CN112176202B - Antimony smelting method adopting oxygen-enriched side-blown column smelting - Google Patents
Antimony smelting method adopting oxygen-enriched side-blown column smelting Download PDFInfo
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- CN112176202B CN112176202B CN202011174765.9A CN202011174765A CN112176202B CN 112176202 B CN112176202 B CN 112176202B CN 202011174765 A CN202011174765 A CN 202011174765A CN 112176202 B CN112176202 B CN 112176202B
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
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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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
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Abstract
The invention discloses an antimony smelting method adopting oxygen-enriched side-blown column smelting, which comprises the steps of blowing oxygen-enriched air into an oxygen-enriched side-blown volatilization furnace, providing heat by coke, controlling the temperature in the furnace to be 1350-1450 ℃, mixing granular ore with a solvent: iron ore, cobblestones, and heat source: and (4) metering coke, and then feeding the coke into the furnace for reaction. High-temperature flue gas and melt are produced; firstly, recovering heat of high-temperature flue gas, utilizing the recovered heat for drying granular ores and other workshop production and utilization, then condensing and collecting dust, sending the flue gas to an acid making system for making acid, and sending the dust obtained by condensation into a crude oxygen powder product to be processed in the next process; high-temperature melt flows into a front bed through a slag channel, the front bed is insulated by natural gas at 1200 ℃, the natural gas is respectively discharged after sedimentation and layering, the slag can be directly used as waste slag after water quenching, a small amount of produced antimony matte is returned for treatment, and the crude antimony is sent to the next procedure for treatment.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of chemical metallurgy, in particular to an antimony smelting method adopting oxygen-enriched side-blown column smelting.
[ background of the invention ]
Antimony is a specific mineral species for protective exploitation in China and is also a dominant mineral resource in China. Antimony is listed as a strategic material in developed countries. As the biggest antimony product production and export country in China, the yield of antimony products accounts for more than 80 percent of the world. Antimony metallurgy is divided into a fire method and a wet method, and the fire metallurgy process in the production of antimony metallurgy has absolute advantages which are more than 95%; at present, the antimony smelting in China mainly adopts a blast furnace volatilization smelting process, and the process flow of 'antimony concentrate blast furnace volatilization smelting-crude antimony trioxide reverberatory furnace reduction smelting' is the basic process of most antimony smelting plants in China at present, wherein antimony concentrate, iron ore, limestone and coke are distributed in the blast furnace layer by layer for oxygen blowing smelting, and antimony oxide powder, antimony matte and calcium-iron-silicon slag are produced by smelting, although the process has the advantages of strong raw material adaptability, large bed capacity and the like, the process has the advantages of low unit productivity, low heat utilization rate, high energy consumption, more expensive metallurgical coke as fuel and reducing agent, and the coke consumption per ton of refined antimony is 700-800 kg, so that the production cost is high; SO in flue gas generated by the same 2 Very low concentration of only 1Percent is 2 percent, the acid can not be prepared and recovered, and smoke dust and smoke gas can leak to pollute air when the furnace condition is not good due to poor sealing of the furnace, so the production environment is poor. The process is inconsistent with the national industrial policy of energy conservation and consumption reduction, and the blast furnace smelting process is eliminated in a technology lagging state along with the more and more strict requirements of the national environmental protection standard.
In order to solve the problems of antimony smelting in a blast furnace, a great deal of research introduces a molten pool smelting technology into antimony smelting, for example, chinese patent application CN200710050357.0 discloses an oxygen molten pool smelting method for lead antimony ore, which adds lead antimony ore or a mixed ore of the lead antimony ore and lead concentrate, a flux (iron ore, limestone or quartz), smoke dust and solid fuel into molten oxidized bottom slag based on FeO-CaO-SiO 2 The slag mold is used for oxidation smelting to directly produce lead-antimony alloy and oxidation smelting slag for fuming treatment. Although the Pb content in the slag produced by oxidation smelting can be lower than 2%, the Sb content in the slag is as high as more than 5%, so that the loss of Sb in the slag is high.
Chinese patent application CN200810031214 discloses a method for smelting antimony by using oxygen-enriched air in a blast furnace, wherein 25-48% of oxygen-enriched air is used for smelting antimony ore or antimony-containing materials, but tail gas SO 2 The concentration is less than 1.1 percent, the desulfurization treatment is still needed, the high-efficiency and low-cost utilization of sulfur resources is difficult to realize, and the environmental risk still exists. Compared with an oxygen-poor blast furnace, the antimony blast furnace oxygen-rich volatilization smelting process has the advantages that the bed capacity is greatly improved, the coke consumption is greatly reduced, but the coke consumption is still high and reaches 25%; the recovery rate of gold and silver in the antimony blast furnace oxygen-enriched volatilization smelting process is 90 percent.
