CN115259221A - Method for preparing nano antimony trioxide by oxygen-enriched blowing under microwave field - Google Patents
Method for preparing nano antimony trioxide by oxygen-enriched blowing under microwave field Download PDFInfo
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- CN115259221A CN115259221A CN202211054403.5A CN202211054403A CN115259221A CN 115259221 A CN115259221 A CN 115259221A CN 202211054403 A CN202211054403 A CN 202211054403A CN 115259221 A CN115259221 A CN 115259221A
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 238000000034 method Methods 0.000 title claims abstract description 58
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000001301 oxygen Substances 0.000 title claims abstract description 55
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 55
- 238000007664 blowing Methods 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 31
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 238000003892 spreading Methods 0.000 claims description 8
- 230000007480 spreading Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052569 sulfide mineral Inorganic materials 0.000 description 16
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 14
- 229910052787 antimony Inorganic materials 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 235000012239 silicon dioxide Nutrition 0.000 description 12
- 239000010453 quartz Substances 0.000 description 11
- 238000003723 Smelting Methods 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
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- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/004—Oxides; Hydroxides; Oxyacids
- C01G30/005—Oxides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention discloses a method for preparing nanometer antimony trioxide by oxygen-enriched blowing under a microwave field, belonging to the technical field of nanometer materials. The preparation method comprises the following steps: and flatly paving the crushed and sieved antimony sulfide ore in a roasting container, introducing oxygen-enriched air with the oxygen volume fraction of more than 20%, roasting in a microwave field, wherein the roasting is divided into a heating stage and a heat preservation stage, continuously blowing by using the oxygen-enriched air in the roasting process, and collecting the generated nano antimony trioxide. The preparation method provided by the invention has the advantages of simple steps, low equipment requirement and low roasting temperature requirement, the size of the prepared nano antimony trioxide is between 100 and 400nm, and the maximum volatilization rate of the antimony trioxide is more than 70 percent.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a method for preparing nano antimony trioxide by oxygen-enriched blowing under a microwave field.
Background
Antimony trioxide is one of the oxides of antimony and has wide application in industrial production. Antimony trioxide is commonly used in flame retardants, catalysts, heat stabilizers, alloying additives, ceramic additives, and specifically relates to a plurality of industries such as chemistry, manufacturing, construction, and the like. The demand of the flame retardant industry for antimony trioxide is huge, and more than 60 percent of antimony products are used for manufacturing the flame retardant globally.
The utilization of antimony ore resources mainly comprises two types of pyrometallurgical smelting and wet leaching, and more than 95% of enterprises at the present stage mainly adopt pyrometallurgical smelting. The main process is divided into two stages of oxidation volatilization in a volatilization furnace and reduction in a reverberatory furnace. In the oxidation stage, part of primary antimony ore with higher grade is placed in a vertical shaft type volatilization furnace for volatilization smelting according to the characteristic that the antimony trioxide is easy to volatilize, and then the volatilized antimony trioxide is collected. The reduction stage is mainly to add a certain amount of reducing agent and fused salt to carry out reduction smelting on volatilized antimony trioxide to prepare the metal antimony ingot. However, conventional pyrometallurgical smelting often requires higher smelting temperatures, which requires the addition of high quality metallurgical coke during compounding to provide the necessary temperatures for chemical reactions and volatilization. This increases the cost of the primary antimony ore utilization process and also increases CO 2 The emission of gas does not meet the requirements of global sustainable development. Although the traditional pyrogenic process can also obtain antimony trioxide with good purity to a certain extent, the antimony trioxide obtained by the traditional pyrogenic process has poor flame retardant property. The main reason is that the size of the antimony trioxide prepared by the pyrogenic process is too large, and the antimony trioxide cannot be directly used as a flame retardant material due to the influence of potential factors such as size effect, quantum size effect, surface effect and the like. Before antimony trioxide obtained by traditional pyrometallurgical smelting is used as a flame-retardant material, the antimony trioxide still needs to be subjected to modification, recrystallization, refinement and other treatments.
