CN110331279B - Method for directly volatilizing and recycling antimony oxide by roasting antimony sulfide concentrate with microwaves - Google Patents
Method for directly volatilizing and recycling antimony oxide by roasting antimony sulfide concentrate with microwaves Download PDFInfo
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- CN110331279B CN110331279B CN201910626967.3A CN201910626967A CN110331279B CN 110331279 B CN110331279 B CN 110331279B CN 201910626967 A CN201910626967 A CN 201910626967A CN 110331279 B CN110331279 B CN 110331279B
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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
- C22B1/02—Roasting processes
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method for directly volatilizing antimony sulfide from antimony sulfide concentrate by microwave roasting, belonging to the technical field of antimony metallurgy. In order to solve the problems of long flow, high energy consumption, large consumption, low recovery rate of metallic antimony and high cost in the existing antimony pyrometallurgy technology, the method for directly volatilizing antimony sulfide from the antimony sulfide concentrate by microwave roasting comprises the following steps: 1) Antimony concentrate is used as a raw material; 2) Placing crushed and ground antimony sulfide concentrate into a quartz boat, and placing the quartz boat into a microwave heating furnace chamber; 3) Starting microwaves, and simultaneously blowing oxygen-enriched air, and oxidizing and roasting to generate antimonous oxide in the process; 4) And due to the characteristic that the antimonous oxide is easy to sublimate, the generated antimonous oxide smoke is discharged through the air outlet of the microwave reactor, and the cooled smoke is collected by the dust recovery device to obtain the antimonous oxide with higher purity. The invention selects microwaves as a heat source, and has the advantages of short process flow, low energy consumption, high heating efficiency, simplicity, easiness in operation and the like.
Description
Technical Field
The invention relates to a method for directly volatilizing antimony sulfide from antimony sulfide concentrate by microwave roasting, belonging to the technical field of antimony metallurgy.
Background
The prior method for smelting antimony comprises a fire method and a wet method, but mainly adopts the fire method for smelting antimony in industry. In the fire method, most enterprises adopt volatile roasting (smelting) -reduction smelting, and the main characteristics are low material column, thin material layer and high coke rate, SO that the process has long flow, high energy consumption and low concentration SO 2 Smoke pollution and the like. The most widely used is the blast furnace volatile smelting process, which mainly uses Sb in antimony sulfide concentrate 2 S 3 Oxidation to volatile Sb by oxidative calcination 2 O 3 . Volatilized Sb 2 O 3 And (3) entering the flue gas, and further cooling and recycling the flue gas to obtain crude antimony oxide. The process has the advantages of long technological process, high energy consumption and low production efficiency.
In order to solve the problems of high energy consumption and low production efficiency, patent CN 103173637B discloses an oxygen-enriched smelting method of antimony sulfide concentrate and a side-blown furnace, wherein the method comprises the steps of proportioning, granulating and then adding the antimony sulfide concentrate into the side-blown furnace for oxygen-enriched oxidation. The method realizes self-heating smelting of the antimony sulfide concentrate, and reduces energy consumption. But the preparation and granulation are firstly carried out, and the process is complex.
Patent CN 107858530A discloses a method for oxygen-enriched smelting of antimony sulfide ore, which increases production efficiency, but requires crushing and granulating of antimony sulfide ore during smelting and preheating of oxygen-enriched air. Resulting in long process flow and inconvenient operation.
Because of the defects and shortcomings, the methods are not applied to industrial production, and the main antimony smelting process in the current stage of China is also blast furnace volatilization smelting. Therefore, there is a need for an antimony-smelting process with short process flow and low energy consumption.
Microwave metallurgy, which is a novel green metallurgical technology, has been applied to metallurgical processes such as ore dressing, ore grinding, drying, roasting, calcining, sintering, reduction, oxidation, smelting, purification, and purification. Compared with the traditional heating mode, the heating device has the following characteristics: (1) The selective heating is performed, the heating rate is high, and the heating efficiency is high; (2) environmental friendly; (3) low energy consumption. Patent CN 105948123A discloses a method for preparing low-sulfur molybdenum trioxide, which achieves efficient roasting of molybdenite by using microwave pretreatment. Comprehensively utilizes the advantages of microwave heating.
