CN116282038A - Production of C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag 2 Is a method of (2) - Google Patents
Production of C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag 2 Is a method of (2) Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 55
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- 239000010703 silicon Substances 0.000 title claims abstract description 54
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/06—Metal silicides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for producing C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag 2 Belongs to the technical field of secondary metal resource recycling. The invention realizes the recycling of diamond wire silicon wafer cutting waste and acid-soluble titanium slag and develops C54-TiSi 2 Provides a new production path for preparing high-purity C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag 2 The method uses acid-soluble titanium slag as a raw material and diamond wire cutting waste as a reducing agent, and prepares the high-purity C54-TiSi through smelting reduction, electromagnetic strengthening separation, alkaline leaching and secondary directional solidification technology 2 . The invention realizes the full utilization of the diamond wire silicon wafer cutting waste and the acid-soluble titanium slag, and avoids other intermediates and TiSi 2 Other crystal forms are generated to obtain high-purity C54-TiSi 2 Has the characteristics of short flow, low cost, high recovery rate of valuable metals, easy mass production and the like.
Description
Technical Field
The invention belongs to the technical field of secondary metal resource recycling and material preparation, and in particular relates to a method for producing C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag 2 Is a method of (2).
Background
Fossil energy sources such as coal, petroleum, natural gas and the like are the main driving forces for national economy development for a long time, but along with the definition of carbon reaching peak and carbon neutralization double carbon targets and the long-term consumption of the fossil energy sources for social development, the development of renewable energy sources is a necessary path for further social development; by 21 st century, renewable energy consumption would occupy more than 80% of the total energy consumption in the world, while solar energy is a novel sustainable energy source, and solar power generation would occupy more than 60% of the total power generation in the world; therefore, solar power generation will take absolute advantage in future energy development and development in rain and is likely to be the dominant energy situation. Currently, solar power generation mainly depends on the photovoltaic industry of crystalline silicon batteries, and polycrystalline silicon occupies the main stream in the crystalline silicon batteries, so the polycrystalline silicon batteries are still one of the main directions of the subsequent electric positive energy batteries; the main process flow for manufacturing the crystalline silicon solar cell is as follows: crystal silicon production, silicon wafer cutting, battery piece production and the like; the silicon wafer is prepared by adopting a diamond wire cutting technology, but in the link, nearly 40% of solar grade polysilicon enters into cutting waste liquid in a powder form, the recovery difficulty is high due to the fact that the lost silicon material is fine in granularity and dispersed in slurry, the cost of secondary preparation of solar grade silicon is high, the recovery utilization rate of the current part of silicon wafer cutting waste is low, and a new process for treating a large quantity of cutting waste is urgently needed to be explored.
Panzhihua has rich vanadium titano-magnetite resources, but the content of CaO and MgO in the vanadium titano-magnetite is higher, mgO and CaO are hardly reduced in the process of smelting titanium slag by adopting an electric furnace, the Panzhihua is in a molten state under a high temperature condition, and FeO in ilmenite is gradually reduced in the electric furnace smelting processAfter being reduced, tiO 2 And forming the black titanium stone after the partially reduced low-valence titanium oxide is in solid solution with the impurity oxide. Therefore, the titanium slag obtained by smelting the Panzhihua ilmenite has higher calcium and magnesium content (MgO+CaO is about 10 percent), and is not suitable for the titanium chloride process; however, because the black titanium stone has good acidolysis performance, the black titanium stone is often used for preparing titanium dioxide by a sulfuric acid process titanium dioxide process; the sulfuric acid process titanium white technology has obvious environmental protection pressure, and mainly because a large amount of low-concentration waste acid is generated in the acidolysis process, a large amount of solid waste is generated in the hydrolysis and freezing process of the titanium liquid, and the waste acid and the solid waste are difficult to treat.
