CN115259221B - 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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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 title claims abstract description 160
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000001301 oxygen Substances 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000007664 blowing Methods 0.000 title claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 229910052569 sulfide mineral Inorganic materials 0.000 claims description 18
- 229910052787 antimony Inorganic materials 0.000 claims description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 8
- 238000003892 spreading Methods 0.000 claims description 7
- 230000007480 spreading Effects 0.000 claims description 7
- 238000004321 preservation Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 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 6
- 238000003723 Smelting Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009853 pyrometallurgy Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000000926 separation method Methods 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
- 239000002253 acid Substances 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
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution 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
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- 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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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a method for preparing nano antimony trioxide by oxygen-enriched blowing in a microwave field, and belongs to the technical field of nano materials. The preparation method comprises the following steps: the crushed and sieved antimony sulfide ore is paved in a roasting container, oxygen-enriched air with the oxygen volume fraction of more than 20% is introduced, roasting is carried out in a microwave field, the roasting is divided into a heating stage and a heat preservation stage, the oxygen-enriched air is continuously utilized for blowing in the roasting process, and the generated nano antimony trioxide is collected. The preparation method provided by the invention has the advantages of simple steps, low equipment requirement and low roasting temperature requirement, and the prepared nano antimony trioxide has the size of 100-400 nm, and the maximum volatilization rate of the antimony trioxide is more than 70%.
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 in a microwave field.
Background
Antimony trioxide, one of the oxides of antimony, has been widely used in industrial production. Antimony trioxide is commonly used in flame retardants, catalysts, heat stabilizers, alloying additives, ceramic additives, and in particular, relates to a number of industries such as chemistry, manufacturing, construction, and the like. Among them, the demand for antimony trioxide in the flame retardant industry is enormous, and about 60% of antimony products are used for flame retardant manufacture worldwide.
The utilization of antimony ore resources mainly comprises two kinds of pyrometallurgy and wet leaching, and more than 95% of enterprises at the present stage mainly adopt pyrometallurgy. The main processes of the method are divided into two steps of oxidation volatilization in a volatilization furnace and reduction in a reverberatory furnaceSegments. The oxidation stage mainly comprises the steps of placing partial high-grade raw antimony ore into a vertical-well volatilization furnace for volatilization smelting according to the characteristic that antimony trioxide is easy to volatilize, and collecting volatilized antimony trioxide. The reduction stage mainly comprises the steps of adding a certain amount of reducing agent and molten salt to carry out reduction smelting on the volatilized antimonous oxide to prepare a metal antimonial ingot. However, conventional pyrometallurgy often requires higher smelting temperatures, which require 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 the CO 2 The gas emissions do not meet the global sustainable development requirements. Although the traditional fire process can obtain the antimonous oxide with good purity to a certain extent, the antimonous oxide obtained by the traditional fire 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 the antimony trioxide obtained by the traditional pyrometallurgy is used as a flame retardant material, the antimony trioxide still needs to be subjected to modification, recrystallization, refinement and other treatments.
Smaller size antimony trioxide tends to be more excellent in flame retardant properties. For this reason, scholars at home and abroad have made a great deal of research on the preparation of small-sized antimony trioxide. Some methods common in the synthesis of materials, such as liquid phase methods, gas phase methods, solid phase methods, etc., have been studied in the preparation of small-sized antimony trioxide. Wherein patent CN 113321240A 'a preparation method of high-dispersity nano antimony trioxide' discloses a preparation method of high-dispersity nano antimony trioxide by taking antimony trichloride as a raw material, adopting an alcoholysis method and a hydrothermal method under an alkaline condition to obtain high-purity micro-grade antimony trioxide, and controlling the form and the particle size of the antimony trioxide through a solvothermal method and surfactant treatment; patent CN 112499680A 'a preparation method of spherical nano antimony trioxide' discloses that ethylene glycol antimony powder is used as a raw material, and solution A is obtained after ultrasonic dispersion in ethanol solution. Adding a certain amount of ultrapure water into a beaker, heating in a water bath, and regulating the pH to be weak acid by using an acid medium to obtain a solution B. And (3) reacting the solution A and the solution B under a certain condition to obtain a precipitate, centrifuging the precipitate, and drying to finally obtain the spherical nano antimony trioxide powder. Although both methods produce nano-scale antimony trioxide, both have high requirements on raw materials, and analytical grade reagents with higher purity are required as reaction raw materials in the preparation. In addition, the solvent method produces a large amount of waste liquid at the same time of production. The production cost is increased in the subsequent waste liquid treatment process, and the environmental pollution is caused if the waste liquid is improperly treated.