Antimony trioxide of smaller size tends to be more excellent in flame retardancy. Therefore, scholars at home and abroad have conducted a great deal of research on the preparation of small-size antimony trioxide. Some methods commonly used in material synthesis, such as liquid phase method, gas phase method, solid phase method, etc., have been studied in the preparation of small-sized antimony trioxide. The patent CN 113321240A "a preparation method of high-dispersibility nanometer antimony trioxide" discloses a method for preparing high-dispersibility nanometer antimony trioxide, which comprises the steps of taking antimony trichloride as a raw material, obtaining high-purity micron-sized antimony trioxide by an alcoholysis method and a hydrothermal method under an alkaline condition, and controlling the form and the particle size of the antimony trioxide by a solvothermal method and surfactant treatment; patent CN 112499680A "preparation method of spherical nano antimony trioxide" discloses that ethylene glycol antimony powder is used as a raw material, and ultrasonic dispersion is performed in an ethanol solution to obtain a solution a. Adding a certain amount of ultrapure water into the beaker, heating in water bath, and adjusting the pH value to subacidity by using an acidic medium to obtain a solution B. And reacting the solution A and the solution B under certain conditions to obtain a precipitate, and centrifuging and drying the precipitate to finally obtain the spherical nano antimony trioxide powder. Although the two methods obtain the nano-scale antimony trioxide, the requirements on raw materials are high, and analytical reagents with higher purity are required to be used as reaction raw materials in the preparation. In addition, the solvent process also produces a large amount of waste liquid at the same time of production. The subsequent waste liquid treatment process can increase the production cost, and if the waste liquid is not properly treated, the environment pollution can be caused.
Disclosure of Invention
The invention aims to provide a method for preparing nano antimony trioxide by oxygen-enriched blowing in a microwave field. Aims to replace the traditional coal-based fuel with a microwave heat source and reduce CO 2 Is discharged. When small-size antimony trioxide is obtained, antimony sulfide ore is utilized cleanly and efficiently, and the problems of high coke rate, high raw material requirement and large product size in the traditional antimony trioxide preparation are solved.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes of the invention is as follows: the method for preparing the nano antimony trioxide by oxygen-enriched blowing under a microwave field comprises the following steps:
the method comprises the steps of spreading crushed and sieved antimony sulfide ore in a roasting container, introducing oxygen-enriched air with oxygen volume fraction of more than 20%, roasting in a microwave field at 600-800 ℃, wherein the roasting is divided into a temperature rise stage and a heat preservation stage, continuously blowing oxygen-enriched air in the roasting process, and collecting generated nano antimony trioxide.
Preferably, the sieving is 100-200 mesh sieving; the grade of the antimony sulfide ore is 40-70%; the thickness of the flat laying is 1.5-5 cm.
Preferably, the blowing air flow is 0.5-2 m 3 /h。
Preferably, the microwave power of the microwave field is 0.2-15 kW, and the microwave frequency is 2450 +/-50 MHz; the heating rate of the heating stage is 20-150 ℃/min; the time of the heat preservation stage is 15-60 min.
Preferably, the step of collecting the nano antimony trioxide further comprises a tail gas absorption step.
More preferably, the absorption liquid adopted in the tail gas absorption step is 1 mol/L-8 mol/L NaOH or Ca (OH) 2 And (3) solution.
The second technical scheme of the invention is as follows: providing the nano antimony trioxide prepared by the method for preparing the nano antimony trioxide by oxygen-enriched blowing under the microwave field, wherein the size of the nano antimony trioxide is between 100 and 400 nm.
