CN117086318A - Preparation method of low-oxygen metal titanium powder - Google Patents

Preparation method of low-oxygen metal titanium powder Download PDF

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Publication number
CN117086318A
CN117086318A CN202210516759.XA CN202210516759A CN117086318A CN 117086318 A CN117086318 A CN 117086318A CN 202210516759 A CN202210516759 A CN 202210516759A CN 117086318 A CN117086318 A CN 117086318A
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powder
reduction
titanium
reducing agent
slurry
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张盈
郑诗礼
蔡涛涛
张懿
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/20—Refractory metals
    • B22F2301/205—Titanium, zirconium or hafnium

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention provides a preparation method of low-oxygen metal titanium powder, which is characterized in that a first reduction powder and a second reduction powder are respectively prepared through aluminum reduction and magnesium reduction, then the first reduction powder and the second reduction powder are mixed and sintered to obtain a titanium oxide solid solution, and the titanium oxide solid solution is subjected to third reduction and third wet treatment, so that the low-oxygen metal titanium powder can be prepared. Compared with the titanium dioxide full magnesium reduction, the preparation method has the characteristics of reducing the cost of the reducing agent, and has the advantages of low oxygen content of the metal titanium powder, low operation temperature of the whole process and easy safe amplification.

Description

Preparation method of low-oxygen metal titanium powder
Technical Field
The invention relates to the technical field of preparation of metal titanium powder, in particular to a preparation method of low-oxygen metal titanium powder.
Background
Titanium and titanium alloy are important functional and structural materials, and are widely applied in the fields of aerospace, marine ships, chemical energy sources, biomedical treatment and the like. Titanium is a typical chemically active metal, and the strong chemical activity of titanium makes the preparation of titanium metal more difficult and costly than common metals, and also makes titanium and titanium alloy easy to be polluted by oxygen in the processing process. The conventional processing method of the titanium forging/workpiece is a forging method, the process is long, the cutting of titanium alloy materials is difficult, the buying-flying ratio of the workpiece manufactured by rolling products is up to 12:1-20:1, the material utilization rate is very low, and the cost of the titanium workpiece is high.
The near-net forming method using high-quality titanium and titanium alloy powder as raw materials is a substitute processing method for some titanium parts with complex shapes and special customization, has short flow and high material utilization rate, and is one of the key points for reducing the preparation cost of the high-quality powder.
There are various methods for preparing metallic titanium/titanium alloy powders. The currently mainstream titanium powder production method is a hydrogenation-dehydrogenation method (HDH), which is a production process of firstly absorbing hydrogen, hydrogenating and embrittling sponge titanium/titanium ingots/titanium scraps and the like, then crushing the sponge titanium/titanium ingots/titanium scraps into a required size range, and finally carrying out vacuum dehydrogenation. The HDH method can produce pure titanium powder and titanium alloy powder, the product morphology is generally irregular, and the granularity control is realized by sieving. However, the HDH method does not have a purification function, and the purity of the powder depends on the purity of the raw material; and the O/N content of the powder obtained is generally increased too much and control is difficult. The high-quality titanium alloy powder with high purity and sphericity is prepared by an atomization method basically, and comprises gas atomization, plasma atomization, centrifugal atomization and the like. Various atomization methods generally include three steps, namely, melting, atomizing and cooling, and the molten liquid metal is atomized into metal droplets by high-pressure air or the metal droplets are manufactured by centrifugal force generated by high-speed rotation and rapidly cooled in a protective atmosphere to become spherical metal particles. The atomization method has low fine powder rate, high consumption of electricity and argon and high cost of atomized powder, and the selling price of atomized powder is hundreds to thousands of yuan per kilogram.
