CN109280742B - Method for preparing ferrosilicon alloy by utilizing diamond wire cutting crystalline silicon waste - Google Patents
Method for preparing ferrosilicon alloy by utilizing diamond wire cutting crystalline silicon waste Download PDFInfo
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- CN109280742B CN109280742B CN201811155542.0A CN201811155542A CN109280742B CN 109280742 B CN109280742 B CN 109280742B CN 201811155542 A CN201811155542 A CN 201811155542A CN 109280742 B CN109280742 B CN 109280742B
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
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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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
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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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention provides a method for preparing a silicon-iron alloy by utilizing diamond wire cutting crystalline silicon waste, which comprises the following steps: mixing 21-63 wt% of crystalline silicon cutting waste, 1-3 wt% of sodium bentonite, 3-6 wt% of modified water glass, 3-20 wt% of iron powder and 30-40 wt% of water according to mass percentage, and then pressing into material balls; dehydrating the pellets at 60-90 ℃ until the weight of the pellets is not changed; organic matters are removed from the dehydrated material balls, the removed organic matters are decomposed, and the decomposed products are absorbed by a spray tower and then discharged into the atmosphere; sintering the pellets in a closed container; smelting the sintered pellets; and slagging off and pouring the smelted product to obtain an alloy, and detecting the alloy components. The method for preparing the silicon-iron alloy by utilizing the diamond wire cutting crystalline silicon waste material provided by the invention is safe and environment-friendly in production, and the dropping strength and the compressive strength of the material balls are good.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for preparing a silicon-iron alloy by cutting crystalline silicon waste materials through diamond wires.
Background
When the crystalline silicon is processed into the solar cell, cutting treatment is needed, and a silicon ingot is processed into a silicon wafer, so that a large amount of silicon-containing waste materials are generated in the process. Compared with the carborundum cutting technology, the diamond wire cutting technology has the advantages of high cutting efficiency, low environmental pollution, good silicon wafer precision, small surface damage, small kerf loss and the like, so the diamond wire cutting technology becomes a mainstream mode for cutting crystalline silicon in recent years.
The crystalline silicon cutting waste is mainly used for preparing crystalline silicon, silicon carbide, aluminum-silicon alloy and the like, the cutting waste is dehydrated to remove organic matters and remove iron without exception, and the ferrosilicon alloy is prepared without removing iron. The ferrosilicon alloy is mainly used as a deoxidizer in the steel-making industry. The traditional production method is that silica, carbonaceous reducing agent and steel scrap are proportioned according to a certain proportion and put into an electric arc furnace for smelting, and the cutting waste material is used for replacing the carbonaceous reducing agent and is directly smelted with the steel scrap, so that the reaction temperature and the reaction time can be reduced. The common steps of producing alloy by using crystalline silicon cutting waste materials at present are 'adding certain metal to the crystalline silicon cutting waste materials-alloy smelting-slagging-casting-alloy', but the pellet strength of most crystalline silicon cutting waste materials formed in the method is poor.
In addition, the method is to directly add powder for high-temperature smelting, and the high-temperature smelting directly utilizes the powder for smelting also has a plurality of problems. First, the bed of material is poorly permeable, reacts insufficiently or at a slow rate. Secondly, the powder smelting is easy to generate splashing and explosion, and the utilization rate of raw materials is low. Thirdly, the powder smelting is to charge and smelt the scrap steel and then blow the scrap steel into the powder, so that the production environment on site is deteriorated, the concentration of inhalable particles is increased, and the human health is harmed.
In addition, the drop strength of the dry and wet balls formed in the prior art is poor, potential safety hazards caused by hydrogen generated by reaction of silicon and water vapor are neglected in the dehydration process, and about 4% of organic matters are directly discharged into the atmosphere to pollute the environment easily.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing silicon-iron alloy by utilizing diamond wire cutting crystalline silicon waste, which is safe and environment-friendly in production and good in ball drop strength and compressive strength.
In order to solve the technical problem, the invention provides a method for preparing a silicon-iron alloy by cutting crystalline silicon waste materials by diamond wires, which comprises the following steps:
mixing 21-63 wt% of crystalline silicon cutting waste, 1-3 wt% of sodium bentonite, 3-6 wt% of modified water glass, 3-20 wt% of iron powder and 30-40 wt% of water according to mass percentage, and then pressing into material balls;
dehydrating the pellets at 60-90 ℃ until the weight of the pellets is not changed;
organic matters are removed from the dehydrated material balls, the removed organic matters are decomposed, and the decomposed products are absorbed by a spray tower and then discharged into the atmosphere;
sintering the pellets in a closed container;
smelting the sintered pellets;
and slagging off and pouring the smelted product to obtain an alloy, and detecting the alloy components.