The microwave is used as a green efficient heating mode, and the material is directly heated through the energy dissipation of the microwave in the material, so that the sample is heated through the microwave, the heat transfer direction of the sample is from inside to outside, and compared with the traditional heating mode from outside to inside, the microwave heating mode is more beneficial to volatilization of antimony oxide. In addition, antimony sulfide concentrate has higher dielectric constant (8-30) and dielectric loss (0.2-0.8) in a microwave frequency band, has stronger response to microwaves, and the dielectric constant (4-12) of other components in minerals has weaker response to microwaves, so that the characteristic of microwave selective heating can be well utilized. Thus, the antimony sulfide concentrate can absorb waves preferentially to perform oxidation reaction, and the antimony oxide product can reach the melting point (655 ℃) rapidly and is easier to volatilize. Therefore, the microwave is applied to roasting the antimony sulfide concentrate to volatilize antimony sulfide therein, and the method has wide application prospect.
Disclosure of Invention
Aiming at the problems of long flow, high energy consumption, high cost and serious environmental pollution of a method for volatilizing and smelting antimony sulfide concentrate by a blast furnace, the invention provides a process method for directly volatilizing antimony sulfide by roasting the antimony sulfide concentrate by microwaves.
A method for directly volatilizing antimony sulfide by roasting antimony sulfide concentrate by microwaves comprises the following specific steps:
(1) Selecting antimony concentrate as a starting material, wherein the mass percentage of Sb is 35-55%, and the mass percentage of S is more than 20%;
(2) Grinding the antimony concentrate material selected in the step (1), putting the antimony sulfide concentrate with the granularity of 40-200 meshes into a quartz boat, tiling the antimony sulfide concentrate to 2.5-5.0 cm, and putting the antimony sulfide concentrate into a heating furnace chamber with the microwave power of 0-20 kW and the frequency of 2450Hz +/-50 Hz or 915Hz +/-50 Hz;
(3) Starting the microwave at 1.5-2.0 m 3 Air is blown in at the speed of/h, the microwave output power is regulated, the temperature of the ground antimony sulfide concentrate is quickly increased to 200-300 ℃ from the room temperature at the temperature rising rate of 50-100 ℃/min in the first temperature rising stage of the roasting process in the step (3) of 50-100/min, and the temperature is kept for 30-60 min; the second temperature rising stage rises to the roasting temperature at a temperature rising rate of 20-40 ℃/min; rapidly heating to 950-1050 ℃ at a speed, and preserving heat for 1-2 hours;
(4) Smoke dust is recovered, smoke gas generated in the rapid heating and roasting processes is discharged through an air outlet of a microwave reactor, the smoke dust is collected, the collected smoke dust is crude antimony oxide powder containing antimony trioxide powder, and the mass percent of the antimony is more than 80%;
(5) And (3) after the heat preservation in the step (2) is carried out for 1-2 hours, the microwaves are closed, and the residual slag is taken out after natural cooling.
Further, the antimony sulfide concentrate in the step (1) comprises the following components in percentage by mass: 42.444% of antimony, 35.075% of sulfur, 17.184% of silicon, 5.026% of iron, 0.122% of arsenic, 0.090% of lead, 0.060% of zinc;
further, in the step (3), during the heating process, the antimony sulfide in the antimony sulfide concentrate reacts as follows and enters the flue gas:
further, the crude antimony oxide obtained by the recovery of the soot in the step (3) can be used for further reduction to obtain metallic antimony.
The beneficial effects of the invention are as follows:
(1) The method adopts microwaves to directly bake the antimony sulfide concentrate to volatilize antimony sulfide in the antimony sulfide concentrate, and has short process flow, small environmental pollution and easier operation;
(2) The antimony sulfide concentrate has the characteristics of higher dielectric constant and dielectric loss in a microwave frequency band, stronger response to microwaves and microwave selective heating, so that the material heating efficiency is high, the reaction rate is high, and the obtained product has good quality;
(3) Due to the characteristic of microwave 'heating', the whole material is heated uniformly, no temperature gradient is generated in the oxidation process, and the components and the particle size of the product are uniform.