The HAMR method is a novel TiO method proposed in recent years 2 The key steps of the magnesian reduction method comprise three main steps of magnesium reduction under the hydrogen atmosphere, heat treatment and magnesium deoxidation under the hydrogen atmosphere. The method is not only hopeful to reduce the smelting cost of the metallic titanium, but also can directly prepare the metallic titanium powder with low oxygen content and high quality, provides a new development direction for the powder metallurgy of the titanium, but has the problem of higher cost of the reducing agent.
Therefore, there is a need to further reduce the cost ratio of the reducing agent in the process and to improve the quality of the low-oxygen titanium powder.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a preparation method of low-oxygen metal titanium powder, which is characterized in that the first reduction powder and the second reduction powder which are respectively obtained through aluminum reduction and magnesium reduction are mixed and sintered and then subjected to third reduction and third wet treatment, so that the low-oxygen titanium powder with low oxygen content can be obtained, a high Wen Zhajin separation method is not needed, the controllability of the reaction process is high, and the industrial application prospect is wider.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of low-oxygen metal titanium powder, which comprises the following steps:
(1) Performing first reduction and first wet treatment on a calcium-titanium-containing source through the action of a first reducing agent and a first auxiliary agent to obtain first reduction powder, wherein the first reduction powder is TiO x Powder, wherein x is more than or equal to 0.333 and less than or equal to 0.5, and the first reducing agent comprises aluminum; sequentially carrying out second reduction and second wet treatment on the titanium dioxide by a second reducing agent to obtain second reduction powder, wherein the oxygen content in the second reduction powder is less than or equal to 3wt%, and the second reducing agent comprises magnesium;
(2) Mixing the first reducing powder and the second reducing powder, and sintering to obtain a titanium oxide solid solution with the oxygen content less than or equal to 8 wt%;
(3) And carrying out third reduction and third wet treatment on the titanyl solid solution by a third reducing agent to obtain low-oxygen metal titanium powder, wherein the third reducing agent comprises magnesium and/or calcium.
The first reduction and the second reduction are not sequential in the invention.
The invention discovers that the calcium-containing substance and the first auxiliary agent are combined, on the basis of aluminum as a reducing agent, the reduced aluminum phase can be controlled to be a calcium aluminum oxide phase which is soluble in dilute acid, so that TiO can be efficiently separated from the aluminum phase by the first wet treatment x The intermediate powder is used as first reducing powder; and the first reducing powder and the second reducing powder with the oxygen content less than or equal to 3 weight percent are mixed and sintered and then subjected to third reduction, so that the sintering effect can be ensured on one hand, and the obtained titanium oxide solid solution can be reduced in the third reduction better, thereby saving the reducing agent The use cost of the metal titanium powder after reduction is higher.
In addition, the method is aimed at aluminum reduction, a self-propagating reduction mode is not needed, a high Wen Zhajin separation method is not needed in the follow-up process, direct wet separation can be achieved, and operation safety is remarkably improved.
The invention firstly carries out the first step of TiO x X in the intermediate powder is controlled to be more than or equal to 0.333 and less than or equal to 0.5, on one hand, the reducing agent aluminum is fully utilized to deoxidize, and on the other hand, the aluminum is favorable for inhibiting the aluminum from flowing into TiO x Alloying in the intermediate powder, ensuring the purity of the metal titanium powder, controlling the oxygen content of the titanium oxide solid solution to be less than or equal to 8wt% in the second step, strengthening the firing of the titanium oxide solid solution and ensuring the deoxidization depth in the third reduction process.
Preferably, the low-oxygen metal titanium powder refers to titanium powder with the oxygen content less than or equal to 0.30wt%, and can be 0.30wt%, 0.25wt%, 0.2wt%, 0.15wt%, 0.12wt%, 0.10wt%, 0.08wt%, or the like.
The x of the present invention is controlled to be 0.333.ltoreq.x.ltoreq.0.5, and may be, for example, 0.333, 0.34, 0.35, 0.36, 0.38, 0.40, 0.42, 0.45, 0.48, 0.49, 0.5 or the like.