Further, the dehydration time of the material balls is 5-20 h.
Further, the organic matter removal of the material balls is to remove the organic matter at the temperature of 200-400 ℃, and the time for removing the organic matter is 1-5 h.
Furthermore, the crystalline silicon cutting waste is subjected to crushing treatment in advance, and more than 90% of the crushed crystalline silicon cutting waste has particle sizes smaller than 100 μm.
Further, the material balls are pressed into the material balls with the diameter of 20-50 mm.
Further, the particle size of the iron powder is 2-300 meshes.
Further, the removed organic matter is decomposed by introducing the organic matter into an incinerator for decomposition.
Furthermore, the sintering temperature of the material ball in the closed container is 350-950 ℃, and the sintering time is 5-15 h.
Further, the ball smelting is carried out in an induction furnace under the protection of vacuum or inert gas, the ball smelting temperature is 1450-.
According to the method for preparing the silicon-iron alloy by utilizing the diamond wire cutting crystalline silicon waste, the formula of bentonite and modified water glass binder is adopted in the material ball ingredients, iron powder with different particle sizes is used as aggregate, and the material ball formed by pressing has good dropping strength and compressive strength. The bentonite forms a fiber structure after absorbing water and expanding, so that the wet material ball has good dropping strength and compressive strength; in the sintering process, the modified sodium silicate colloidal particles are bonded by Si-O-Si bonds to form a stable space network structure to firmly bond the particles together, so that the dry material ball also has good dropping strength and compressive strength; the iron powder is added as the aggregate, so that the interior of the pellet ball can be more tightly combined together, and the falling and compressive strength of the dry and wet pellets are further increased. In addition, the invention adopts low-temperature section dehydration when dehydrating the wet material balls, thereby avoiding or greatly reducing the generation of hydrogen and being convenient for safe production. Meanwhile, the organic matters removed from the material balls are subjected to incineration spray tower adsorption treatment, so that elements such as N, P, S and the like remained in the crystalline silicon cutting waste material by the water-based cutting fluid used for cutting the crystalline silicon are avoided, harmful gas generated in production sintering is discharged into the air to pollute the air, the pollution to the environment is reduced, and the method is green and environment-friendly.
Drawings
Fig. 1 is a process flow chart of a method for preparing a silicon-iron alloy by cutting crystalline silicon waste materials with diamond wires according to an embodiment of the invention.
Detailed Description
Referring to fig. 1, a method for preparing a silicon-iron alloy by cutting crystalline silicon waste with diamond wires according to an embodiment of the present invention includes the following steps:
step 1: according to the mass percentage, 21-63 wt% of crystalline silicon cutting waste, 1-3 wt% of sodium bentonite, 3-6 wt% of modified water glass, 3-20 wt% of iron powder and 30-40 wt% of water are mixed, and then the mixture is pressed into a material with the diameter of 10-50mm by a high-pressure roll-to-roll press; the crystalline silicon cutting waste is subjected to crushing treatment in advance, more than 90% of particles in the crushed crystalline silicon cutting waste are smaller than 100 mu m in size, and the particle size of the iron powder is 2-300 meshes.
Step 2: placing the pellets in a tunnel kiln or a mesh belt dryer, dehydrating at 60-90 ℃, and controlling the dehydration time to be 5-20h until the weight of the pellets is not changed any more.
And step 3: placing the dehydrated pellets in a tunnel kiln, removing organic matters at the temperature of 200-400 ℃, and controlling the time for removing the organic matters to be 1-5 h. And introducing the separated organic matters into an incinerator for incineration and decomposition, and then discharging the flue gas generated by decomposition into the atmosphere after being absorbed by a spray tower, so that the harmful gas generated by the incineration of the organic matters is prevented from polluting the air.
And 4, step 4: sintering the pellets in a closed container, wherein the sintering temperature is controlled to be 350-950 ℃, and the sintering time is controlled to be 5-15 h.
And 5: smelting 1450-1650 ℃ in an induction furnace under the protection of vacuum or inert gas, smelting the sintered pellets in the induction furnace, controlling the smelting temperature to 1450-1650 ℃, and keeping the temperature for 0.5-3 h.
Step 6: and carrying out slagging-off and pouring on the smelted product to obtain an alloy, and finally detecting the alloy components.
The method for preparing the silicon-iron alloy by cutting the crystalline silicon waste material by the diamond wire provided by the invention is specifically described by the following specific embodiment.