TiSi 2 The material has lower resistivity, good thermal stability and lower contact sheet resistance, so that TiSi 2 Preparation of gate, gate and drain materials for electronic devices in wide application, thus TiSi 2 Are also considered to be very suitable materials for the fabrication of very large scale integrated circuits. TiSi (TiSi) 2 There are two typical crystal structures: C49-TiSi of body-centered cubic structure 2 C54-TiSi with dough-kneading dough-core oblique square structure 2 Their crystal structure constants are respectively: C49-TiSi 2 ：
C54-TiSi 2 ：/>
C49-TiSi 2 The resistivity of (2) is: 60-90 mu omega cm, and C54-TiSi 2 Only the resistivity of (2): 12-20 mu omega cm, thus C54-TiSi 2 Is the first choice material in the preparation process of the ultra-large scale integrated circuit. TiSi (TiSi) 2 The current traditional preparation methods are chemical deposition, high temperature self-propagating technology and solid phase reaction, but are used for C54-TiSi 2 The preparation method of (C) is usually only a chemical deposition-annealing method, and the process mainly comprises the steps of depositing Ti in a film shape on a Si substrate, but the crystal structure is easily transformed into C49-TiSi during annealing 2 . Therefore, the C54-TiSi is prepared by the traditional process 2 Inevitably, C49-TiSi is generated 2 Resulting in an increase in resistivity. There is therefore an urgent need to explore a new process for preparing C54-TiSi 2 。
Disclosure of Invention
The invention realizes the recycling of diamond wire silicon wafer cutting waste and acid-soluble titanium slag and develops a high-purity C54-TiSi 2 Provides a production path for preparing high-purity C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag 2 The method adopts acid-soluble titanium slag as a raw material, adopts silicon in diamond wire cutting waste as a reducing agent, and carries out high-temperature smelting reduction, electromagnetic strengthening separation, alkaline leaching and secondary directional solidification technical route on the acid-soluble titanium slag to prepare high-purity C54-TiSi 2 。
The invention provides a method for producing C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag 2 Comprising the steps of:
A. cutting acid-soluble titanium slag, diamond linear silicon wafer waste, caO and Al 2 O 3 According to the mass ratio of 1:1 to 1.5:0.85 to 1.0:
0.23 to 0.4, and then ball milling is carried out to obtain a mixture;
B. reducing and smelting the mixture, and cooling, crushing and separating slag from gold after smelting to obtain Ti-Si alloy;
C. carrying out primary refining coupling directional solidification on Ti-Si alloy to obtain coarse C54-TiSi 2 The method comprises the steps of carrying out a first treatment on the surface of the The parameters for controlling the primary refining coupling directional solidification are as follows: the smelting temperature is 1500-1600 ℃, the directional solidification pull-down speed is 10-100 mu m/s, and the magnetic field strength is 0.1-20T;
D. crude C54-TiSi 2 Crushing, and then performing ultrasonic alkaline leaching to deeply remove Si;
E. C54-TiSi after deep Si removal 2 Powder is subjected toSecondary directional solidification to obtain high-purity C54-TiSi 2 The method comprises the steps of carrying out a first treatment on the surface of the The parameters for controlling the secondary directional solidification are as follows: the smelting temperature is 1500-1600 ℃, the directional solidification pull-down speed is 1-10 mu m/s, and the magnetic field strength is 0.1-20T.
In the above method, in the step A, the acid-soluble titanium slag contains TiO 2 ：71.56～83.27wt.％，FeO：2.29～7.84wt.％，MnO：0.59～1.02wt.％，CaO：1.86～2.16wt.％，MgO：5.87～7.14wt％，SiO 2 ：2.28～5.82wt.％，Al 2 O 3 ：1.48～2.66wt.％；
In the above method, in the step a, the diamond wire silicon wafer cutting waste material contains Si: 81.56-92.13 wt.% SiO 2 ：7.26～17.46wt.％。
In the method, in the step A, the ball milling time is 5-15 min.
In the method, in the step A, the particle size of the mixture is 82-89% of the particle size of minus 74 mu m.
In the method, in the step B, the reduction smelting temperature is 1500-1600 ℃.
In the method, in the step B, the reduction smelting time is 60-240 min.
In the above method, in step B, ti in the Ti-Si alloy: 27-38 wt.%, si: 57-60 wt.%, fe:2.1 to 3.0wt.%, mn:0.4 to 0.6wt.%.
In the step C, the cast ingot obtained by primary refining coupling directional solidification is subjected to head cutting and tail cutting, and is cut along a phase separation boundary line to obtain crude C54-TiSi 2 。
Wherein, in the step D, the method comprises the steps of coarse C54-TiSi 2 Crushing to particle size of-74 μm with a ratio of more than 90%.
In the above method, in step D, the parameters of the ultrasonic alkaline leaching depth for removing Si are: the mass concentration of NaOH solution is 5-15%, the alkaline leaching temperature is 75-85 ℃, the alkaline leaching time is 5-20 min, the liquid (NaOH solution is calculated by volume) is solid (coarse C54-TiSi) 2 In mass) is 2.5-3.5: 1, the power of the ultrasonic generator is 0-150W.