The oxygen content in the second reducing powder is less than or equal to 3wt%, for example, 3wt%, 2.8wt%, 2.7wt%, 2.6wt%, 2.5wt%, 2.4wt%, 2wt%, 1.8wt%, 1.5wt%, or the like.
The oxygen content in the titanium oxide solid solution is 8wt% or less, for example, 8wt%, 7.5wt%, 7.6wt%, 7.2wt%, 7.0wt%, 6.5wt%, 6.2wt% or 6.0wt% or the like.
Preferably, the calcium-containing titanium source in step (1) comprises any one or a combination of at least two of a first titanium source, a second titanium source, a third titanium source, or a fourth titanium source; the first titanium source is a mixture of titanium dioxide and calcium oxide, the second titanium source is a mixture of calcium oxide and calcined titanium dioxide, and the third titanium source is a mixture of titanium dioxide and calcium oxide according to CaTiO 3 The fourth titanium source is a mixture of calcined product and calcium oxide after mixing calcium oxide and titanium dioxide according to the ratio exceeding CaTiO 3 Is prepared by mixing calcium oxide and titanium dioxide and calcining the mixture.
The calcination temperature in the second titanium source, the third titanium source, or the fourth titanium source is preferably 1000 to 1400 ℃ each independently, and may be 1000 ℃, 1044 ℃, 1088 ℃, 1132 ℃, 1176 ℃, 1220 ℃, 1264 ℃, 1308 ℃, 1352 ℃, 1400 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the molar ratio of the calcium in the calcium-containing titanium source to the first reducing agent in the step (1) is 0.6-2:1, for example, may be 0.6:1, 0.75:1, 0.9:1, 1.05:1, 1.2:1, 1.35:1, 1.5:1, 1.65:1, 1.8:1 or 2:1, etc.
Preferably, the molar ratio of the first reducing agent to titanium in the calcic-titaniferous source is 1 to 1.22:1, for example, 1:1, 1.04:1, 1.07:1, 1.11:1, 1.14:1, 1.18:1, 1.19:1, 1.20:1, 1.21:1, or 1.22:1, etc.
The present invention further preferably provides that the molar ratio of calcium, titanium and the first reducing agent in the first reduction is within the above-described range, and that the formation of an insoluble aluminum phase can be avoided while ensuring that the first reduction reaches a set oxygen content level.
Preferably, the first adjuvant in step (1) comprises anhydrous CaCl 2 、CaCl 2 KCl eutectic salt and CaCl 2 NaCl eutectic salt or CaCl 2 Any one or a combination of at least two of LiCl co-molten salts, wherein typical but non-limiting combinations are: caCl (CaCl) 2 With CaCl 2 -combination of KCl co-molten salts, caCl 2 With CaCl 2 -combination of NaCl eutectic salts, caCl 2 With CaCl 2 Combinations of LiCl co-molten salts, caCl 2 LiCl eutectic salt and CaCl 2 -combination of NaCl eutectic salts, caCl 2 -KCl eutectic salt and CaCl 2 -combinations of LiCl co-molten salts.
The invention further preferably uses calcium-containing substances as a first auxiliary agent, which can better control the formation of aluminum into an aluminum phase which is easily dissolved in dilute acid, and avoid aluminum in TiO x Residue in the powder, and simultaneously guaranteeing TiO x The oxygen content in the meal reaches a set level.
Preferably, the first auxiliary agent and the titanium in the calcium-containing titanium source are mixed with TiO 2 The weight ratio of the components is 0.05 to 3:1, for example, 0.05:1, 0.1:1 and 0.15:1. 0.2:1, 0.5:1, 1.0:1, 1.5:1, 2.0:1, 2.5:1, 2.8:1, or 3.0:1, etc.
Preferably, the shape of the first reducing agent comprises any one or a combination of at least two of powder, flake or granule, wherein typical but non-limiting combinations are combinations of powder and flake, combinations of granule and flake, combinations of powder and granule.