Example 1
A method for preparing ferrosilicon alloy by utilizing diamond wire cutting crystalline silicon waste materials comprises the following steps:
(1) and (3) crushing the crystalline silicon cutting waste, wherein the granularity of more than 90% of particles is less than 100 mu m after crushing. 0.2 kg of sodium bentonite, 0.5 kg of modified water glass, 1 kg of 2-300-mesh iron powder, 4.3 kg of crystalline silicon cutting material and 4 kg of water are mixed according to the proportion and pressed into balls with the diameter of 25mm by a high-pressure double-roll press.
(2) And (4) dehydrating at the temperature of 80 ℃ for 10h until the weight of the wet ball is not changed any more, and no hydrogen generation is detected.
(3) Organic matters are removed at the temperature of 200 ℃, the time of removing the organic matters is 5 hours, the removed organic matters enter an incinerator for decomposition, and the flue gas is finally discharged into the atmosphere after being eluted by a spray tower.
(4) And (5) filling the balls with the organic matters removed into a closed container. Sintering at 350 ℃ for 8 h.
(5) Adding the mixture into an induction furnace for smelting under the nitrogen atmosphere condition of 1450 ℃, and keeping the temperature for 3 hours.
(6) And carrying out slagging-off and pouring to obtain the alloy, and detecting the silicon content of the alloy to be 60.50%.
Example 2
A method for preparing ferrosilicon alloy by utilizing diamond wire cutting crystalline silicon waste materials comprises the following steps:
(1) and (3) crushing the crystalline silicon cutting waste, wherein the granularity of more than 90% of particles is less than 100 mu m after crushing. 0.2 kg of sodium bentonite, 0.6 kg of modified water glass, 0.8 kg of 2-300-mesh iron powder, 4.6 kg of crystalline silicon cutting material and 3.8 kg of water are mixed according to the proportion, and the mixture is pressed into a ball with the diameter of 25mm by a high-pressure double-roller press.
(2) And (4) dehydrating at 70 ℃ for 12h until the weight of the wet ball is not changed any more, and no hydrogen generation is detected.
(3) Organic matters are removed at the temperature of 250 ℃, the time for removing the organic matters is 1.5h, the removed organic matters enter an incinerator for decomposition, and the flue gas is finally discharged into the atmosphere after being eluted by a spray tower.
(4) And (5) filling the balls with the organic matters removed into a closed container. Sintering at 450 ℃ for 8 h.
(5) Adding the mixture into an induction furnace for smelting under the condition of 1550 ℃ nitrogen atmosphere, and keeping the temperature for 2 hours.
(6) And carrying out slagging-off and pouring to obtain an alloy, and detecting the silicon content of the alloy to be 65.74%.
Example 3
A method for preparing ferrosilicon alloy by utilizing diamond wire cutting crystalline silicon waste materials comprises the following steps:
(1) and (3) crushing the crystalline silicon cutting waste, wherein the granularity of more than 90% of particles is less than 100 mu m after crushing. 0.2 kg of sodium bentonite, 0.6 kg of modified water glass, 0.6 kg of 2-300-mesh iron powder, 5 kg of crystalline silicon cutting material and 3.6 kg of water are mixed according to the proportion and pressed into balls with the diameter of 25mm by a high-pressure double-roller press.
(2) And (4) dehydrating at 70 ℃ for 12h until the weight of the wet ball is not changed any more, and no hydrogen generation is detected.
(3) Removing organic matters at 350 deg.C for 0.5h, decomposing the removed organic matters in an incinerator, and discharging the flue gas into atmosphere after eluting with a spray tower.
(4) And (5) filling the balls with the organic matters removed into a closed container. Sintering at 500 deg.c for 6 hr.
(5) Adding the mixture into an induction furnace for smelting under the vacuum condition of 1550 ℃ and keeping the temperature for 2 hours.
(6) And carrying out slagging-off and pouring to obtain an alloy, and detecting the silicon content of the alloy to be 71.74%.
Example 4
A method for preparing ferrosilicon alloy by utilizing diamond wire cutting crystalline silicon waste materials comprises the following steps:
(1) and (3) crushing the crystalline silicon cutting waste, wherein the granularity of more than 90% of particles is less than 100 mu m after crushing. 0.2 kg of sodium bentonite, 0.8 kg of modified water glass, 0.6 kg of 2-300-mesh iron powder, 4.7 kg of crystalline silicon cutting material and 3.7 kg of water are mixed according to the proportion, and the mixture is pressed into a ball with the diameter of 25mm by a high-pressure double-roller press.