The Chinese patent application CN201310070398 discloses an antimony sulfide concentrate oxygen-enriched molten pool smelting method and a side-blown converter, wherein the method only aims at antimony sulfide concentrate, the raw material is single in treatment, and the raw material needs to be granulated; the product is metallic antimony, but the direct yield is low, only 10-25%, the impurity content of the metallic antimony is high, and the treatment is difficult; the slag adopts high-iron slag, the flux consumption is high, the slag rate is high, and the recovery rate is low; the required oxygen-enriched pressure is as high as 1.6MPa, and the industrialization is difficult to realize.
Chinese patent application CN20131007039 discloses a method for smelting antimony sulfide concentrate in an oxygen-enriched molten pool, wherein raw materials are only treated aiming at antimony sulfide concentrate, the treated raw materials are single, and the raw materials need to be granulated; the product is dispersed, and the treatment process is long; the yield of the antimony in the slag is as high as 30-40%, the percentage content of the antimony is as high as 30%, and secondary treatment is needed to recover antimony metal; the slag is high-iron slag, so that the flux consumption is high, the slag rate is high, and the recovery rate is low; the gold in the raw materials basically enters the furnace slag, the gold recovery process is long, the efficiency is low, and the industrialization is difficult to realize.
The antimony blast furnace volatilization smelting process has the advantages of strong raw material adaptability, large processing capacity and easy mechanical operation, but the special operating conditions of low stock column, thin stock layer, high coke rate and high temperature furnace top also determine that the process has high energy consumption, the coke rate is 30-45 percent, and especially the tail gas SO 2 The concentration is less than 0.5 percent, the ecological environment is seriously polluted, the recovery rate of metals, particularly noble metals, is low, the return product rate is high, and the direct yield is low. The new antimony smelting technology developed at present adopts more advanced molten pool smelting devices such as an oxygen top-blown furnace, a bottom-blown furnace and the like, but the smelting principle still follows the technical characteristics of blast furnace volatilization smelting, and iron ore, limestone and quartz stone are adopted as slagging agents based on FeO-CaO-SiO 2 And smelting the slag mould.
Therefore, the existing oxygen-enriched bath antimony smelting technology cannot meet the industrial application requirements, the existing antimony smelting still adopts the original blast furnace volatilization smelting technology, and the development of an industrially feasible oxygen-enriched side-blown column smelting technology for antimony smelting is urgently needed.
[ summary of the invention ]
Aiming at the defects that the energy consumption of the traditional blast furnace is high, the tail gas contains low sulfur, the acid making requirement cannot be met and the like in the prior art, the invention provides the antimony smelting method adopting oxygen-enriched side-blown column smelting by combining the characteristics of the smelting process of the absorption molten pool and the advantages of the traditional smelting technology.
The invention relates to an antimony smelting method adopting oxygen-enriched side-blown column smelting, which is characterized in that oxygen-enriched air is blown into an oxygen-enriched side-blown volatilization furnace, coke provides heat, the temperature in the furnace is controlled to 1350-1450 ℃, and grain ore and solvent are mixed: iron ore, cobblestones, and heat source: coke is measured and then enters a furnace to react to produce high-temperature flue gas and a melt; firstly, recovering heat of high-temperature flue gas, utilizing the recovered heat for drying granular ores and other workshop production and utilization, then condensing and collecting dust, sending the flue gas to an acid making system for making acid, and sending the dust obtained by condensation into a crude oxygen powder product to be processed in the next process; high-temperature melt flows into a front bed through a slag channel, the front bed is insulated by natural gas at 1200 ℃, the natural gas is respectively discharged after sedimentation and layering, the slag can be directly used as waste slag after water quenching, a small amount of produced antimony matte is returned for treatment, and the crude antimony is sent to the next procedure for treatment.