Preferably, the temperature of the first reduction is 700 to 1200 ℃, and may be 700 ℃, 750 ℃, 800 ℃, 820 ℃, 855 ℃, 930 ℃, 1010 ℃, 1080 ℃, 1160 ℃, 1200 ℃ or the like, for example.
Preferably, the time of the first reduction is 0.3 to 24 hours, for example, 0.3 hours, 3.0 hours, 5.6 hours, 8.2 hours, 10.7 hours, 13.5 hours, 16.1 hours, 18.8 hours, 21.5 hours, 24 hours, or the like.
Preferably, the atmosphere of the first reduction comprises a vacuum or a protective atmosphere.
Preferably, the protective atmosphere for the first reduction comprises any one or a combination of at least two of argon, hydrogen or helium, wherein typical but non-limiting combinations are: argon and hydrogen, argon and helium, hydrogen and helium, and argon, hydrogen and helium.
Preferably, the temperature of the second reduction in the step (1) is 600 to 900 ℃, and may be 600 ℃, 650 ℃, 677 ℃, 705 ℃, 732 ℃, 760 ℃, 787 ℃, 815 ℃, 842 ℃, 868 ℃, 900 ℃ or the like, for example.
Preferably, the time of the second reduction is 0.25 to 48 hours, for example, 0.25 hours, 1.0 hours, 5.0 hours, 10.5 hours, 15 hours, 21 hours, 28 hours, 35 hours, 40 hours or 48 hours, etc.
Preferably, the molar ratio of the second reducing agent to the titanium dioxide is 2 to 4:1, for example, it may be 2:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.8:1, 2.9:1, 3.0:1, 3.2:1, 3.3:1, 3.5:1 or 4:1, etc.
The invention preferably controls the mole ratio of the second reducing agent to the titanium dioxide in the above range, which is more favorable for ensuring the oxygen content in the second reducing powder obtained in the second reduction process.
Preferably, the shape of the second reducing agent comprises any one or a combination of at least two of powder, flake or granule, wherein typical but non-limiting combinations are powder and flake combinations, granule and flake combinations, powder and granule combinations.
Preferably, the second reducing atmosphere is any one or a combination of at least two of argon, hydrogen or helium, wherein typical but non-limiting combinations are combinations of argon and hydrogen, combinations of helium and hydrogen, and combinations of argon and helium.
Preferably, a second adjuvant is added to the second reduction in step (1).
Preferably, the weight ratio of the second auxiliary agent to the titanium dioxide is 0.05-3:1, for example, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.5:1, 1.0:1, 1.5:1, 2.0:1, 2.5:1, 2.8:1 or 3.0:1, etc.
Preferably, the second auxiliary comprises anhydrous MgCl 2 、MgCl 2 -CaCl 2 Eutectic salt, mgCl 2 -NaCl co-molten salt or MgCl 2 -any one or a combination of at least two of KCl co-molten salts, wherein a typical but non-limiting combination is: mgCl 2 With MgCl 2 -CaCl 2 Combination of co-fused salts, mgCl 2 With MgCl 2 Combination of NaCl eutectic salts, mgCl 2 With MgCl 2 Combination of KCl co-fused salts, mgCl 2 -KCl co-molten salt and MgCl 2 Combination of NaCl eutectic salts, mgCl 2 -KCl co-molten salt and MgCl 2 -CaCl 2 And (3) combination of the eutectic salts.
Preferably, the mixing in step (2) comprises dry powder mixing, or the mixing comprises mixing, crushing and granulating the first and second reducing powders.
Preferably, the dry powder blend includes any one or a combination of at least two of three-dimensional blend, V-blend, or roller blend, wherein typical but non-limiting combinations are combinations of three-dimensional blend and V-blend, combinations of roller blend and V-blend, combinations of three-dimensional blend and roller blend.
Preferably, the means of crushing includes any one or a combination of at least two of ball milling, tumbling, stirred milling or air flow milling, wherein typical but non-limiting combinations are ball milling and stirred milling, air flow milling and stirred milling, and air flow milling.