The invention has the following beneficial technical effects:
compared with the roasting temperature (over 1000 ℃) of a conventional volatilization furnace, the method for preparing the spherical nano antimony trioxide by oxygen-enriched blowing under the microwave field needs the temperature of only 600-800 ℃, and has obvious low-temperature smelting advantage. The specific advantage of low-temperature smelting is that the heat conduction direction is from inside to outside in the microwave heating process, and the volatilization direction of the antimony trioxide is from inside to outside, so that the interface resistance in the volatilization process is smaller. In addition, the microwave heating process has the advantages of rapid heating, hot spot effect and the like, and the local temperature in the mineral can rapidly reach the temperature required by volatilization of the antimony trioxide, so that the beneficial effect of low-temperature smelting is achieved. The invention does not depend on the traditional coal-based fuel and reducesReduce CO 2 The discharge of (2) is beneficial to sustainable development. The prepared spherical nano antimony trioxide is smaller than that prepared by a conventional volatilization furnace, and the size range is within 100-400 nm. The raw material for preparing the spherical nano antimony trioxide is antimony sulfide ore with the antimony grade of 40-70%, and the preparation method has the characteristics of strong raw material adaptability, low requirement and the like, and the volatilization rate of the whole process for preparing the spherical nano antimony trioxide by oxygen-enriched blowing is 70-90%.
Drawings
FIG. 1 is a diagram of an apparatus for preparing spherical nano antimony trioxide by oxygen-enriched blowing under a microwave field.
FIG. 2 is an SEM image of nano antimony trioxide prepared in example 1 of the present invention.
FIG. 3 is a size distribution diagram of nano antimony trioxide prepared in example 1 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated value or intervening value in a stated range, and any other stated or intervening value in a stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The invention provides a method for preparing spherical nano antimony trioxide by oxygen-enriched blowing in a microwave field, which comprises the following steps:
(1) Crushing antimony sulfide ore with antimony grade of 40-70%, sieving with 100-200 mesh sieve to remove large particle impurities brought in the process of antimony sulfide ore mining and ore dressing.
(2) And paving the antimony sulfide mineral in a quartz boat, wherein the thickness of the material is 1.5-5 cm. In the process of tiling, the antimony sulfide minerals are normally dispersed in the quartz boat, and briquetting treatment on the antimony sulfide minerals is not needed.
(3) And (3) putting the quartz boat containing the antimony sulfide minerals into a tubular microwave oven loaded with a quartz tube for oxidation, volatilization and roasting, wherein the quartz tube is made of silicon dioxide with good microwave transmission performance. Before roasting, oxygen-enriched air is blown in at a certain flow rate, and the equipment flow chart of the oxygen-enriched blowing process is shown in figure 1. In the roasting process, the gas flow range is 0.5-2 m 3 /h。
(4) Before the oxidizing roasting, the temperature control mode of the tubular furnace is set as automatic temperature control. The microwave roasting power is 0.2-15 kW, and the microwave frequency is 2450 +/-50 MHz. The temperature measurement mode is selected as infrared temperature control, and magnetron cooling water and antimony trioxide dust condenser pipe circulating water of the microwave tube furnace are started.
(5) And opening the microwave tube type furnace for oxidizing roasting on the premise that gas is discharged from the tail gas absorption bottle. The first stage of roasting is a heating-up stage, and the heating-up rate in the heating-up process is 20-150 ℃/min. After the equipment reaches the required roasting temperature, setting the heat preservation time and entering a heat preservation stage. The roasting temperature is 600-800 ℃, and the heat preservation time is 15-60 min.
(6) The nanometer antimony trioxide prepared by oxygen-enriched blowing is collected in a collecting bottle, and the purity of the nanometer antimony trioxide is more than 97%. SO generated in the whole process 2 The gas is absorbed by a tail gas absorption bottle, and the tail gas absorption solution is NaOH solution or Ca (OH) with the concentration of 1 mol/L-8 mol/L 2 And (3) solution.
(7) And (3) closing magnetron cooling water and antimony trioxide dust condensation pipe circulating water of the microwave tube type furnace 20min after the reaction is finished, naturally cooling the instrument to room temperature, and then closing the power supply of the instrument.