Disclosure of Invention
The invention aims to provide a method for preparing nano antimony trioxide by oxygen-enriched blowing in a microwave field. The purpose is to replace the traditional coal-based fuel by using a microwave heat source to reduce CO 2 Is arranged in the air. The method can clean and efficiently utilize antimony sulfide ore while obtaining small-size antimony trioxide, and solves the problems of high coke rate, high raw material requirement and large product size in the traditional preparation of the antimony trioxide.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows: the method for preparing the nano antimony trioxide by oxygen-enriched blowing in a microwave field comprises the following steps:
the crushed and sieved antimony sulfide ore is paved in a roasting container, oxygen-enriched air with the oxygen volume fraction of more than 20% is introduced, roasting is carried out in a microwave field, the roasting temperature is 600-800 ℃, the roasting is divided into a heating stage and a heat preservation stage, oxygen-enriched air is continuously utilized to blow in the roasting process, and the generated nano antimony trioxide is collected.
Preferably, the sieving is through a 100-200 mesh sieve; the grade of the antimony sulfide ore is 40-70%; the thickness of the tiling is 1.5-5 cm.
Preferably, the air flow of the blowing 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 temperature rising rate of the temperature rising stage is 20-150 ℃/min; the time of the heat preservation stage is 15-60 min.
Preferably, the step of collecting nano antimony trioxide further comprises an exhaust gas absorption step.
More preferably, the absorption liquid used in the tail gas absorption step is NaOH or Ca (OH) with the concentration of 1mol/L to 8mol/L 2 A solution.
The second technical scheme of the invention is as follows: the nano antimony trioxide prepared by the method for preparing the nano antimony trioxide by oxygen-enriched blowing under the microwave field has the size of 100-400 nm.
The beneficial technical effects of the invention are as follows:
compared with the roasting temperature (above 1000 ℃) of a conventional volatilizing furnace, the method for preparing the spherical nano antimony trioxide by oxygen-enriched blowing under the microwave field only needs to be 600-800 ℃, and has obvious low-temperature smelting advantage. The specific low-temperature smelting has the advantages that the heat conduction direction is heat transfer from inside to outside in the microwave heating process, and the volatilization direction of the antimonous oxide is also the volatilization process from inside to outside, so that the interface resistance 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, reduces CO 2 Is beneficial to sustainable development. The size of the prepared spherical nano antimony trioxide is smaller than that of the antimony trioxide prepared by a conventional volatilizing furnace, and the size range is within 100-400 nm. The preparation raw material adopted by the invention is antimony sulfide ore with the antimony grade of 40-70%, and has the characteristics of strong raw material adaptability, low requirement and the like, and the volatilization rate of the whole process of preparing the spherical nano antimony trioxide by oxygen-enriched blowing is between 70% and 90%.
Drawings
FIG. 1 is a diagram of an apparatus for preparing spherical nano antimony trioxide by oxygen-enriched blowing in a microwave field according to the present invention.
Fig. 2 is an SEM image of nano antimony trioxide prepared in example 1 of the present invention.
FIG. 3 is a graph showing the size distribution of nano antimony trioxide prepared in example 1 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions 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.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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 intended to be inclusive and mean an inclusion, 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 mining and dressing processes of antimony sulfide ore.
(2) Spreading antimony sulfide minerals in a quartz boat, wherein the thickness of the materials is 1.5-5 cm. In the tiling process, antimony sulfide minerals are normally dispersed in a quartz boat, and briquetting treatment is not required for the antimony sulfide minerals.
(3) Putting quartz boat containing antimony sulfide mineral into tubular microwave with quartz tubeOxidizing, volatilizing and roasting in the furnace, wherein the quartz tube is made of silicon dioxide with good microwave permeability. Before roasting, blowing oxygen-enriched air with a certain flow, wherein the flow chart of the oxygen-enriched blowing process is shown in figure 1. In the roasting process, the air flow range is 0.5-2 m 3 /h。
(4) Before oxidizing roasting, setting the temperature control mode of the tube furnace as automatic temperature control. The microwave roasting power is 0.2-15 kW, and the microwave frequency is 2450+/-50 MHz. The temperature measuring mode is selected as infrared temperature control, and magnetron cooling water and antimony trioxide dust condensing tube circulating water of a microwave tube type furnace are started.