In the method, in the step E, the cast ingot obtained by the secondary directional solidification is subjected to head cutting and tail cutting, and is cut along a phase separation boundary line to obtain the high-purity C54-TiSi 2 。
Wherein, in the method, in the step E, the obtained high-purity C54-TiSi 2 The purity of (3) is 99.93-99.98%.
Wherein, in the method, in the step E, the obtained high-purity C54-TiSi 2 The crystal structure constants (XRD diffraction curves obtained after Rietveld refinement using Jade software) of (a) are:
the invention also provides the C54-TiSi prepared by the method 2 。
The invention has the beneficial effects that:
the invention utilizes the metal wire silicon wafer cutting waste to treat the acid-soluble titanium slag to realize valuable metal recycling, and controls the addition amount of the reducing agent diamond wire silicon wafer cutting waste, thereby fully utilizing the acid-soluble titanium slag with high calcium and magnesium content and the diamond wire silicon wafer cutting waste with high SiO in the reduction smelting process 2 The content characteristics of the additive CaO and Al are accurately controlled 2 O 3 Slag formation smelting is carried out, and alloy component regulation and control, efficient recovery of valuable metals and effective separation of slag and gold can be carried out after smelting; the primary refining coupling directional solidification is carried out on the alloy melt obtained after smelting by combining the electromagnetic directional solidification technology, so that the deep removal of nonmetallic inclusions and the preliminary removal of metallic elements Fe and Mn in the alloy can be realized, and the C54-TiSi can be realized 2 The steps of conventional acid washing to remove metal impurities are omitted, and TiSi is realized by ultrasonic alkaline leaching 2 Deep desilication, and finally, crystal form control and deep removal of metal impurities Fe and Mn are further realized through secondary directional solidification, so that other intermediate compounds and TiSi are avoided 2 Other crystal forms appear.
The invention realizes the full utilization and consumption of the diamond wire silicon wafer cutting waste and the acid-soluble titanium slag, and avoids the waste acid and the waste acid generated when the acid-soluble titanium slag is applied to the sulfuric acid process titanium white processThe solid waste expands and explores a high-quality technical route for the application of acid-soluble titanium slag to the downstream of the titanium industry chain, and can further expand C54-TiSi 2 The preparation process realizes comprehensive utilization of resources. The method has the characteristics of short flow, low cost, high recovery rate of valuable metals, high utilization rate of raw materials, easiness in large-scale production and the like.
Drawings
FIG. 1 is a schematic diagram of the process flow of the present invention.
Detailed Description
Specifically, the diamond wire silicon wafer cutting waste and acid-soluble titanium slag are utilized to produce C54-TiSi 2 In the method of (a),
A. cutting acid-soluble titanium slag, diamond linear silicon wafer waste, caO and Al 2 O 3 According to the mass ratio of 1:1 to 1.5:0.85 to 1.0:0.23 to 0.4, and then ball milling is carried out to obtain a mixture;
B. reducing and smelting the mixture, and cooling, crushing and separating slag from gold after smelting to obtain Ti-Si alloy;
C. carrying out primary refining coupling directional solidification on Ti-Si alloy to obtain coarse C54-TiSi 2 The method comprises the steps of carrying out a first treatment on the surface of the The parameters for controlling the primary refining coupling directional solidification are as follows: the smelting temperature is 1500-1600 ℃, the directional solidification pull-down speed is 10-100 mu m/s, and the magnetic field strength is 0.1-20T;
D. crude C54-TiSi 2 Crushing, and then performing ultrasonic alkaline leaching to deeply remove Si;
E. C54-TiSi after deep Si removal 2 Performing secondary directional solidification on the powder to obtain the high-purity C54-TiSi 2 The method comprises the steps of carrying out a first treatment on the surface of the The parameters for controlling the secondary directional solidification are as follows: the smelting temperature is 1500-1600 ℃, the directional solidification pull-down speed is 1-10 mu m/s, and the magnetic field strength is 0.1-20T.
In the step A of the invention, acid-soluble titanium slag, diamond wire silicon wafer cutting waste, caO and Al 2 O 3 After fully mixing, the materials are put into a ball mill together for crushing and secondary fully mixing for sample preparation. Due to the valuable metal oxides of acid-soluble titanium slag: tiO (titanium dioxide) 2 FeO and MnO are dissolved in the black titanium stone phase (m [ (Mg, fe, mn, ti) O.2TiO) 2 ]·n[(Al、Cr、Ti) 2 O 3 ·TiO 2 ]) In order to fully expose the valuable metal element oxide in the reduction process, the particle size of the mixture is controlled to be 82-89% of the particle size of-74 μm.