The method for calculating the volatilization rate of the antimony trioxide of the roasted sample after the steps is as follows:
M g ＝m 2 ×w 2
wherein beta is the volatilization rate m of antimony trioxide prepared by oxygen-enriched blowing under a microwave field 1 Mass m of the sample before calcination 2 The mass of the sample after roasting; w 1 Is the content of antimony sulfide in the mineral, W 2 The content of antimony trioxide in the slag phase after roasting.
The specific embodiment is as follows:
example 1
Sieving the obtained antimony sulfide mineral after mineral separation with 100 mesh sieve, spreading the antimony sulfide mineral with antimony grade of 42.8% in a quartz boat, wherein the material thickness is 2.5cm, and the flow rate of the introduced oxygen-enriched air (the volume fraction of oxygen is more than 20%) in the oxygen-enriched blowing roasting process is 1m 3 H is used as the reference value. Before the oxidizing roasting, the circulating water of the microwave tube furnace and the antimony trioxide dust condensing device is started. After the whole roasting system is ensured to be ventilated smoothly, the microwave tube type furnace is started to carry out oxygen-enriched volatilization roasting. In the roasting process, the microwave roasting frequency is 2450MHz, and the microwave roasting power in the heating process is 2kW. The selected roasting temperature is 800 ℃, and the average heating rate in the heating stage is 50 ℃/min. When the temperature reaches 800 ℃, the microwave roasting power is 0.8-2 kW, and the sample is kept warm for 30min. After the reaction was complete, the calculated volatility of antimony trioxide was 82%. The SEM image of the collected antimony trioxide is shown in figure 2, the size distribution diagram of the obtained spherical nano antimony trioxide is shown in figure 3,the particle size d is 188.18 +/-72.48 nm.
Example 2
Sieving the antimony sulfide mineral obtained after mineral separation with a 200-mesh sieve, spreading the antimony sulfide mineral with 70% antimony grade in a quartz boat, wherein the material thickness is 2.5cm, and the flow rate of the introduced oxygen-enriched air (the volume fraction of oxygen is more than 20%) in the oxygen-enriched blowing roasting process is 1m 3 H is the ratio of the total weight of the catalyst to the total weight of the catalyst. Before the oxidizing roasting, the circulating water of the microwave tube furnace and the antimony trioxide dust condensing device is started. After the whole roasting system is ensured to be ventilated smoothly, the microwave tube type furnace is started to carry out oxygen-enriched volatilization roasting. In the roasting process, the microwave roasting frequency is 2450MHz, and the microwave roasting power in the heating process is 1.8kW. The selected roasting temperature is 800 ℃, and the average heating rate in the heating stage is 70 ℃/min. When the temperature reaches 800 ℃, the microwave roasting power is 0.8-1.8 kW, and the sample is kept warm for 30min. After the reaction was complete, the calculated volatility of antimony trioxide was 90%. The obtained antimony trioxide has a particle size d of 190 +/-80 nm.
Example 3
Sieving the antimony sulfide mineral obtained after mineral separation with 100 mesh sieve, spreading the antimony sulfide mineral with antimony grade of 42.8% in a quartz boat, wherein the material thickness is 1.5cm, and the flow rate of the introduced oxygen-enriched air (the volume fraction of oxygen is more than 20%) in the oxygen-enriched blowing roasting process is 0.8m 3 H is used as the reference value. Before the oxidizing roasting, the circulating water of the microwave tube furnace and the antimony trioxide dust condensing device is started. After the whole roasting system is ensured to be ventilated smoothly, the microwave tube type furnace is started to carry out oxygen-enriched volatilization roasting. In the roasting process, the microwave roasting frequency is 2450MHz, and the microwave roasting power in the heating process is 1.8kW. The selected roasting temperature is 700 ℃, and the average heating rate in the heating stage is 35 ℃/min. When the temperature reaches 700 ℃, the microwave roasting power is 0.8-1.8 kW, and the sample is kept warm for 45min. After the reaction was complete, the calculated volatility of antimony trioxide was 78%. The obtained antimony trioxide has a particle size d of 200 +/-60 nm.