Preferably, the granulating means comprises any one of spray granulation, roller granulation or compression granulation.
Preferably, the mass ratio of the first reducing powder to the second reducing powder is 1:0.267-10, which may be, for example, 1:0.267, 1:0.3, 1:0.34, 1:0.38, 1:0.4, 1:0.5, 1:0.8, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, etc.
Preferably, the sintering temperature in the step (2) is 800 to 1200 ℃, and may be 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, or the like, for example.
Preferably, the sintering time is 0.25 to 24 hours, and may be, for example, 0.25 hours, 0.5 hours, 0.8 hours, 1 hour, 1.2 hours, 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 24 hours, or the like.
Preferably, the sintering atmosphere is a vacuum or a protective atmosphere.
Preferably, the protective atmosphere for sintering comprises any one or a combination of at least two of hydrogen, argon or helium, wherein typical but non-limiting combinations are combinations of hydrogen and argon, combinations of helium and argon, combinations of hydrogen and helium.
Preferably, the shape of the third reducing agent in step (3) comprises any one or a combination of at least two of powder, flake or granule, wherein typical but non-limiting combinations are combinations of powder and flake, combinations of granule and flake, combinations of powder and granule.
Preferably, a third adjuvant is added to the third reduction.
Preferably, when the third reducing agent contains magnesium, the mass ratio of magnesium to titanyl solid solution is 0.033-0.6:1, for example, may be 0.033:1, 0.04:1, 0.05:1, 0.07:1, 0.09:1, 0.1:1, 0.12:1, 0.14:1, 0.15:1, 0.17:1, 0.19:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, or 0.6:1, etc.
Preferably, when the third reducing agent contains magnesium, the third auxiliary comprises anhydrous MgCl 2 、MgCl 2 -CaCl 2 Eutectic salt, mgCl 2 -NaCl co-molten salt or MgCl 2 Any one or a combination of at least two of KCl co-molten salts, wherein a typical but non-limiting combination is anhydrous MgCl 2 And MgCl 2 -CaCl 2 Combination of co-fused salts, mgCl 2 -KCl co-molten salt and MgCl 2 -CaCl 2 Combination of co-fused salts, anhydrous MgCl 2 And MgCl 2 -a combination of KCl co-molten salts.
Preferably, when the third reducing agent contains magnesium, the weight ratio of the third auxiliary agent to the titanium oxide solid solution is 0.05-3:1, for example, 0.05:1, 0.38:1, 0.70:1, 1.05:1, 1.35:1, 1.65:1, 2.05:1, 2.35:1, 2.65:1, or 3:1, etc.
Preferably, when the third reducing agent contains magnesium, the temperature of the third reduction is 650 to 900 ℃, and for example, 650 ℃, 670 ℃, 700 ℃, 730 ℃, 760 ℃, 780 ℃, 810 ℃, 840 ℃, 870 ℃, 900 ℃ or the like may be used.
Preferably, when the third reducing agent contains magnesium, the time of the third reduction is 0.25 to 48 hours, for example, 0.25 hours, 5 hours, 10 hours, 16 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 48 hours, or the like.
Preferably, when the third reducing agent contains magnesium, the third reducing atmosphere includes a hydrogen-argon mixed atmosphere or a pure hydrogen atmosphere.
Preferably, the volume fraction of hydrogen in the hydrogen-argon mixed atmosphere is 5-100%, for example, 5%, 16%, 27%, 37%, 48%, 58%, 69%, 79%, 90% or 100% or the like.
Preferably, when the third reducing agent contains calcium, the mass ratio of calcium to titanyl solid solution is 0.033 to 0.8:1, for example, 0.033:1, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.6:1, 0.7:1, or 0.8:1, etc.