In the invention, the acid-soluble titanium slag is titanium slag directly smelted in an electric furnace, can be directly utilized without carrying out magnetic separation and iron removal, and generally contains TiO 2 ：71.56～83.27wt.％，FeO：2.29～7.84wt.％，MnO：0.59～1.02wt.％，CaO：1.86～2.16wt.％，MgO：5.87～7.14wt％，SiO 2 ：2.28～5.82wt.％，Al 2 O 3 :1.48 to 2.66wt.%; diamond wire silicon wafer cutting waste generally contains Si: 81.56-92.13 wt.% SiO 2 ：7.26～17.46wt.％。
Acid-soluble titanium slag is produced by TiO 2 The content is lower, but is only about 71.56-83.27%, but the content of calcium and magnesium is higher (CaO+MgO is about 8-10%), compared with other high titanium slag, the slag has low TiO 2 The content and the high MgO and CaO content are not suitable for the generation of titanium chloride white, but only can be used in the sulfuric acid method titanium white industry. The invention adopts the diamond wire silicon wafer cutting waste as the reducing agent, and can rely on acid-soluble titanium slag and high-content MgO, caO and SiO in the diamond wire silicon wafer cutting waste in the melting reduction process 2 Based on this, the addition of the reducing agent and the addition of slag formers (CaO and Al) 2 O 3 ) The adding amount of the alloy is controlled to be within 1400-1500 ℃ in the melting temperature range, and the high-efficiency slag-gold separation and alloy component regulation can be realized under the condition of the melting temperature, so that Si in the Ti-Si alloy obtained in the step B: 57-60 wt.% and simultaneously reducing SiO in the smelted slag 2 CaO and Al 2 O 3 The mass ratio of (2) is 1:1.15 to 1.35:0.35 to 0.5 of SiO contained in the acid-soluble titanium slag 2 CaO and Al 2 O 3 SiO contained in diamond wire silicon wafer cutting waste 2 Controlling acid-soluble titanium slag, diamond wire silicon wafer cutting waste, caO and Al in the step A 2 O 3 The mass ratio of (2) is 1:1 to 1.5:0.85 to 1.0:0.23 to 0.4. Therefore, the scheme provides the slag former by fully utilizing the raw materials, and the low-temperature smelting and good slag gold can be realized by less addition of the slag formerThe separation effect and the regulation and control of alloy components can save the addition of reducing agent and slag former.
In the invention, the acid-soluble titanium slag is reduced and smelted by utilizing the diamond wire silicon wafer cutting waste to realize the preliminary enrichment of valuable metals, and the obtained alloy comprises the following components: si alloy of 57-60 wt.% Ti (27-38 wt.% Ti, 57-60 wt.% Si, 2.1-3.0 wt.% Fe and 0.4-0.6 wt.% Mn), and after reduction smelting, the recovery rate of Ti in acid-soluble titanium slag can reach 98.23%, and TiO in residue 2 The minimum content can reach 0.18%, and the recycling of Ti is fully realized. In the invention, in the step B, the reduction smelting temperature is controlled to be 1500-1600 ℃, and the reduction smelting time is controlled to be 60-240 min.
Conventional directional solidification relies solely on gravitational and temperature fields as the driving force for atoms and clusters during crystal growth during solidification; while the present invention is directed to C54-TiSi 2 In the process of directional solidification, an electromagnetic field is applied, besides the action of a gravity field and temperature, the electromagnetic field can also generate an electromagnetic force in the melt, the electromagnetic force acts on the melt to enable the melt to axially rotate and continuously homogenize the melt components, so that atoms and clusters can be continuously provided for the solidification front in the process of crystal growth, and the crystals are promoted to fully grow to reach C54-TiSi 2 And finally enriching. In addition, because electromagnetic force acts on the melt, the mass transfer characteristic of impurities in the melt can be improved, so that metal impurities Fe, mn and the like in the melt are continuously migrated to the rest melt, and the removal of the impurities is enhanced. Therefore, after the reduction smelting, the TiSi is obtained after primary vacuum electromagnetic directional solidification refining and enhanced separation 2 The purity can reach 99.26wt percent, and the removal rate of Fe and Mn can reach 99.88 percent.