[ description of the drawings ]
Fig. 1 is a schematic view of a microwave tube type oven apparatus used in the present invention.
In the figure: the device comprises a 1-oxygen-enriched air storage tank, a 2-flow controller, a 3-air inlet, a 4-quartz tube, a 5-quartz crucible, a 6-digital display system, a 7-current and voltage display instrument, an 8-microwave power controller, a 9-emergency stop button, a 10-air outlet and a 11-dust recovery device.
FIG. 2 is a flow chart of an embodiment of the present invention.
Detailed description of the preferred embodiments
The invention will be further described with reference to specific embodiments.
Example 1
Firstly grinding antimony sulfide concentrate into 150 meshes, then taking 40g of the ground antimony sulfide concentrate into a quartz boat, tiling until the thickness is 2.5cm, and placing the antimony sulfide concentrate in a wave heating furnace chamber.
Turning on the power supply at the same time of 1.5cm 3 And (3) blowing air into the microwave cavity at the speed of/h, and regulating the output microwave power to be 6kW and the output frequency to be 2450MHz +/-50 Hz through a microwave controller of the microwave equipment.
And observing the temperature change rate in real time through a device display, controlling the heating rate to be 50 ℃/min, rapidly heating to 200 ℃, preserving heat for 40min, heating to 950 ℃ at the temperature rise rate of 20 ℃/min, and recovering flue gas generated by roasting in the heating process. Adjusting microwave power, controlling heating temperature at 950 deg.C, and maintaining the temperature for 40min.
After the roasting is finished, the air blowing is stopped and the microwaves are turned off. And taking out the residue after natural cooling. And (5) recycling and analyzing the cooled flue gas. The mass percentage of the antimony contained in the collected antimony oxide powder is more than 80 percent.
Example 2
Firstly grinding antimony sulfide concentrate into 180 meshes, then taking 60g of the ground antimony sulfide concentrate into a quartz boat, tiling until the thickness is 3.0cm, and placing the antimony sulfide concentrate in a wave heating furnace chamber.
Turning on the power supply at the same time of 1.8cm 3 And (3) blowing air into the microwave cavity at the speed of/h, and regulating the output microwave power to be 12kW and the output frequency to be 2450MHz +/-50 Hz through a microwave controller of the microwave equipment.
And observing the temperature change rate in real time through a device display, controlling the heating rate to be 70 ℃/min, rapidly heating to 250 ℃, preserving heat for 40min, heating to 1000 ℃ at the temperature rise rate of 40 ℃/min, and recovering flue gas generated by roasting in the heating process. Adjusting microwave power, controlling heating temperature at 1000 deg.C, and maintaining temperature for 50min.
After the roasting is finished, the air blowing is stopped and the microwaves are turned off. And taking out the residue after natural cooling. And (5) recycling and analyzing the cooled flue gas. The mass percentage of the antimony contained in the collected antimony oxide powder is more than 80 percent.
Example 3
Firstly grinding antimony sulfide concentrate into 200 meshes, then taking 90g of the ground antimony sulfide concentrate into a quartz boat, tiling until the thickness is 4.0cm, and placing the antimony sulfide concentrate in a wave heating furnace chamber.
Turning on the power supply at the same time of 1.8cm 3 And (3) blowing air into the microwave cavity at the speed of/h, and regulating the output microwave power to be 18kW and the output frequency to be 2450MHz +/-50 Hz through a microwave controller of the microwave equipment.
And observing the temperature change rate in real time through a device display, controlling the heating rate to be 100 ℃/min, rapidly heating to 300 ℃, preserving heat for 50min, heating to 1050 ℃ at the temperature rise rate of 50 ℃/min, and recovering flue gas generated by roasting in the heating process. Adjusting microwave power to control heating temperature at 1050 deg.C, and maintaining for 60min.