The invention relates to an antimony smelting method adopting oxygen-enriched side-blown column smelting, which comprises the following steps:
1) And (3) granulating: antimony concentrate, quicklime powder and water are uniformly mixed according to the weight ratio of (9-10) to (1) (0.3-0.5), and are processed into granulated ore by a disc granulator, and the granulated ore is prepared to be fed into a furnace after being dried;
2) Feeding materials into a furnace: feeding the coke, iron ore, cobblestones, returned materials and the granulated ore obtained in the previous step into an oxygen-enriched side-blown volatilization furnace according to the weight ratio of (170-190): (135-145): (38-42): (47-53): 880-920, wherein the materials fed into the furnace and the synthetic silicate gangue meet the following proportion: si0 2 Fe0, ca0=1, (0.7-0.9) and (0.6-0.7), feeding is carried out once every 15-20 minutes, and feeding is carried out continuously for 24 hours;
3) And (3) volatilizing and smelting in an oxygen-enriched side-blown volatilization furnace: after the material is fed into the furnace, oxygen-enriched air with 25-35% of oxygen content is continuously blown into the furnace through the bottom, the side and the top of the furnace, the pressure is controlled at 10-15kPa, and the flow rate is 110-130m 3 Min, controlling the temperature in the furnace to 1350-1450 ℃ and the height of the material column to be 800-1000mm;
(1) oxidizing antimony sulfide in the ore particles in the step 2) into antimony oxide to form high-temperature high-concentration antimony-containing flue gas, performing flue gas sedimentation and evaporative cooling to obtain antimony trioxide powder, or performing flue gas sedimentation, evaporative cooling, surface cooling and cloth bag dust collection to obtain antimony trioxide powder, and conveying the treated flue gas to an acid making system for making acid;
(2) forming ferrosilicon-calcium ternary system slag by the granular ore, cobblestones and iron ore in the step 2), flowing into a front bed through a slag passage at the bottom of the oxygen-enriched side-blown volatilization furnace, performing gravity separation, then discharging the slag periodically through a front bed slag tap, performing water quenching to form water-quenched slag (slag), separating antimony matte, returned materials and crude antimony, discharging the antimony matte through the front bed antimony matte tap, returning the antimony matte and the returned materials to the step 1) for production, and returning the crude antimony to the step 2) for production or to a subsequent reverberatory furnace for treatment;
(3) the flue gas containing more than or equal to 15 percent of sulfur permeates a cloth bag to collect dust, enters an acid making system, and is trapped and oxidized by the acid making system to ensure that most SO 2 Converting into sulfuric acid, and removing residual SO from residual flue gas in a desulfurization system 2 After that, the tail gas is exhausted.
Antimony concentrate, quicklime powder and water in the step 1) are mixed according to the weight ratio of 9; the granularity of the ore particles in the step 1) is 10-20 mm; the drying in the step 1) refers to drying by a waste heat recovery system until the moisture content is less than 10%.
The material charging in the step 2) is to mix coke, iron ore, cobblestone, return material and the granulated ore obtained in the previous step according to the weight ratio of 180: si0 2 Fe0: ca0=1:0.8, wherein after the materials are weighed and measured by hoppers, the materials are conveyed to a material clock of a feeding port at the top of an oxygen-enriched side-blown volatilization furnace through a transfer belt, the materials are fed into the oxygen-enriched side-blown volatilization furnace twice through a fuel solvent and ore particles of the material clock, the feeding is carried out once every 15 minutes, the materials are fed continuously for 24 hours, and the materials are subjected to melting, dissociation, desulfurization, oxidation, volatilization and slagging reactions in the furnace.
And 3) volatilizing and smelting in the oxygen-enriched side-blown volatilization furnace, namely blowing oxygen-enriched air with the oxygen content of 35% into the furnace continuously after the materials are put into the furnace, controlling the temperature in the furnace to be 1400 ℃, and the height of a material column to be 800-1000mm, strongly stirring the high-temperature melt by the blown oxygen-enriched air and participating in the reaction, greatly optimizing the gas-liquid-solid reaction conditions, strengthening the progress of various reactions in the furnace, producing high-temperature high-concentration antimony-containing flue gas and high-temperature melt, feeding more than 75% of antimony into the flue gas, allowing the high-temperature melt to flow to a front bed through a slag channel for automatic layering, wherein the upper layer is furnace slag, the middle layer is antimony matte, and the bottom layer is crude antimony.
The flue gas sedimentation in the step 3) refers to that the high-temperature high-concentration antimony-containing flue gas enters a flue gas sedimentation chamber through a gooseneck when passing through the furnace top.
And 3) preserving the temperature of the front bed in the step 3) by adopting natural gas at 1200 ℃.