Example 4
Sieving the obtained antimony sulfide mineral after mineral separation with 200 mesh sieve, spreading the antimony sulfide mineral with 70% antimony grade in a quartz boat with material thickness of 1.5cm, and blowing with oxygen-enriched airThe flow rate of oxygen-enriched air (the volume fraction of oxygen is more than 20%) introduced in the roasting process is 0.8m 3 H is used as the reference value. Before the oxidizing roasting, the circulating water of the microwave tube furnace and the antimony trioxide dust condensing device is started. After the whole roasting system is ensured to be ventilated smoothly, the microwave tube type furnace is started to carry out oxygen-enriched volatilization roasting. In the roasting process, the microwave roasting frequency is 2450MHz, and the microwave roasting power in the temperature rise process is 1.6kW. The selected roasting temperature is 700 ℃, and the average heating rate in the heating stage is 55 ℃/min. When the temperature reaches 700 ℃, the microwave roasting power is 0.8-1.6 kW, and the sample is kept warm for 45min. After the reaction was complete, the calculated volatility of antimony trioxide was 82%. The obtained antimony trioxide is determined to have a particle size d of 210 +/-55 nm.
Example 5
Sieving the antimony sulfide mineral obtained after mineral separation with a 200-mesh sieve, spreading the antimony sulfide mineral with 42.8% of antimony grade in a quartz boat, wherein the material thickness is 1cm, and the flow rate of the introduced oxygen-enriched air (the volume fraction of oxygen is more than 20%) in the oxygen-enriched blowing roasting process is 0.8m 3 H is used as the reference value. Before the oxidizing roasting, the circulating water of the microwave tube furnace and the antimony trioxide dust condensing device is started. After the whole roasting system is ensured to be ventilated smoothly, the microwave tube type furnace is started to carry out oxygen-enriched volatilization roasting. In the roasting process, the microwave roasting frequency is 2450MHz, and the microwave roasting power in the heating process is 1.8kW. The selected roasting temperature is 600 ℃, and the average temperature rise rate in the temperature rise stage is 20 ℃/min. When the temperature reaches 600 ℃, the microwave roasting power is 0.4-1.6 kW, and the sample is kept warm for 60min. After the reaction was complete, the calculated volatility of antimony trioxide was 70%. The antimony trioxide has a particle size d of 220 +/-80 nm.
Example 6
Sieving the antimony sulfide mineral obtained after mineral separation with a 200-mesh sieve, spreading the antimony sulfide mineral with 70% antimony grade in a quartz boat, wherein the material thickness is 1cm, and the flow rate of the oxygen-enriched air (the volume fraction of oxygen is more than 20%) introduced in the oxygen-enriched blowing roasting process is 0.8m 3 H is the ratio of the total weight of the catalyst to the total weight of the catalyst. Before the oxidizing roasting, the circulating water of the microwave tube furnace and the antimony trioxide dust condensing device is started. After the whole roasting system is ensured to be ventilated smoothly, the microwave tube type furnace is opened to volatilize the oxygen-enriched airAnd (4) roasting. In the roasting process, the microwave roasting frequency is 2450MHz, and the microwave roasting power in the temperature rise process is 1.6kW. The selected roasting temperature is 700 ℃, and the average heating rate in the heating stage is 40 ℃/min. When the temperature reaches 600 ℃, the microwave roasting power is 0.4-1.6 kW, and the sample is kept warm for 60min. After the reaction was complete, the calculated volatility of antimony trioxide was 73%. The obtained antimony trioxide has the particle size d of 235 +/-90 nm through measurement.
Comparative example 1
Comparative example 1 differs from example 1 in that the oxidative roasting is carried out using a conventional tube furnace, the average rate of temperature rise during the temperature rise phase being 10 ℃/min, the roasting temperature being selected to be 1000 ℃. The size of the obtained antimony trioxide is larger than 1 mu m, and the volatilization rate of the antimony trioxide is only 78 percent.
