxidation furnace, and basically realizing self-heating smelting, wherein the raw materials entering the furnace do not need or only need a small amount of coal blending for heat supplement; the hot slag produced by the oxygen-enriched smelting oxidation furnace directly flows into the oxygen-enriched reduction furnace through the slag groove to carry out reduction reaction, so that the heat energy is fully utilized, and the fuel consumption is correspondingly greatly saved. The comprehensive energy consumption of the refined antimony product is 1521.32kgce/t, which is far lower than that of the existing sintering-blast furnace process, and the energy-saving effect is very obvious. Secondly, the waste heat boiler can be matched to recover the waste heat of the smoke of the smelting furnace, and a large amount of heat energy is utilized.
(4) The recovery rate of the valuable elements is listed as follows:
| Sb | Pb | S | Ag |
| >94％ | >96％ | >95％ | >98％ |
(5) the automation level is high: the whole process of the invention adopts a DCS control system, and realizes the centralized control of the whole process and all equipment such as batching, granulating, oxygen supplying, smelting, waste heat boilers, boiler circulating water, electric dust collection, high temperature fans and the like.
(6) The operation rate is high: the effective feeding operation rate of actual production is more than 95%, and the effective annual operation time is more than 8000h, namely more than 330 d.
(7) The production cost is reduced: the oxygen-enriched smelting process flow is simplified, powder returning and sintering processes are not needed, and the oxygen-enriched reinforced smelting is adopted, so that the production efficiency is greatly improved, and the power and fuel consumption are low. And because the new process flow is short, the equipment and the device can be manufactured and installed at home, compared with the original process, the system can save the cost by 40-60 percent and the land area by about 40 percent.
[ detailed description ] embodiments
Example 1
A production process for lead-antimony mixed ore oxygen-enriched molten pool low-temperature oxidation smelting comprises the following steps:
(1) preparing materials: uniformly mixing jamesonite, quartz sand and limestone according to the mass ratio of 100:9:4 to obtain a mixture;
(2) and (3) granulating: preparing the mixture into spherulites with the particle size of 12-15 mm, wherein the water content of the spherulites is 5-8%;
(3) oxidizing and smelting: the prepared spherulites are sent into an oxygen-enriched oxidizing furnace with oxygen-enriched air bottom blowing for oxidation smelting, and the oxygen-enriched smelting is carried out according to the steps of feeding, heating and deslaggingAnd (5) line cycle operation. Firstly, the mixture is desulfurized and dearsenized by adopting a low-temperature oxygen-enriched oxidation process, the temperature of a flue gas outlet at the top of a furnace is controlled to be 750 ℃, and the oxygen-material ratio is controlled to be 220Nm3And (2) performing charging operation at the charging speed of 12t/h and the negative pressure of-0.1 to-10 Pa at a smoke outlet at the top of the furnace, stopping charging after 70min of charging, adding smokeless coal particles, performing heating operation for 20min, stopping adding the smokeless coal particles after the temperature of the smoke outlet at the top of the furnace is raised to 850 ℃, performing deslagging operation, and enabling the produced liquid lead-antimony oxide slag to enter oxygen-enriched reduction smelting through a chute.
(4) Recovering dust-containing flue gas: through detection, SO in the dust-containing flue gas produced in the feeding period of the oxygen-enriched oxidation furnace2The smoke concentration reaches more than 10 percent, and the smoke dust rate produced by the oxygen-enriched oxidation furnace is less than 10 percent; the dust-containing flue gas is sent to a sulfuric acid workshop for acid production after waste heat recovery by a waste heat boiler, dust collection by an electric dust collector, quenching dearsenification and cloth bag dust collection, the smoke produced by the waste heat boiler returns to smelting, and the smoke produced by the electric dust collector is sent to a reverberatory furnace for producing No. 2 antimony.
In the embodiment of the invention, the whole process of the production process is controlled by adopting a DCS control system so as to improve the automation degree of the whole process.
Example 2
A production process for lead-antimony mixed ore oxygen-enriched molten pool low-temperature oxidation smelting comprises the following steps:
(1) preparing materials: uniformly mixing jamesonite, smoke dust, quartz sand and limestone according to the mass ratio of 100:15:10:5 to obtain a mixture;
(2) and (3) granulating: preparing the mixture into spherulites with the particle size of 15-20 mm, wherein the water content of the spherulites is 8-10%;
(3) oxidizing and smelting: the prepared spherulites are sent into an oxygen-enriched oxidation furnace of oxygen-enriched air bottom blowing for oxidation smelting, and periodic operation is carried out according to feeding, temperature rising and slag discharging. Firstly, the mixture is desulfurized and dearsenized by adopting a low-temperature oxygen-enriched oxidation process, the temperature of a flue gas outlet at the top of a furnace is controlled to be 850 ℃, and the oxygen-material ratio is controlled to be 200Nm3The charging operation is carried out at the charging speed of 13t/h and the negative pressure of-10-20 Pa at the top of the furnace, the charging is stopped after 80min, the smokeless coal particles are added for heating operation for 30min, the smokeless coal particles are stopped being added after the temperature of the flue gas outlet at the top of the furnace is raised to 950 ℃, and the slag is dischargedAnd (4) operating, wherein the produced liquid lead-antimony oxide slag enters reduction smelting through a chute.