Compared with the prior art, the invention has the following advantages:
1. the traditional blast furnace has high energy consumption and low sulfur content in tail gas, and can not meet the acid making requirement; the furnace hearth of the existing molten pool smelting technology mainly adopts high-temperature liquid melt, and the liquid melt is solidified due to the fact that a large amount of antimony sulfide volatilizes to carry away the heat in the furnace, so that the production cannot be continuously carried out, and the working procedure is stopped. The invention combines the advantages of the traditional smelting technology on the basis of absorbing the smelting technology of a molten pool, develops an antimony smelting oxygen-enriched side-blown column smelting process, continuously blows oxygen-enriched air with the oxygen content of 25-35% into a furnace through the bottom part of the furnace, the side part of the furnace and the top part of the furnace, strengthens the progress of various reactions in the furnace, produces high-temperature high-concentration antimony-containing flue gas and high-temperature melt, enables more than 75% of antimony in raw materials to enter the flue gas, enables the remaining antimony to enter antimony matte and crude antimony, enables the antimony to be enriched at the end of a cloth bag chamber, reduces the antimony content in the antimony matte and crude antimony as much as possible, and collects silver in the raw materials in the crude antimony.
2. According to the smelting scheme, a columnar smelting mode mainly comprising solid particles is adopted in a hearth of the oxygen-enriched side-blown volatilization furnace, oxygen-enriched air with the oxygen content of 25-35% is continuously blown into the furnace through the bottom, the side and the top of the furnace, the fluctuation of material columns in the furnace is controlled between 800-1000mm, the air consumption is greatly reduced, on one hand, the sulfur concentration of flue gas is improved to be more than 15% (the sulfur content of a traditional blast furnace is lower than 2%), on the other hand, sulfides in the furnace are rapidly oxidized to release heat, so that the coke consumption is reduced, and experiments prove that the coke can be reduced to be lower than 20% (coke/furnace antimony concentrate powder).
3. In order to ensure that sulfides volatilized from a traditional blast furnace can be completely oxidized and a large amount of air leaks from a system, the sulfur content in flue gas is reduced, andoxygen-enriched air with the oxygen content of 25-35% is blown into the furnace from the top of the furnace, so that sulfides volatilized from the furnace are quickly oxidized, and on one hand, the sulfides are completely oxidized; on the other hand, the air consumption is reduced, the sulfur content of the flue gas is improved, and the high-temperature flue gas SO discharged from the furnace 2 The concentration of the sulfur-containing compound is more than 15 percent, meets the requirement of low-concentration acid preparation, can stably prepare acid, not only recovers sulfur resources, but also eliminates low-concentration SO 2 Harm to the environment.
[ description of the drawings ]
FIG. 1 is a process flow diagram of an antimony smelting process using oxygen-rich side-blown column smelting according to the present invention.
[ detailed description ] embodiments
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1:
an antimony smelting method adopting oxygen-enriched side-blown column smelting comprises the following steps:
1) And (3) granulating: antimony concentrate, quicklime powder and water are uniformly mixed according to the weight ratio of 9 to 0.5, the mixture is processed into granulated ore with the granularity of 10-20 mm by a disc granulator, and the granulated ore is dried by a waste heat recovery system until the moisture content is less than 10% and then is ready to be put into a furnace;
2) Feeding materials into a furnace: feeding coke, iron ore, cobblestones, return materials and the granulated ore obtained in the previous step into an oxygen-enriched side-blown volatilization furnace according to the weight ratio of 180: si0 2 Fe0: ca0=1:0.8, wherein each bin is weighed by a hopper, then a material clock conveyed to a charging port at the top of the oxygen-enriched side-blown volatilization furnace by a transfer belt is put into the oxygen-enriched side-blown volatilization furnace twice through a material clock by fuel solvent and ore particles, and the material is fed once every 15 minutesContinuously feeding for 24 hours, and carrying out melting, dissociation, desulfurization, oxidation, volatilization and slagging reaction on the materials in the furnace;
3) And (3) volatilizing and smelting in an oxygen-enriched side-blown volatilization furnace: after the material is fed into the furnace, oxygen-enriched air with the oxygen content of 35 percent is continuously blown into the furnace through the bottom, the side and the top of the furnace, the pressure is controlled at 15kPa, and the flow rate is 120m 3 Controlling the temperature in the furnace to 1350-1450 ℃, the height of the material column to be 800-1000mm, strongly stirring the high-temperature melt by blown oxygen-enriched air and participating in the reaction, greatly optimizing the gas-liquid-solid reaction conditions, strengthening the progress of various reactions in the furnace, producing high-temperature high-concentration antimony-containing flue gas and high-temperature melt, wherein more than 75% of antimony enters the flue gas, the high-temperature melt flows to a front bed through a slag channel to be automatically layered, the upper layer is furnace slag, the middle layer is antimony matte and the bottom layer is crude antimony;