(5) On the premise of exhausting gas in the tail gas absorbing bottle, a microwave tube furnace is started to perform oxidizing roasting. The first roasting stage is a heating stage, and the heating rate in the heating process is 20-150 ℃/min. After the equipment reaches the required roasting temperature, the equipment enters a heat preservation stage after heat preservation time is set. The roasting temperature is 600-800 ℃, and the heat preservation time is 15-60 min.
(6) The nanometer antimonous oxide prepared by oxygen-enriched blowing is collected in a collecting bottle, and the purity of the nanometer antimonous oxide is more than 97%. SO produced by the whole process 2 The gas is absorbed by a tail gas absorbing bottle, and the tail gas absorbing solution is NaOH solution or Ca (OH) with the concentration of 1mol/L to 8mol/L 2 A solution.
(7) And after the reaction is finished for 20min, closing magnetron cooling water and circulating water of an antimony trioxide dust condensing pipe of the microwave tube type furnace, naturally cooling the instrument to room temperature, and closing a power supply of the instrument.
The volatilization rate of the antimony trioxide of the roasted sample after the steps is calculated as follows:
M g ＝m 2 ×w 2
wherein beta is the volatilization rate and m of antimony trioxide prepared by oxygen-enriched blowing under a microwave field 1 For the mass of the sample before calcination, m 2 The mass of the sample after roasting; w (W) 1 For the content of antimony sulphide in minerals, W 2 Is the content of antimony trioxide in the slag phase after roasting.
Specific examples are as follows:
example 1
Sieving the antimony sulfide mineral obtained after ore dressing with 100 mesh sieve, spreading antimony sulfide mineral with antimony grade of 42.8% in quartz boat, material thickness of 2.5cm, and oxygen-enriched air (oxygen volume fraction greater than 20%) flow rate of 1m 3 And/h. Before oxidizing roasting, starting a microwave tube furnace and circulating water of an antimony trioxide dust condensing device. After ensuring smooth ventilation of the whole roasting system, starting a microwave tube furnace 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. And after the temperature reaches 800 ℃, the microwave roasting power is 0.8-2 kW, and the sample is kept for 30min. After the reaction was completed, the volatilization rate of antimony trioxide was calculated to be 82%. The SEM image of the collected antimonous oxide is shown in figure 2, the size distribution diagram of the obtained spherical nanometer antimonous oxide is shown in figure 3, and the particle size d is 188.18 +/-72.48 nm.
Example 2
Sieving antimony sulfide mineral obtained after mineral separation with 200 mesh sieve, spreading antimony sulfide mineral with antimony grade of 70% in quartz boat, material thickness of 2.5cm, and oxygen-enriched air (oxygen volume fraction greater than 20%) flow rate of 1m 3 And/h. Before oxidizing roasting, starting a microwave tube furnace and circulating water of an antimony trioxide dust condensing device. After ensuring smooth ventilation of the whole roasting system, starting a microwave tube furnace 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 workThe rate is 0.8-1.8 kW, and the sample is kept for 30min. After the reaction was completed, the volatilization rate of antimony trioxide was calculated to be 90%. The obtained antimonous oxide has the particle size d of 190+/-80 nm after measurement.
Example 3
Sieving the antimony sulfide mineral obtained after ore dressing with 100 mesh sieve, spreading antimony sulfide mineral with antimony grade of 42.8% in quartz boat with material thickness of 1.5cm, and oxygen-enriched air (oxygen volume fraction is greater than 20%) flow rate of 0.8m 3 And/h. Before oxidizing roasting, starting a microwave tube furnace and circulating water of an antimony trioxide dust condensing device. After ensuring smooth ventilation of the whole roasting system, starting a microwave tube furnace 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. After the temperature reaches 700 ℃, the microwave roasting power is 0.8-1.8 kW, and the sample is kept for 45min. After the reaction was completed, the volatilization rate of antimony trioxide was calculated to be 78%. The obtained antimonous oxide has a particle size d of 200+/-60 nm.