Preferably, the third auxiliary agent comprises anhydrous CaCl when the third reducing agent contains calcium 2 、CaCl 2 -MgCl 2 Eutectic salt, caCl 2 NaCl eutectic salt, caCl 2 KCl co-fused salt or CaCl 2 Any one or a combination of at least two of LiCl co-molten salts, wherein a typical but non-limiting combination is anhydrous CaCl 2 And CaCl 2 -MgCl 2 Co-molten salt combination and CaCl 2 KCl eutectic salt and CaCl 2 -MgCl 2 Co-molten salt combination and anhydrous CaCl 2 And CaCl 2 -combinations of LiCl co-molten salts.
Preferably, when the third reducing agent contains calcium, the weight ratio of the third auxiliary agent to the titanyl solid solution is 0.05-3:1, for example, 0.05:1, 0.35:1, 0.75:1, 1.05:1, 1.35:1, 1.65:1, 2.05:1, 2.35:1, 2.65:1, or 3:1, etc.
Preferably, when the third reducing agent contains calcium, the temperature of the third reduction is 700 to 1100 ℃, and may be 700 ℃, 740 ℃, 780 ℃, 830 ℃, 870 ℃, 920 ℃, 960 ℃, 1010 ℃, 1050 ℃, 1100 ℃, or the like, for example.
Preferably, when the third reducing agent contains calcium, the time of the third reduction is 0.25 to 48 hours, for example, 0.25 hours, 5 hours, 10 hours, 15 hours, 21 hours, 26 hours, 32 hours, 35 hours, 40 hours, 48 hours, or the like.
Preferably, when the third reducing agent contains calcium, the atmosphere for the third reduction comprises a vacuum or a protective atmosphere.
Preferably, the protective atmosphere for the third reduction comprises any one or a combination of at least two of argon, hydrogen or helium, wherein typical but non-limiting combinations are combinations of argon and hydrogen, combinations of helium and hydrogen, and combinations of argon and helium.
Preferably, the first wet treatment in step (1) comprises: slurrying the first reduced product with water and/or acid liquor to obtain slurry; and sequentially carrying out pH adjustment and solid-liquid separation on the slurry, and sequentially washing and drying the obtained solid phase to obtain the first reduction powder.
Preferably, the second wet treatment in step (1) comprises: slurrying the second reduced product with water and/or acid liquor to obtain slurry; and sequentially carrying out pH adjustment and solid-liquid separation on the slurry, and sequentially washing and drying the obtained solid phase to obtain second reduction powder.
Preferably, the third wet treatment in step (3) comprises: pulping the third reduced product by water and/or acid liquor to obtain slurry; and sequentially carrying out pH adjustment and solid-liquid separation on the slurry, and sequentially washing and drying the obtained solid phase to obtain the low-oxygen metal titanium powder.
Preferably, the pH of the acid solution in the first wet process, the second wet process and the third wet process is not less than 0.5, for example, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0, etc. independently.
Preferably, the liquid to solid ratios of slurried in the first, second and third wet treatments are each independently 1 to 100:1mL/g, which may be, for example, 1:1mL/g, 12:1mL/g, 20:1mL/g, 30:1mL/g, 45:1mL/g, 50:1mL/g, 60:1mL/g, 70:1mL/g, 80:1mL/g, or 100:1mL/g, etc.
Preferably, the acid used for pH adjustment in the first wet process, the second wet process and the third wet process is each independently hydrochloric acid.
Preferably, the pH of the slurry is controlled to be more than or equal to 0.8 in each of the first wet treatment, the second wet treatment and the third wet treatment independently, and the pH may be, for example, 0.8, 0.9, 1.0, 1.1, 1.2, 1.5 or 2.0.
Preferably, the pH of the slurry after pH adjustment in the first wet process, the second wet process and the third wet process is each independently 1.5 to 3.0, and may be, for example, 1.5, 1.7, 1.9, 2, 2.2, 2.4, 2.5, 2.7, 2.9 or 3.0, etc.