(1) oxidizing antimony sulfide in the ore particles in the step 2) into antimony oxide to form high-temperature high-concentration antimony-containing flue gas, allowing the high-temperature high-concentration antimony-containing flue gas to enter a smoke dust settling chamber through a gooseneck when the high-temperature high-concentration antimony-containing flue gas passes through a furnace top, and performing evaporative cooling to obtain antimony trioxide powder, or allowing the high-temperature high-concentration antimony-containing flue gas to enter the smoke dust settling chamber through the gooseneck when the high-temperature high-concentration antimony-containing flue gas passes through the furnace top, performing evaporative cooling, performing surface cooling, and collecting dust by using a cloth bag to obtain antimony trioxide powder, and conveying the treated flue gas to an acid making system to prepare acid;
(2) forming ferrosilicon-calcium ternary system slag by the granular ore, cobblestones and iron ore in the step 2), allowing the slag to flow into a front bed through a slag passage at the bottom of an oxygen-enriched side-blown volatilization furnace to perform gravity separation, and then discharging the slag periodically through a front bed slag tap, keeping the temperature of the front bed at 1200 ℃ by using natural gas, performing water quenching to form water-quenched slag, separating antimony matte, returned materials and crude antimony, wherein the slag contains 0.4-1.0% of antimony, the antimony matte and the crude antimony contain more than 21% of antimony, the crude antimony contains more than 60% of silver, the antimony matte is discharged through the front bed antimony tap, the antimony matte and the returned materials are returned to the step 1) for production, and the crude antimony is returned to the step 2) for production or enters a subsequent reverberatory furnace for treatment;
(3) the flue gas containing more than or equal to 15 percent of sulfur permeates through the cloth bag to collect dust, enters an acid making system, and is trapped and oxidized by the acid making system to ensure that most of SO 2 Converting into sulfuric acid, and removing residual SO from residual flue gas in desulfurizing system 2 After that, the tail gas is exhausted.
Example 2:
an antimony smelting method adopting oxygen-enriched side-blown column smelting comprises the following steps:
1) And (3) granulating: antimony concentrate, quicklime powder and water are uniformly mixed according to the weight ratio of 10 to 1 to 0.3, the mixture is processed into granulated ore with the granularity of 10-20 mm by a disc granulator, and the granulated ore is dried by a waste heat recovery system until the moisture content is less than 10% and then is prepared to be fed into a furnace;
2) Feeding materials into a furnace: feeding the coke, the iron ore, the cobblestones, the return materials and the granulated ores obtained in the previous step into an oxygen-enriched side-blown volatilization furnace according to the weight ratio of 170: si0 2 Fe0: ca0=1:0.7, wherein after the materials are weighed and measured by each bin through a hopper, the materials are conveyed to a material clock at a feeding port at the top of the oxygen-enriched side-blown volatilization furnace through a transfer belt, the materials are fed into the oxygen-enriched side-blown volatilization furnace twice through a fuel solvent and ore particles of the material clock, the materials are fed once every 20 minutes and are continuously fed for 24 hours, and the materials are subjected to melting, dissociation, desulfurization, oxidation, volatilization and slagging reaction in the furnace;
3) And (3) volatilizing and smelting in an oxygen-enriched side-blown volatilization furnace: after the material is fed into the furnace, oxygen-enriched air with the oxygen content of 30 percent is continuously blown into the furnace through the bottom, the side and the top of the furnace, the pressure is controlled at 10kPa, and the flow rate is 110m 3 Controlling the temperature in the furnace to 1350 ℃, the height of a material column to be 800-1000mm, strongly stirring the high-temperature melt by blown oxygen-enriched air and participating in reaction, greatly optimizing gas-liquid-solid reaction conditions, strengthening the progress of various reactions in the furnace, producing high-temperature high-concentration antimony-containing flue gas and high-temperature melt, allowing more than 75% of antimony to enter the flue gas, allowing the high-temperature melt to flow to a front bed through a slag channel for automatic layering, wherein the upper layer is furnace slag, the middle layer is antimony sulfonium, and the bottom layer is crude antimony;
(1) oxidizing antimony sulfide in the ore particles in the step 2) into antimony oxide to form high-temperature high-concentration antimony-containing flue gas, allowing the high-temperature high-concentration antimony-containing flue gas to enter a smoke dust settling chamber through a gooseneck when the high-temperature high-concentration antimony-containing flue gas passes through a furnace top, and performing evaporative cooling to obtain antimony trioxide powder, or allowing the high-temperature high-concentration antimony-containing flue gas to enter the smoke dust settling chamber through the gooseneck when the high-temperature high-concentration antimony-containing flue gas passes through the furnace top, performing evaporative cooling, performing surface cooling, and collecting dust by using a cloth bag to obtain antimony trioxide powder, and conveying the treated flue gas to an acid making system to prepare acid;