In the step C, the cast ingot obtained by primary refining coupling directional solidification is subjected to head cutting and tail cutting, and is cut along a phase separation boundary line to obtain crude C54-TiSi 2 。
In the invention, since the deep removal of metal impurities can be realized by one-time refining coupling directional solidification, no acid washing is needed to removeMetal impurities Fe and Mn; but is TiSi after directional solidification due to primary refining coupling 2 The main impurity in the enriched layer of (C) is Si, the invention leads to coarse C54-TiSi 2 Crushing to granularity of-74 μm with a ratio of more than 90%, and directly carrying out ultrasonic alkaline leaching deep desilication to ensure that the Si removal rate can reach>99.92％，C54-TiSi 2 Can reach the purity of>99.23%. In the step D, the parameters of the ultrasonic alkaline leaching depth Si removal are as follows: the mass concentration of the NaOH solution is 5-15%, the alkaline leaching temperature is 75-85 ℃, the alkaline leaching time is 5-20 min, and the liquid-solid ratio is 2.5-3.5: 1 (wherein NaOH solution is by volume and crude C54-TiSi) 2 By mass), the power of the ultrasonic generator is 0-150W.
In the invention, the crystal form control and the deep removal of Fe and Mn as metal impurities can be realized through the secondary directional solidification, and other intermediate compounds and TiSi can be avoided 2 Other crystal forms appear. Thus, in the present invention, although the two directional solidification aims at deeply removing the metal impurities, the second directional solidification can suppress C54-TiSi more than removing the metal impurities 2 To ensure the transformation of the crystal structure of C54-TiSi 2 Is high in purity.
In the step E, the cast ingot obtained by the secondary directional solidification is subjected to head cutting and tail cutting, and is cut along a phase separation boundary line to obtain the high-purity C54-TiSi 2 。
The invention takes cheap acid-soluble titanium slag and diamond wire silicon wafer cutting waste as raw materials, and can obtain high-purity C54-TiSi by optimizing the process 2 The purity can reach 99.93-99.98%, and the crystal structure constant range is as follows:
in the step B, the crucible used for smelting is a graphite crucible or an MgO crucible, but the crucible is not limited to the graphite crucible or the MgO crucible; in step C, E, charge directional solidification is performed in a high purity graphite crucible, but is not limited to such a crucible.
The present invention will be described in further detail by way of examples, which are not intended to limit the scope of the invention.
Example 1
As shown in the flow chart of fig. 1, the specific steps are as follows:
(1) Firstly, 150g of acid-soluble titanium slag (TiO) 2 ：78wt.％，FeO：4.69wt.％，MnO：0.89wt.％，CaO：2.12wt.％，MgO：5.87wt％，SiO 2 ：5.32wt.％，Al 2 O 3 :2.52 wt.%) cutting waste material (Si: 90wt.% SiO 2 :10 wt.%) CaO and Al 2 O 3 According to the mass ratio of 1:1.08:0.887:0.385 g of diamond wire silicon wafer cutting waste material, 133g of CaO and 57.8g of Al are respectively weighed 2 O 3 ；
(2) Weighing acid-soluble titanium slag, diamond wire silicon wafer cutting waste, caO and Al 2 O 3 Mixing, and then placing into a planetary ball mill for ball milling treatment for 5min to obtain the mixture with the particle size of-74 mu m accounting for 82%;
(3) Loading the ball-milled raw materials into a high-purity MgO crucible;
(4) Placing a high-purity MgO crucible filled with raw materials into a high-temperature box-type resistance furnace for reduction smelting; the smelting temperature is 1500 ℃ and the smelting time is 60min;
(5) After smelting, cooling to room temperature, taking out a high-purity MgO crucible, crushing a sample, and separating slag from gold to obtain Ti-57.38wt.% Si alloy (wherein, the Ti is 37.98wt.%, the Si is 57.38wt.%, and the contents of Fe and Mn are 2.96wt.% and 0.57wt.% respectively);
(6) Placing Ti-57.38wt.% Si alloy into a high-purity graphite crucible, and placing the graphite crucible filled with the alloy into a vacuum induction furnace for primary refining, coupling, directional solidification, phase separation and impurity removal; controlling the smelting temperature of the directional solidification furnace to be 1500 ℃, controlling the directional solidification pull-down speed to be 10 mu m/s and controlling the magnetic field strength to be 0.1T;
(7) Cutting the ingot obtained by primary refining coupling directional solidification into a head and a tail, and then cutting along a phase separation boundary line to obtain TiSi at the bottom 2 Purity of (3)99.82%, and the removal rates of Fe and Mn are 99.88% and 99.89%, respectively;
(8) Crude TiSi 2 Crushing and sampling, wherein the granularity is controlled to be more than 90 percent with the proportion of-74 mu m;