Example 4
Sieving antimony sulfide mineral obtained after mineral separation with 200 mesh sieve, spreading antimony sulfide mineral with antimony grade of 70% in quartz boat with material thickness of 1.5cm, and oxygen-enriched air (oxygen volume fraction greater than 20%) flow rate of 0.8m 3 And/h. Before oxidizing roasting, starting a microwave tube furnace and circulating water of an antimony trioxide dust condensing device. After ensuring smooth ventilation of the whole roasting system, starting a microwave tube furnace 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 1.6kW. The selected roasting temperature is 700 ℃, and the average heating rate in the heating stage is 55 ℃/min. After the temperature reaches 700 ℃, the microwave roasting power is 0.8-1.6 kW, and the sample is kept for 45min. After the reaction was completed, the volatilization rate of antimony trioxide was calculated to be 82%. The obtained antimonous oxide has the particle size d of 210+/-55 nm after measurement.
Example 5
Beneficiation is carried outThe obtained antimony sulfide mineral is sieved by a 200-mesh sieve, the antimony sulfide mineral with the antimony grade of 42.8 percent is paved in a quartz boat, the thickness of the material is 1cm, and the flow rate of oxygen-enriched air (the volume fraction of oxygen is more than 20 percent) which is introduced in the oxygen-enriched blowing roasting process is 0.8m 3 And/h. Before oxidizing roasting, starting a microwave tube furnace and circulating water of an antimony trioxide dust condensing device. After ensuring smooth ventilation of the whole roasting system, starting a microwave tube furnace 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 calcination temperature was 600℃and the average temperature rise rate in the temperature rise stage was 20℃per minute. After the temperature reaches 600 ℃, the microwave roasting power is 0.4-1.6 kW, and the sample is kept for 60min. After the reaction was completed, the volatilization rate of antimony trioxide was calculated to be 70%. The obtained antimonous oxide has the particle size d of 220+/-80 nm after measurement.
Example 6
Sieving antimony sulfide mineral obtained after mineral separation with 200 mesh sieve, spreading antimony sulfide mineral with antimony grade of 70% in quartz boat, material thickness of 1cm, and oxygen-enriched air (oxygen volume fraction greater than 20%) flow rate of 0.8m 3 And/h. Before oxidizing roasting, starting a microwave tube furnace and circulating water of an antimony trioxide dust condensing device. After ensuring smooth ventilation of the whole roasting system, starting a microwave tube furnace 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 1.6kW. The selected roasting temperature is 700 ℃, and the average heating rate in the heating stage is 40 ℃/min. After the temperature reaches 600 ℃, the microwave roasting power is 0.4-1.6 kW, and the sample is kept for 60min. After the reaction was completed, the volatilization rate of antimony trioxide was calculated to be 73%. The obtained antimonous oxide has a particle size d of 235+/-90 nm.
Comparative example 1
Comparative example 1 differs from example 1 in that the oxidative calcination was carried out using a conventional tube furnace, the average temperature rise rate in the temperature rise stage was 10 ℃/min, and the calcination temperature was selected to be 1000 ℃. The size of the obtained antimonous oxide is larger than 1 mu m, and the volatilization rate of the antimonous oxide is only 78 percent.
Comparative example 2
Comparative example 2 differs from example 1 in that the oxidative calcination was carried out using a conventional tube furnace, the average temperature rise rate in the temperature rise stage was 10 ℃/min, and the calcination temperature was selected to be 900 ℃. The size of the obtained antimonous oxide is larger than 1 mu m, and the volatilization rate of the antimonous oxide is only 62 percent.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (1)
1. The nanometer antimonous oxide prepared by oxygen-enriched blowing under a microwave field is characterized by comprising the following preparation steps:
sieving the antimony sulfide mineral obtained after ore dressing with 100 mesh sieve, spreading antimony sulfide mineral with antimony grade of 42.8% in quartz boat, wherein the thickness of the material is 2.5cm, and introducing oxygen-enriched air with oxygen volume fraction of more than 20% in the oxygen-enriched blowing roasting process, and the flow rate is 1m 3 /h; before oxidizing roasting, starting circulating water of a microwave tube furnace and an antimony trioxide dust condensing device, and after ensuring that the whole roasting system is smoothly ventilated, starting the microwave tube furnace to carry out oxygen-enriched volatilizing roasting, wherein the microwave roasting frequency is 2450MHz in the roasting process, 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 for 30min to obtain the nano antimony trioxide.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Direct preparation of micro and nano antimony trioxide using antimony concentrate via microwave roasting: Mechanism and process;Yongli Wang等;《Ceramics International》;23828-23839 * |
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