(2) forming ferrosilicon-calcium ternary system slag by the granular ore, cobblestones and iron ore in the step 2), allowing the slag to flow into a front bed through a slag passage at the bottom of an oxygen-enriched side-blown volatilization furnace to perform gravity separation, and then discharging the slag periodically through a front bed slag tap, keeping the temperature of the front bed at 1200 ℃ by using natural gas, performing water quenching to form water-quenched slag, separating antimony matte, returned materials and crude antimony, wherein the slag contains 0.4-1.0% of antimony, the antimony matte and the crude antimony contain more than 21% of antimony, the crude antimony contains more than 60% of silver, the antimony matte is discharged through the front bed antimony tap, the antimony matte and the returned materials are returned to the step 1) for production, and the crude antimony is returned to the step 2) for production or enters a subsequent reverberatory furnace for treatment;
(3) the flue gas containing more than or equal to 15 percent of sulfur permeates through the cloth bag to collect dust, enters an acid making system, and is trapped and oxidized by the acid making system to ensure that most of SO 2 Converting into sulfuric acid, and removing residual SO from residual flue gas in a desulfurization system 2 After that, the tail gas is exhausted.
Example 3:
an antimony smelting method adopting oxygen-enriched side-blown column smelting comprises the following steps:
1) And (3) granulating: antimony concentrate, quicklime powder and water are uniformly mixed according to the weight ratio of 9.5;
2) Feeding materials into a furnace: feeding the coke, iron ore, cobblestones, return materials and the granulated ore obtained in the previous step into an oxygen-enriched side-blown volatilization furnace according to the weight ratio of 190 to 920, wherein the comprehensive silicate gangue components in the materials fed into the furnace through the bottom, the side and the top of the furnace meet the following ratio: si0 2 Fe0: ca0=1:0.9, wherein after the materials are weighed and measured by hoppers, the materials are conveyed to a material clock of a feeding port at the top of an oxygen-enriched side-blown volatilization furnace through a transfer belt, the materials are fed into the oxygen-enriched side-blown volatilization furnace twice through a fuel solvent and ore particles of the material clock, the materials are fed once every 15 minutes and are continuously fed for 24 hours, and the materials are subjected to melting, dissociation, desulfurization, oxidation, volatilization and slagging reactions in the furnace;
3) And (3) volatilizing and smelting in an oxygen-enriched side-blown volatilization furnace: after the material is fed into the furnace, oxygen-enriched air with 25% oxygen content is continuously blown into the furnace, and the pressure is controlled to be 12kPa, flow rate 130m 3 The temperature in the furnace is controlled at 1450 ℃, the height of a material column is 800-1000mm, blown oxygen-enriched air intensively stirs the high-temperature melt and participates in the reaction, the gas-liquid-solid reaction condition is greatly optimized, the progress of various reactions in the furnace is enhanced, high-temperature high-concentration antimony-containing flue gas and high-temperature melt are produced, more than 75% of antimony enters the flue gas, the high-temperature melt flows to a front bed through a slag channel and is automatically layered, the upper layer is furnace slag, the middle layer is antimony matte, and the bottom layer is crude antimony;
(1) oxidizing antimony sulfide in the ore particles in the step 2) into antimony oxide to form high-temperature high-concentration antimony-containing flue gas, allowing the high-temperature high-concentration antimony-containing flue gas to enter a smoke dust settling chamber through a gooseneck when the high-temperature high-concentration antimony-containing flue gas passes through a furnace top, and performing evaporative cooling to obtain antimony trioxide powder, or allowing the high-temperature high-concentration antimony-containing flue gas to enter the smoke dust settling chamber through the gooseneck when the high-temperature high-concentration antimony-containing flue gas passes through the furnace top, performing evaporative cooling, performing surface cooling, and collecting dust by using a cloth bag to obtain antimony trioxide powder, and conveying the treated flue gas to an acid making system to prepare acid;
(2) the granular ore, cobblestones and iron ore in the step 2) form ferrosilicon-calcium ternary system slag, the slag flows into a front bed through a slag passage at the bottom of an oxygen-enriched side-blown volatilization furnace and is subjected to gravity separation, and then the slag is discharged periodically through a slag discharge port of the front bed, the front bed is insulated by natural gas at 1200 ℃, water quenching is performed to form water-quenched slag, antimony matte, returned materials and crude antimony are separated, the slag contains 0.4-1.0% of antimony, the antimony in the antimony matte and the crude antimony contains more than 21% of antimony, the crude antimony contains more than 60% of silver, the antimony matte is discharged through an antimony discharge port of the front bed, the antimony matte and the returned materials are returned to the step 1) for production, and the crude antimony is returned to the step 2) for production or is subjected to subsequent reverberatory furnace treatment;
(3) the flue gas containing more than or equal to 15 percent of sulfur permeates a cloth bag to collect dust, enters an acid making system, and is trapped and oxidized by the acid making system to ensure that most SO 2 Converting into sulfuric acid, and removing residual SO from residual flue gas in a desulfurization system 2 After that, the tail gas is exhausted.