(4) Recovering dust-containing flue gas: through detection, SO in the dust-containing flue gas produced in the feeding period of the oxygen-enriched oxidation furnace2The smoke concentration reaches more than 10 percent, and the smoke dust rate produced by the oxygen-enriched oxidation furnace is less than 10 percent; the dust-containing flue gas is sent to a sulfuric acid workshop for acid production after waste heat recovery by a waste heat boiler, dust collection by an electric dust collector, quenching dearsenification and cloth bag dust collection, the smoke produced by the waste heat boiler returns to smelting, and the smoke produced by the electric dust collector is sent to a reverberatory furnace for producing No. 2 antimony.
In the embodiment of the invention, the whole process of the production process is controlled by adopting a DCS control system so as to improve the automation degree of the whole process.
Example 3
A production process for lead-antimony mixed ore oxygen-enriched molten pool low-temperature oxidation smelting comprises the following steps:
(1) preparing materials: uniformly mixing jamesonite, middle-low grade antimony ore, quartz sand and limestone according to the mass ratio of 100:15:3:3 to obtain a mixture;
(2) and (3) granulating: preparing the mixture into spherulites with the particle size of 15-20 mm, wherein the water content of the spherulites is 8-10%;
(3) oxidizing and smelting: the prepared spherulites are sent into an oxygen-enriched oxidation furnace of oxygen-enriched air bottom blowing for oxidation smelting, and periodic operation is carried out according to feeding, temperature rising and slag discharging. Firstly, the mixture is desulfurized and dearsenized by adopting a low-temperature oxygen-enriched oxidation process, the temperature of a flue gas outlet at the top of a furnace is controlled to be 750 ℃, and the oxygen-material ratio is controlled to be 240Nm3And (2) performing charging operation at the charging speed of 13t/h and the negative pressure of-20-30 Pa on the furnace top, stopping charging after 75min of charging, adding the smokeless coal particles, performing heating operation for 25min, stopping adding the smokeless coal particles after the temperature of a flue gas outlet at the furnace top is increased to 900 ℃, performing slag discharging operation, producing liquid lead-antimony oxide slag, and performing reduction smelting through a chute.
(4) Recovering dust-containing flue gas: through detection, SO in the dust-containing flue gas produced in the feeding period of the oxygen-enriched oxidation furnace2The smoke concentration reaches more than 10 percent, and the smoke dust rate produced by the oxygen-enriched oxidation furnace is less than 10 percent; the dust-containing flue gas is passed through the processes of waste heat recovery by waste heat boiler, dust collection by electric dust collector, quenching dearsenification and dust collection by cloth bag, and then fed into sulfurAcid is produced in an acid workshop, the smoke generated by the waste heat boiler returns to smelting, and the smoke generated by the electric dust collector is sent to a reverberatory furnace to produce No. 2 antimony.
In the embodiment of the invention, the whole process of the production process is controlled by adopting a DCS control system so as to improve the automation degree of the whole process.
Example 4
A production process for lead-antimony mixed ore oxygen-enriched molten pool low-temperature oxidation smelting comprises the following steps:
(1) preparing materials: uniformly mixing jamesonite, quartz sand and limestone according to the mass ratio of 100:8:4 to obtain a mixture;
(2) and (3) granulating: preparing the mixture into spherulites with the particle size of 12-15 mm, wherein the water content of the spherulites is 5-8%;
(3) oxidizing and smelting: the prepared spherulites are sent into an oxygen-enriched oxidation furnace of oxygen-enriched air bottom blowing for oxidation smelting, and periodic operation is carried out according to feeding, temperature rising and slag discharging. Firstly, the mixture is desulfurized and dearsenized by adopting a low-temperature oxygen-enriched oxidation process, the temperature of a flue gas outlet at the top of a furnace is controlled to be 800 ℃, and the oxygen-material ratio is controlled to be 220Nm3And (2) performing charging operation at the charging speed of 12t/h and the negative pressure of a smoke outlet at the top of the furnace of-40 to-50 Pa, stopping charging after 80min of charging, adding the smokeless coal particles, performing heating operation for 25min, stopping adding the smokeless coal particles after the temperature of the smoke outlet at the top of the furnace is raised to 950 ℃, performing deslagging operation, and enabling the produced liquid lead-antimony oxide slag to enter oxygen-enriched reduction smelting through a chute.