(9) Crude TiSi after sample preparation treatment 2 And (3) performing alkaline leaching deep Si removal, wherein the control process parameters are as follows: the mass concentration of the NaOH solution is 5%, the alkaline leaching temperature is 75 ℃, the alkaline leaching time is 5min, and the liquid-solid ratio is 3.5:1, the power of the ultrasonic generator is 10W; tiSi after alkaline leaching 2 The purity of the silicon can reach 99.94wt percent, and the silicon removal rate reaches 99.93 percent;
(10) C54-TiSi after deep Si removal 2 Performing secondary directional solidification depth impurity removal on the powder; C54-TiSi after alkaline leaching 2 Placing the powder into a high-purity graphite crucible, and placing the crucible into a vacuum induction furnace for secondary refining coupling directional solidification crystal form control; controlling the smelting temperature of the directional solidification furnace to be 1500 ℃, controlling the directional solidification pull-down speed to be 1 mu m/s and controlling the magnetic field strength to be 0.1T;
(11) Cutting the ingot after the secondary directional solidification, performing head and tail removal, cutting along a separation boundary line, performing XRD diffraction analysis and quantitative analysis on a bottom separation phase, and performing Rietveld refinement on a diffraction curve by adopting Jade software to obtain the following crystal structure constants:
is in line with C54-TiSi 2 Crystal structure constant requirements; bottom C54-TiSi 2 The purity of (2) was 99.96%.
Example 2
As shown in the flow chart of fig. 1, the specific steps are as follows:
(1) Firstly, 150g of acid-soluble titanium slag (TiO) 2 ：78wt.％，FeO：4.69wt.％，MnO：0.89wt.％，CaO：2.12wt.％，MgO：5.87wt％，SiO 2 ：5.32wt.％，Al 2 O 3 :2.52 wt.%) cutting waste material (Si: 90wt.% SiO 2 :10 wt.%) CaO and Al 2 O 3 According to the mass ratio of 1:1.25:0.924:0.308 g of diamond wire silicon wafer cutting waste 187.5g, 138.7g of CaO and 46.2g of Al are weighed respectively 2 O 3 ；
(2) Weighing acid-soluble titanium slag, diamond wire silicon wafer cutting waste, caO and Al 2 O 3 Mixing, and ball milling in a planetary ball mill for 10min to obtain a mixture with particle size of-74 μm accounting for 85.26%;
(3) Loading the ball-milled raw materials into a high-purity graphite crucible;
(4) Placing the high-purity graphite crucible filled with the raw materials into a high-temperature box-type resistance furnace for reduction smelting; the smelting temperature is 1550 ℃ and the smelting time is 120min;
(5) After smelting, cooling to room temperature, taking out a high-purity graphite crucible, crushing a sample, and separating slag from gold to obtain Ti-58.68wt.% Si alloy (wherein 34.58wt.% Ti, 58.68wt.% Si, and 2.68wt.% Fe and 0.508wt.% Mn respectively);
(6) Placing Ti-58.68wt.% Si alloy into a high-purity graphite crucible, and placing the graphite crucible filled with the alloy into a vacuum induction furnace for primary refining, coupling, directional solidification, phase separation and impurity removal; controlling the smelting temperature of the directional solidification furnace to 1550 ℃, controlling the directional solidification pull-down speed to 100 mu m/s and controlling the magnetic field strength to 10T;
(7) Cutting the ingot obtained by primary refining coupling directional solidification into a head and a tail, and then cutting along a phase separation boundary line to obtain TiSi at the bottom 2 The purity of (2) is 99.46%, and the removal rates of Fe and Mn are 99.89% and 99.90%, respectively;
(8) Crude TiSi 2 Crushing and sampling, wherein the granularity is controlled to be more than 92% with the proportion of-74 mu m;
(9) Crude TiSi after sample preparation treatment 2 And (3) performing alkaline leaching deep Si removal, wherein the control process parameters are as follows: the mass concentration of the NaOH solution is 10%, the alkaline leaching temperature is 80 ℃, the alkaline leaching time is 10min, and the liquid-solid ratio is 3:1, the power of the ultrasonic generator is 100W; tiSi after alkaline leaching 2 The purity of the silicon can reach 99.90wt percent, and the silicon removal rate reaches 99.96 percent;
(10) C54-TiSi after deep Si removal 2 Performing secondary directional solidification depth impurity removal on the powder; alkali-leached TiSi 2 Placing the powder into a high-purity graphite crucible, and placingPerforming secondary refining coupling directional solidification crystal form control in a vacuum induction furnace; controlling the smelting temperature of the directional solidification furnace to 1600 ℃, controlling the directional solidification pull-down speed to 10 mu m/s and controlling the magnetic field strength to 20T;
(11) Cutting the ingot after the secondary directional solidification, performing head and tail removal, cutting along a separation boundary line, performing XRD diffraction analysis and quantitative analysis on a bottom separation phase, and performing Rietveld refinement on a diffraction curve by adopting Jade software to obtain the following crystal structure constants:
is in line with C54-TiSi 2 Crystal structure constant requirements; bottom C54-TiSi 2 The purity of (2) was 99.93%.