Comparative example 1:
the process for smelting antimony continuously by using a bottom-blowing molten pool is different from the process of example 1 in that:
uniformly mixing the coke, the iron ore, the cobblestones, the return materials and the granular ore obtained in the previous step in a weight ratio of 190 to 135; the supplied gas is combusted to release heat, the furnace temperature of the antimony reduction furnace is ensured, the gas participates in oxidation and reduction reactions of furnace materials, and the melt is stirred violently, so that the furnace materials react rapidly to produce reducing slag, crude antimony and flue gas; the reducing slag returns to the step 1) to participate in the burdening of the bottom blowing oxidation smelting furnace; the obtained flue gas is emptied after cooling and dust collection, and the flue dust obtained after flue gas purification and the flue dust obtained in the step 1) are combined and granulated and then return to a bottom blowing antimony smelting furnace; the obtained crude antimony is sent to subsequent procedures for refining into finished antimony.
Comparative example 2:
compared with the embodiment 1, the height of the material column in the step 3) is controlled to be 3-25mm by controlling the blowing of the oxygen-enriched air, and the rest is the same as the embodiment 1.
Comparative example 3:
compared with the embodiment 1, the method is the same as the embodiment 1 except that after the materials in the step 3) are put into the furnace, oxygen-enriched air with the oxygen content of 35 percent is continuously blown into the furnace through the bottom part and the side part (lack of the top part) of the furnace.
As a result:
and (4) analyzing results:
1. compared with the comparative example 1, the embodiment shows that the hearth of the existing molten pool smelting technology mainly adopts high-temperature liquid melt, the liquid melt is solidified due to the fact that a large amount of antimony sulfide volatilizes to carry away heat in the furnace, and finally, antimony in antimony matte and crude antimony is low, and high-temperature flue gas SO is generated 2 Is low.
2. Compared with the comparative example 2, the embodiment shows that the hearth of the oxygen-enriched side-blown volatilization furnace adopts a columnar smelting mode which takes solid particles as main materials, the fluctuation of the material columns in the furnace is controlled between 800 and 1000mm, oxygen-enriched air with the oxygen content of 35 percent is blown into the furnace, the air consumption is greatly reduced, on one hand, the smoke sulfur concentration is improved, on the other hand, sulfides in the furnace are quickly oxidized and release heat, so that the coke consumption is reduced, and tests prove that the coke can be reduced to below 20 percent (coke/antimony concentrate powder in the furnace).
3. Compared with the comparative example 3, the embodiment shows that in order to ensure that the volatile sulfide in the blast furnace can be completely oxidized, a large amount of air leaks in the system, so that the sulfur content in flue gas is reduced, the oxygen-enriched air with the oxygen content of 25-35% is blown into the blast furnace from the top of the blast furnace, so that the volatile sulfide in the blast furnace is rapidly oxidized, and on one hand, the sulfide is ensured to be completely oxidized; on the other hand, the air consumption is reduced, and the sulfur content of the flue gas is improved.
The above examples are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the invention.