(4) Recovering dust-containing flue gas: through detection, SO in the dust-containing flue gas produced in the feeding period of the oxygen-enriched oxidation furnace2The smoke concentration reaches more than 10 percent, and the smoke dust rate produced by the oxygen-enriched oxidation furnace is less than 10 percent; the dust-containing flue gas is sent to a sulfuric acid workshop for acid production after waste heat recovery by a waste heat boiler, dust collection by an electric dust collector, quenching dearsenification and cloth bag dust collection, the smoke produced by the waste heat boiler returns to smelting, and the smoke produced by the electric dust collector is sent to a reverberatory furnace for producing No. 2 antimony.
In the embodiment of the invention, the whole process of the production process is controlled by adopting a DCS control system so as to improve the automation degree of the whole process.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (6)
1. A production process for lead-antimony mixed ore oxygen-enriched molten pool low-temperature oxidation smelting is characterized by comprising the following steps:
(1) preparing materials: uniformly mixing raw materials and auxiliary materials comprising lead-antimony mixed ore, quartz sand and limestone according to a mass ratio to obtain a mixture; the lead-antimony mixed ore is represented by jamesonite, and contains more than 15% of lead by mass and more than 10% of antimony by mass; the mass ratio of the lead-antimony mixed ore to the quartz sand to the limestone is 100: 3-10: 3-5;
(2) and (3) granulating: preparing the mixture into spherulites with the particle size of 12-20 mm, wherein the water content of the spherulites is 5-10%;
(3) oxidizing and smelting: feeding the prepared spherulites into an oxygen-enriched oxidation furnace for oxidation smelting, and carrying out periodic operation according to feeding, heating and slag discharging; firstly, desulfurizing and dearsenizing a mixture by adopting a low-temperature oxygen-enriched oxidation process, controlling the temperature of a flue gas outlet at the top of a furnace to be 750-850 ℃, and performing feeding operation according to the oxygen-material ratio, the feeding speed and the micro-negative pressure of the flue gas outlet at the top of the furnace, which are determined by the components of the raw materials and the furnace condition; secondly, stopping feeding after feeding of each furnace is finished, and heating the oxygen-enriched oxidation furnace; then, after the temperature of the flue gas outlet at the top of the furnace rises to 850-950 ℃, stopping heating, carrying out slag discharging operation, and enabling the produced liquid lead-antimony oxide slag to enter reduction smelting through a chute; the oxygen-material ratio is 200-240Nm3The charging speed is 12-14t/h, the micro negative pressure of a smoke outlet at the top of the furnace is-0.1 to-50 Pa, the charging time is 70-80min, and the heating time is 20-30 min.
2. The production process of oxygen-enriched melting pool low-temperature oxidation smelting of lead-antimony mixed ore according to claim 1, characterized by further comprising the step (4) of recycling dust-containing flue gas: the dust-containing smoke gas produced by the oxygen-enriched oxidation furnace is sent to a sulfuric acid workshop for acid production after waste heat recovery by a waste heat boiler, dust collection by an electric dust collector, quenching dearsenification and cloth bag dust collection, the smoke dust produced by the waste heat boiler returns to smelting, and the smoke dust produced by the electric dust collector is sent to a reverberatory furnace for producing No. 2 antimony.
3. The production process of the low-temperature oxidation smelting of the lead-antimony mixed ore oxygen-rich melting pool as claimed in claim 1, wherein the blowing mode of the oxygen-rich air in the oxygen-rich oxidizing furnace is a bottom blowing mode.
4. The production process of oxygen-enriched molten pool low-temperature oxidation smelting of lead-antimony mixed ore according to claim 1, characterized in that SO in dust-containing flue gas produced in the oxygen-enriched oxidation furnace2The concentration of the gas is more than 10%.
5. The production process of oxygen-enriched melting pool low-temperature oxidation smelting of lead-antimony mixed ore according to claim 1, characterized in that the smoke dust rate produced by the oxygen-enriched oxidation furnace is below 10%.
6. The production process of oxygen-enriched melting pool low-temperature oxidation smelting of lead-antimony mixed ore according to claim 1, characterized in that the whole process of the production process is controlled by a DCS control system.
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| CN117488092B (en) * | 2023-12-29 | 2024-04-02 | 湘潭中创电气有限公司 | Molten pool smelting and flue gas treatment process for antimony-gold concentrate |
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| CN103173636B (en) * | 2013-03-06 | 2014-09-03 | 中南大学 | Antimony sulfide concentrate oxygen-enriched melting tank melting method |
| CN104278162B (en) * | 2014-11-01 | 2016-08-17 | 中南大学 | A kind of antimonial lead complex materials selectivity fused bath smelting method |
| CN104894380B (en) * | 2015-05-18 | 2016-04-13 | 张圣南 | The directed melting process for cleanly preparing of a kind of closed oxygen-enriched sub-pressure high-efficient smelting furnace |
| CN106521189A (en) * | 2016-10-21 | 2017-03-22 | 河池市生富冶炼有限责任公司 | Oxygen-enriched molten pool antimony refining production process |
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