After the roasting is finished, the air blowing is stopped and the microwaves are turned off. And taking out the residue after natural cooling. And (5) recycling and analyzing the cooled flue gas. The mass percentage of the antimony contained in the collected antimony oxide powder is more than 85 percent.
Claims (7)
1. A method for directly volatilizing and recycling antimony oxide by roasting antimony sulfide concentrate with microwaves is characterized by comprising the following specific steps:
(1) Selecting antimony concentrate as a starting material, wherein the mass percentage of Sb is 35-55%, and the mass percentage of S is more than 20%;
(2) Grinding the antimony concentrate material selected in the step (1), putting antimony sulfide concentrate into a quartz boat, and putting the quartz boat into a microwave heating furnace chamber with microwave frequency of 2450MHz or 915 MHz;
(3) Starting microwaves, simultaneously blowing oxygen-enriched air, adjusting the output power of the microwaves, heating the ground antimony sulfide concentrate from room temperature to 850-1050 ℃ in two stages, roasting, and preserving heat for 0.5-2 h;
(4) Smoke dust is recovered, smoke gas generated in the heating and roasting processes is discharged through an air outlet of the microwave reactor, and the smoke dust is collected; after the heat preservation in the step (2) is carried out for 0.5 to 2 hours, the microwaves are closed, and the residual slag is taken out after natural cooling;
in the step (2), the particle size range of the antimony sulfide concentrate is 40-200 meshes, wherein the proportion of the particle size of the antimony sulfide concentrate to the particle size of the antimony sulfide concentrate is 200 meshes is more than 80%;
in the step (3), the reaction of the antimony sulfide in the antimony sulfide concentrate in the roasting process is as follows:
2Sb 2 S 3 +9O 2 ＝2Sb 2 O 3 +6SO 2 ；
2Sb 2 O 3 +2O 2 ＝2Sb 2 O 5 ；
generated Sb 2 O 3 And Sb (Sb) 2 O 5 And entering the flue gas.
2. The method for directly volatilizing and recycling antimony oxide by roasting antimony sulfide concentrate with microwaves according to claim 1, wherein the method comprises the following steps: in the step (2), the thickness of the antimony sulfide concentrate laid in a quartz boat is 2.5-5.0 cm.
3. The method for directly volatilizing and recovering antimony oxide by roasting antimony sulfide concentrate with microwave according to claim 1, wherein the velocity of bubbling oxygen-enriched air in the step (3) is 1.5-2.0 m 3 /h。
4. The method for directly volatilizing and recycling antimony oxide by roasting antimony sulfide concentrate with microwaves according to claim 1, wherein the microwave output power in the step (3) is 0-20 kW, and the frequency is 2450Hz + -50 Hz or 915Hz + -50 Hz.
5. The method for directly volatilizing and recycling antimony oxide by roasting antimony sulfide concentrate with microwaves according to claim 1, wherein the first temperature rising stage in the roasting process in the step (3) is characterized in that the temperature rises to 300-400 ℃ at a temperature rising rate of 50-100 ℃/min, and the temperature is kept for 30-60 min; and the second temperature rising stage rises to the roasting temperature at a temperature rising rate of 20-40/min.
6. The method for directly volatilizing and recovering antimony oxide by roasting antimony sulfide concentrate with microwave according to claim 1, wherein the roasting temperature in the step (3) is preferably 950-1050 ℃.
7. The method for directly volatilizing and recovering antimony oxide by roasting antimony sulfide concentrate with microwave according to claim 1, wherein in the step (4), after the smoke is discharged through the air outlet, the smoke is collected by a dust recovery device or an electric dust collector, and the obtained antimony compound can be used for further reduction to obtain metallic antimony.
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| CN115259221B (en) * | 2022-08-31 | 2023-10-31 | 云南民族大学 | Method for preparing nano antimony trioxide by oxygen-enriched blowing under microwave field |
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