Example 3
As shown in the flow chart of fig. 1, the specific steps are as follows:
(1) Firstly, 150g of acid-soluble titanium slag (TiO) 2 ：78wt.％，FeO：4.69wt.％，MnO：0.89wt.％，CaO：2.12wt.％，MgO：5.87wt％，SiO 2 ：5.32wt.％，Al 2 O 3 :2.52 wt.%) cutting waste material (Si: 90wt.% SiO 2 :10 wt.%) CaO and Al 2 O 3 According to the mass ratio of 1:1.46:1: 219.4g of diamond wire silicon wafer cutting waste, 150g of CaO and 34.67g of Al are weighed out by 0.23 g 2 O 3 ；
(2) Weighing acid-soluble titanium slag, diamond wire silicon wafer cutting waste, caO and Al 2 O 3 Mixing, and then placing into a planetary ball mill for ball milling treatment for 15min to obtain the mixture with the particle size of-74 mu m accounting for 89%;
(3) Loading the ball-milled raw materials into a high-purity MgO crucible;
(4) Placing the high-purity graphite crucible filled with the raw materials into a high-temperature box-type resistance furnace for reduction smelting; the smelting temperature is 1600 ℃ and the smelting time is 240min;
(5) After smelting, cooling to room temperature, taking out a high-purity graphite crucible, crushing a sample, and separating slag from gold to obtain Ti-60wt.% Si alloy (wherein, ti is 35.46wt.%, si is 60wt.%, and the contents of Fe and Mn are 2.14wt.% and 0.404wt.% respectively);
(6) Placing Ti-60wt.% Si alloy into a high-purity graphite crucible, and placing the graphite crucible filled with the alloy into a vacuum induction furnace for primary refining, coupling, directional solidification, phase separation and impurity removal; controlling the smelting temperature of the directional solidification furnace to 1600 ℃, controlling the directional solidification pull-down speed to 50 mu m/s and controlling the magnetic field strength to 20T;
(7) Cutting the ingot obtained by primary refining coupling directional solidification into a head and a tail, and then cutting along a phase separation boundary line to obtain TiSi at the bottom 2 The purity of (2) is 99.59%, and the removal rates of Fe and Mn are 99.91% and 99.94%, respectively;
(8) Crude TiSi 2 Crushing and sampling, wherein the granularity is controlled to be more than 95% with the proportion of-74 mu m;
(9) Crude TiSi after sample preparation treatment 2 And (3) performing alkaline leaching deep Si removal, wherein the control process parameters are as follows: the mass concentration of the NaOH solution is 15%, the alkaline leaching temperature is 85 ℃, the alkaline leaching time is 20min, and the liquid-solid ratio is 2.5:1, the power of the ultrasonic generator is 150W; tiSi after alkaline leaching 2 The purity of the silicon can reach 99.97wt percent, and the silicon removal rate reaches 99.98 percent;
(10) C54-TiSi after deep Si removal 2 Performing secondary directional solidification depth impurity removal on the powder; alkali-leached TiSi 2 Placing the powder into a high-purity graphite crucible, and placing the crucible into a vacuum induction furnace for secondary refining coupling directional solidification crystal form control; controlling the smelting temperature of the directional solidification furnace to 1550 ℃, controlling the directional solidification pull-down speed to 5 mu m/s and controlling the magnetic field strength to 20T;
(11) Cutting the ingot after the secondary directional solidification, performing head and tail removal, cutting along a separation boundary line, performing XRD diffraction analysis and quantitative analysis on a bottom separation phase, and performing Rietveld refinement on a diffraction curve by adopting Jade software to obtain the following crystal structure constants:
is in line with C54-TiSi 2 Crystal structure constant requirements; bottom C54-TiSi 2 The purity of (2) was 99.98%.