In the invention, in order to prevent the first reducing powder, the second reducing powder and the low-oxygen metal titanium powder from carrying out dissolution reaction with acid in the pH adjusting process, the slurry in the pH adjusting process is preferably controlled to be more than 0.8, and the pH adjusting process is regarded as ending when the pH value is stable between 1.5 and 3.0.
Preferably, the temperature of the washing in the first wet process, the second wet process and the third wet process is each independently 0 to 60 ℃, for example, may be 0 ℃, 7 ℃, 14 ℃, 20 ℃, 27 ℃, 34 ℃, 40 ℃, 47 ℃, 54 ℃, 60 ℃, or the like.
Preferably, the washing comprises water washing.
Preferably, the drying temperatures in the first wet process, the second wet process and the third wet process are each independently 60 ℃ or less, and may be, for example, 0 ℃, 7 ℃, 14 ℃, 20 ℃, 27 ℃, 34 ℃, 40 ℃, 47 ℃, 54 ℃, 60 ℃ or the like. The drying mode is one of normal pressure drying or vacuum drying or freeze drying at the temperature of not more than 60 ℃, and the temperature of the drying can be controlled to effectively prevent the excessive oxidation of the surface of the titanium powder, thereby being more beneficial to controlling the oxygen content level of the final metal titanium powder.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing a calcium-containing titanium source, a first reducing agent and a first auxiliary agent, wherein the molar ratio of calcium in the calcium-containing titanium source to the first reducing agent is 0.6-2:1, the molar ratio of the first reducing agent to titanium in the calcium-containing titanium source is 1-1.22:1, and the first auxiliary agent and the titanium in the calcium-containing titanium source are prepared by adopting TiO (titanium oxide) 2 The weight ratio is 0.05-3:1, and the first reduction is carried out for 0.3-24 h at 700-1200 ℃ sequentially through vacuum or protective atmosphere, thus obtaining a first reduction product;
slurrying the first reduced product by water and/or acid liquor with the pH value of more than or equal to 0.5, wherein the liquid-solid ratio is 1-100:1 mL/g, so as to obtain slurry; the slurry is subjected to pH adjustment in sequence, the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized to be 1.5-3.0, and solid-liquid separation is carried out, and the obtained solid phase is washed at 0-60 ℃ and dried at less than or equal to 60 ℃ in sequence to obtain first reduction powder;
Carrying out second reduction on the titanium dioxide for 0.25-48 h in a protective atmosphere at 600-900 ℃ by using a second reducing agent and a second auxiliary agent, wherein the molar ratio of the second reducing agent to the titanium dioxide is 2-4:1, and the weight ratio of the second auxiliary agent to the titanium dioxide is 0.05-3:1, so as to obtain a second reduced product;
slurrying the second reduced product by water and/or acid liquor with the pH value of more than or equal to 0.5, wherein the liquid-solid ratio is 1-100:1 mL/g, so as to obtain slurry; the slurry is subjected to pH adjustment in sequence, the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 1.5-3.0, and the obtained solid phase is subjected to solid-liquid separation, washing at 0-60 ℃ and drying at less than or equal to 60 ℃ in sequence, so that second reduction powder is obtained;
(2) Mixing the first reducing powder and the second reducing powder according to the mass ratio of 1:0.267-10, and sintering for 0.25-24 hours at 800-1200 ℃ under vacuum or protective atmosphere to obtain a titanium oxide solid solution with the oxygen content less than or equal to 8 wt%;
(3) The titanium oxide solid solution is subjected to third reduction under the action of a third reducing agent and a third auxiliary agent to obtain a third reduction product;
slurrying the third reduced product by water and/or acid liquor with the pH value of more than or equal to 0.5, wherein the liquid-solid ratio is 1-100:1 mL/g, so as to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized to be 1.5-3.0, and the solid phase obtained through solid-liquid separation is washed at 0-60 ℃ and dried at less than or equal to 60 ℃ in sequence, so that the low-oxygen metal titanium powder is obtained.