Claims (6)
1. An antimony smelting method adopting oxygen-enriched side-blown column smelting is characterized in that: the method comprises the following steps:
1) And (3) granulating: antimony concentrate, quicklime powder and water are uniformly mixed according to the weight ratio of (9-10) to (1) (0.3-0.5), are processed into granulated ore by a disc granulator, and are dried by a waste heat recovery system until the moisture content is less than 10 percent to prepare for entering a furnace;
2) Feeding materials into a furnace: feeding the coke, iron ore, cobblestones, return materials and the granulated ores obtained in the previous step into an oxygen-enriched side-blown volatilization furnace according to the weight ratio of (170-190): (135-145): (38-42): (47-53): 880-920, wherein the feeding materials and the synthetic silicate gangue components meet the following ratio: si0 2 Fe0: ca0=1 (0.7-0.9) and (0.6-0.7), feeding is carried out once every 15-20 minutes, and feeding is carried out continuously for 24 hours;
3) And (3) volatilizing and smelting in an oxygen-enriched side-blown volatilization furnace: after the material is fed into the furnace, oxygen-enriched air with 25-35% of oxygen content is continuously blown into the furnace through the bottom, the side and the top of the furnace, the pressure is controlled at 10-15kPa, and the flow rate is 110-130m 3 Min, controlling the temperature in the furnace to be1350-1450 deg.c and material column height of 800-1000mm; the blown oxygen-enriched air intensively stirs the high-temperature melt and participates in the reaction, the gas-liquid-solid reaction condition is optimized, the proceeding of various reactions in the furnace is strengthened, high-temperature high-concentration antimony-containing smoke and high-temperature melt are produced, more than 75% of antimony enters the smoke, the high-temperature melt flows to a front bed through a slag channel and is automatically layered, the upper layer is furnace slag, the middle layer is antimony matte, and the bottom layer is crude antimony;
(1) oxidizing antimony sulfide in the ore particles in the step 2) into antimony oxide to form high-temperature high-concentration antimony-containing flue gas, performing flue gas sedimentation and evaporative cooling to obtain antimony trioxide powder, or performing flue gas sedimentation, evaporative cooling, surface cooling and cloth bag dust collection to obtain antimony trioxide powder, and conveying the treated flue gas to an acid making system for making acid;
(2) forming ferrosilicon-calcium ternary system slag by the granular ore, cobblestones and iron ore in the step 2), flowing into a front bed through a slag passage at the bottom of the oxygen-enriched side-blown volatilization furnace, performing gravity separation, then discharging the slag periodically through a front bed slag tap, performing water quenching to form water-quenched slag, separating antimony matte, returned materials and crude antimony, discharging the antimony matte through a front bed antimony discharging matte tap, returning the antimony matte and the returned materials to the step 1) for production, and returning the crude antimony to the step 2) for production or to a subsequent reverberatory furnace for treatment;
(3) the flue gas containing more than or equal to 15 percent of sulfur permeates through the cloth bag to collect dust, enters an acid making system, and is trapped and oxidized by the acid making system to ensure that most of SO 2 Converting into sulfuric acid, and removing residual SO from residual flue gas in desulfurizing system 2 After that, the tail gas is exhausted.
2. The antimony smelting method adopting oxygen-enriched side-blown column smelting according to claim 1, characterized in that: the antimony concentrate, the quicklime powder and the water in the step 1) are mixed according to the weight ratio of 9; the granularity of the ore particles in the step 1) is 10-20 mm.
3. The antimony smelting method adopting oxygen-enriched side-blown column smelting according to claim 1, characterized in that: feeding the materials in the step 2) into a furnace, wherein the materials in the furnace are fully mixed according to the weight ratio of 180The silicate-containing gangue satisfies the following proportion: si0 2 Fe0: ca0=1:0.8, weighing and metering by each bin through a hopper, conveying to a bell of a charging port at the top of the oxygen-enriched side-blown volatilization furnace through a transfer belt, feeding into the oxygen-enriched side-blown volatilization furnace twice through a bell minute fuel solvent and ore particles, feeding once every 15 minutes, and continuously feeding for 24 hours.
4. The antimony smelting method adopting oxygen-enriched side-blown column smelting according to claim 1, characterized in that: and 3) volatilizing and smelting in the oxygen-enriched side-blown volatilization furnace, namely continuously blowing oxygen-enriched air with the oxygen content of 35% into the furnace after the material is fed into the furnace, controlling the temperature in the furnace to be 1400 ℃, and controlling the height of a material column to be 800-1000mm.
5. The antimony smelting method adopting oxygen-enriched side-blown column smelting as claimed in claim 1, is characterized in that: the flue gas sedimentation in the step 3) refers to that the high-temperature high-concentration antimony-containing flue gas enters a flue gas sedimentation chamber through a gooseneck when passing through the furnace top.
6. The antimony smelting method adopting oxygen-enriched side-blown column smelting according to claim 1, characterized in that: and 3) preserving the temperature of the front bed in the step 3) by adopting natural gas at 1200 ℃.
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