(2) And (4) dehydrating at 70 ℃ for 12h until the weight of the wet ball is not changed any more, and no hydrogen generation is detected.
(3) Organic matters are removed at the temperature of 300 ℃, the time for removing the organic matters is 1 hour, the removed organic matters enter an incinerator for decomposition, and the flue gas is finally discharged into the atmosphere after being eluted by a spray tower.
(4) And (5) filling the balls with the organic matters removed into a closed container. Sintering at 550 ℃ for 9 h.
(5) Adding the mixture into an induction furnace for smelting under the condition of argon atmosphere at 1550 ℃ and keeping the temperature for 1.5 h.
(6) And carrying out slagging-off and pouring to obtain an alloy, and detecting the silicon content of the alloy to be 68.26%.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (7)
1. A method for preparing a silicon-iron alloy by utilizing diamond wire cutting crystalline silicon waste is characterized by comprising the following steps:
according to the mass percentage, 21-63 wt% of crystalline silicon cutting waste, 1-3 wt% of sodium bentonite, 3-6 wt% of modified water glass, 3-20 wt% of iron powder with the granularity of 2-300 meshes and 30-40 wt% of water are mixed and then pressed into material balls;
dehydrating the pellets for 5-20h at 60-90 ℃ until the weight of the pellets is not changed any more;
organic matters are removed from the dehydrated material balls, the removed organic matters are decomposed, and the decomposed products are absorbed by a spray tower and then discharged into the atmosphere;
sintering the pellets in a closed container;
smelting the sintered pellets;
and slagging off and pouring the smelted product to obtain an alloy, and detecting the alloy components.
2. The method for preparing the silicon-iron alloy by utilizing the diamond wire cutting crystalline silicon waste material as claimed in claim 1, wherein the silicon-iron alloy comprises the following steps: the organic matter removal of the material balls is to remove the organic matter at the temperature of 200-400 ℃, and the time for removing the organic matter is 1-5 h.
3. The method for preparing the silicon-iron alloy by utilizing the diamond wire cutting crystalline silicon waste material as claimed in claim 1, wherein the silicon-iron alloy comprises the following steps: the crystalline silicon cutting waste is subjected to crushing treatment in advance, and more than 90% of the crushed crystalline silicon cutting waste has particle size smaller than 100 mu m.
4. The method for preparing the silicon-iron alloy by utilizing the diamond wire cutting crystalline silicon waste material as claimed in claim 1, wherein the silicon-iron alloy comprises the following steps: the material balls are pressed into the material balls with the diameter of 20-50 mm.
5. The method for preparing the silicon-iron alloy by utilizing the diamond wire cutting crystalline silicon waste material as claimed in claim 1, wherein the silicon-iron alloy comprises the following steps: the removed organic matter is decomposed by introducing the organic matter into an incineration kiln.
6. The method for preparing the silicon-iron alloy by utilizing the diamond wire cutting crystalline silicon waste material as claimed in claim 1, wherein the silicon-iron alloy comprises the following steps: the sintering temperature of the material ball in the closed container is 350-950 ℃, and the sintering time is 5-15 h.
7. The method for preparing the silicon-iron alloy by utilizing the diamond wire cutting crystalline silicon waste material as claimed in claim 1, wherein the silicon-iron alloy comprises the following steps: the ball smelting is carried out in an induction furnace under vacuum or inert gas protection, the ball smelting temperature is 1450-.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU417488A2 (en) * | 1972-09-15 | 1974-02-28 | ||
| SU1285016A1 (en) * | 1985-04-12 | 1987-01-23 | Коммунарский Горнометаллургический Институт | Slag-forming mixture for refining molten metal |
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| CN104962763B (en) * | 2015-05-25 | 2016-11-30 | 北京科技大学 | A kind of crystalline silicon cutting waste material produces the method for chromium system ferroalloy |
| CN105088052A (en) * | 2015-09-22 | 2015-11-25 | 刘来宝 | Method for producing ferrosilicon through cut waste in photovoltaic industry |
| CN105567968A (en) * | 2016-02-01 | 2016-05-11 | 四川川投峨眉铁合金（集团）有限责任公司 | Production method for smelting ferrosilicon by utilizing crystalline silicon cutting waste powder |
| CN108529630A (en) * | 2018-07-17 | 2018-09-14 | 东北大学 | A method of silicon carbide is prepared using synthesis by internal resistance electric melting |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU417488A2 (en) * | 1972-09-15 | 1974-02-28 | ||
| SU1285016A1 (en) * | 1985-04-12 | 1987-01-23 | Коммунарский Горнометаллургический Институт | Slag-forming mixture for refining molten metal |
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