Comparative example 2
Comparative example 2 differs from example 1 in that the oxidative roasting is carried out using a conventional tube furnace, the average rate of temperature rise during the temperature rise phase being 10 ℃/min, the roasting temperature being selected to be 900 ℃. The size of the obtained antimony trioxide is larger than 1 mu m, and the volatilization rate of the antimony trioxide is only 62 percent.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. A method for preparing nanometer antimony trioxide by oxygen-enriched blowing under a microwave field is characterized by comprising the following steps:
the method comprises the steps of spreading crushed and sieved antimony sulfide ore in a roasting container, introducing oxygen-enriched air with oxygen volume fraction of more than 20%, roasting in a microwave field at 600-800 ℃, wherein the roasting is divided into a temperature rise stage and a heat preservation stage, continuously blowing oxygen-enriched air in the roasting process, and collecting generated nano antimony trioxide.
2. The method for preparing nano antimony trioxide by oxygen-enriched blowing under the microwave field according to claim 1, characterized in that the sieving is a 100-200 mesh sieve; the grade of the antimony sulfide ore is 40-70%; the thickness of the flat laying is 1.5-5 cm.
3. The method for preparing nano antimony trioxide by oxygen-enriched blowing under microwave field according to claim 1, wherein the blowing flow rate is 0.5-2 m 3 /h。
4. The method for preparing nano antimony trioxide by oxygen-enriched blowing under the microwave field as claimed in claim 1, wherein the microwave power of the microwave field is 0.2-15 kW, and the microwave frequency is 2450 +/-50 MHz; the heating rate of the heating stage is 20-150 ℃/min; the time of the heat preservation stage is 15-60 min.
5. The method for preparing nano antimony trioxide by oxygen-enriched blowing under the microwave field according to claim 1, wherein the step of collecting nano antimony trioxide further comprises a tail gas absorption step.
6. The method for preparing nanometer antimony trioxide by oxygen-enriched blowing under the microwave field as claimed in claim 5, wherein the absorption liquid adopted in the tail gas absorption step is NaOH or Ca (OH) with the concentration of 1 mol/L-8 mol/L 2 And (3) solution.
7. The nano antimony trioxide prepared by the method for preparing the nano antimony trioxide through oxygen-enriched blowing under the microwave field according to any one of claims 1 to 6, wherein the size of the nano antimony trioxide is between 100 and 400 nm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106319199A (en) * | 2016-10-17 | 2017-01-11 | 北京矿冶研究总院 | Pretreatment method of antimony-and arsenic-containing refractory gold ore |
| CN110331279A (en) * | 2019-07-12 | 2019-10-15 | 云南民族大学 | A kind of microwave calcining stibnite concentrate directly volatilizees the method for recycling antimony oxide |
| CN114480880A (en) * | 2022-02-09 | 2022-05-13 | 云南民族大学 | Method for preparing metallic antimony by directly reducing antimony oxide powder by microwave |
| CN217202884U (en) * | 2022-02-07 | 2022-08-16 | 云南民族大学 | Device for recovering antimony oxide from medium-low-grade antimony sulfide in microwave blast combined roasting |
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| CN106319199A (en) * | 2016-10-17 | 2017-01-11 | 北京矿冶研究总院 | Pretreatment method of antimony-and arsenic-containing refractory gold ore |
| CN110331279A (en) * | 2019-07-12 | 2019-10-15 | 云南民族大学 | A kind of microwave calcining stibnite concentrate directly volatilizees the method for recycling antimony oxide |
| CN217202884U (en) * | 2022-02-07 | 2022-08-16 | 云南民族大学 | Device for recovering antimony oxide from medium-low-grade antimony sulfide in microwave blast combined roasting |
| CN114480880A (en) * | 2022-02-09 | 2022-05-13 | 云南民族大学 | Method for preparing metallic antimony by directly reducing antimony oxide powder by microwave |
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| Title |
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| YONGLI WANG等: "Direct preparation of micro and nano antimony trioxide using antimony concentrate via microwave roasting: Mechanism and process", 《CERAMICS INTERNATIONAL》, pages 23828 - 23839 * |
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