Claims (10)
1. Production of C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag 2 Is characterized in that: the method comprises the following steps:
A. cutting acid-soluble titanium slag, diamond linear silicon wafer waste, caO and Al 2 O 3 According to the mass ratio of 1:1 to 1.5:0.85 to 1.0:0.23 to 0.4, and then ball milling is carried out to obtain a mixture;
B. reducing and smelting the mixture, and cooling, crushing and separating slag from gold after smelting to obtain Ti-Si alloy;
C. carrying out primary refining coupling directional solidification on Ti-Si alloy to obtain coarse C54-TiSi 2 The method comprises the steps of carrying out a first treatment on the surface of the The parameters for controlling the primary refining coupling directional solidification are as follows: the smelting temperature is 1500-1600 ℃, the directional solidification pull-down speed is 10-100 mu m/s, and the magnetic field strength is 0.1-20T;
D. crude C54-TiSi 2 Crushing, and then performing ultrasonic alkaline leaching to deeply remove Si;
E. C54-TiSi after deep Si removal 2 Performing secondary directional solidification on the powder to obtain the high-purity C54-TiSi 2 The method comprises the steps of carrying out a first treatment on the surface of the The parameters for controlling the secondary directional solidification are as follows: the smelting temperature is 1500-1600 ℃, the directional solidification pull-down speed is 1-10 mu m/s, and the magnetic field strength is 0.1-20T.
2. The method for producing C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag according to claim 1 2 Is characterized in that: in step a, at least one of the following is satisfied:
the acid-soluble titanium slag contains TiO 2 ：71.56～83.27wt.％，FeO：2.29～7.84wt.％，MnO：0.59～1.02wt.％，CaO：1.86～2.16wt.％，MgO：5.87～7.14wt％，SiO 2 ：2.28～5.82wt.％，Al 2 O 3 ：1.48～2.66wt.％；
The diamond wire silicon wafer cutting waste contains Si: 81.56-92.13 wt.% SiO 2 ：7.26～17.46wt.％；
The ball milling time is 5-15 min;
the particle size of the mixture is-74 mu m, and the proportion is 82-89%.
3. The method for producing C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag according to claim 1 2 Is characterized in that: in the step B, the reduction smelting temperature is 1500-1600 ℃; the reduction smelting time is 60-240 min.
4. The method for producing C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag according to claim 1 2 Is characterized in that: in the step B, ti in the Ti-Si alloy: 27-38 wt.%, si: 57-60 wt.%, fe:2.1 to 3.0wt.%, mn:0.4 to 0.6wt.%.
5. The method for producing C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag according to claim 1 2 Is characterized in that: in the step C, the cast ingot obtained by primary refining coupling directional solidification is subjected to head cutting and tail cutting, and is cut along a phase separation boundary line to obtain crude C54-TiSi 2 。
6. The method for producing C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag according to claim 1 2 Is characterized in that: in step D, crude C54-TiSi 2 Crushing to particle size of-74 μm with a ratio of more than 90%.
7. The method for producing C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag according to claim 1 2 Is characterized in that: in the step D, parameters of the ultrasonic alkaline leaching depth for removing Si are as follows: the mass concentration of the NaOH solution is 5-15%, the alkaline leaching temperature is 75-85 ℃, the alkaline leaching time is 5-20 min, and the liquid-solid ratio is 2.5-3.5: 1, the power of the ultrasonic generator is 0-150W.
8. The method for producing C54-TiSi by utilizing diamond wire silicon wafer cutting waste and acid-soluble titanium slag according to claim 1 2 Is characterized in that: in step E, the secondary directional solidification is carried out to obtainCutting the obtained cast ingot into a head and a tail, and cutting along a phase separation boundary line to obtain high-purity C54-TiSi 2 。
9. The production of C54-TiSi using diamond wire silicon wafer cutting waste and acid-soluble titanium slag according to any one of claims 1 to 8 2 Is characterized in that: in the step E, the obtained high-purity C54-TiSi 2 The purity of (2) is 99.93-99.98%; the crystal structure constant is as follows:
10. the C54-TiSi obtained by the process of any one of claims 1 to 9 2 。
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