The method can control the oxygen content to be between 10 and 14.3 percent in the first reduction, and can effectively inhibit the aluminum from being converted into TiO x Solid solution in (3); the second reducing powder has low additional cost compared with the return of low-oxygen titanium powder, good crushing performance and TiO x The effect of the mixed reinforced sintering is equivalent to that of the returned low-oxygen titanium powder, the sintering temperature is low, and the energy consumption is reduced.
The solid-liquid separation in the above process is not particularly limited, and any device and method for solid-liquid separation known to those skilled in the art can be used, and can be adjusted according to the actual process, for example, filtration, centrifugation or sedimentation separation, or the like, or a combination of different methods.
The drying in the above process is not particularly limited, and any device and method known to those skilled in the art for drying may be used, or may be modified according to the actual process, for example, air drying, vacuum drying, drying or freeze drying, or may be a combination of different methods.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) Compared with the full magnesium reduction process of oxygen in titanium dioxide, the preparation method of the low-oxygen metal titanium powder provided by the invention has the advantages that the cost of the reducing agent can be saved by more than 20%, and the reduction efficiency is obviously improved;
(2) According to the preparation method of the low-oxygen metal titanium powder, provided by the invention, the calcium-containing substance and the first auxiliary agent are added and the proper proportion is controlled, so that the alumina enrichment byproduct phase which is easy to dissolve in acid is obtained, the separation of the titanium product and the byproduct phase is more thorough, the temperature requirement on the first reduction process is greatly reduced, and the operation safety is greatly improved;
(3) The preparation method of the low-oxygen metal titanium powder can ensure that the oxygen content in the prepared titanium powder is low and is lower than 0.30 weight percent, and the oxygen content is less than 0.1 weight percent under the preferred condition.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of low-oxygen metal titanium powder according to an embodiment of the invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
As a specific embodiment of the invention, a preparation method of low-oxygen metal titanium powder is provided, and a flow chart of the method is shown in fig. 1, and specifically comprises the following steps:
(1) Mixing a calcium-titanium-containing source (calcined or uncalcined titanium dioxide and calcium oxide), a first reducing agent Al and a first auxiliary agent, and carrying out first reduction to obtain a first reduced product;
the first reduced product is subjected to a first wet process, wherein the first wet process comprises slurrying the first reduced product with water and/or acid liquor to obtain slurry; the slurry is subjected to pH adjustment and solid-liquid separation, and the obtained solid phase is washed and dried in sequence to obtain first reduction powder (TiO) x ，0.333≤x≤0.5)；
Carrying out a second reduction of the titanium dioxide by a second reducing agent and optionally a second auxiliary agent (indicated by a dotted line) to obtain a second reduced product;
the second reduced product is subjected to a second wet process, wherein the second wet process comprises slurrying the second reduced product with water and/or acid liquor to obtain slurry; the slurry is subjected to pH adjustment and solid-liquid separation, and the obtained solid phase is washed and dried in sequence to obtain second reduction powder (the oxygen content is less than or equal to 3 wt%);
(2) Mixing the first reducing powder and the second reducing powder, and sintering to obtain a titanium oxide solid solution with the oxygen content less than or equal to 8 wt%;
(3) The titanyl solid solution is subjected to a third reduction under the action of a third reducing agent (magnesium and/or calcium) and optionally a third auxiliary agent (shown by a dotted line) to obtain a third reduced product;
The third reduced product is subjected to third wet treatment, wherein the third wet treatment comprises slurrying the third reduced product with water and/or acid liquor to obtain slurry; and (3) carrying out pH adjustment on the slurry, carrying out solid-liquid separation, and washing and drying the obtained solid phase in sequence to obtain the low-oxygen metal titanium powder.
Example 1
The embodiment provides a preparation method of low-oxygen metal titanium powder, which comprises the following steps:
(1) Mixing calcium-containing titanium source (mixture of calcium oxide and calcined titanium dioxide), aluminum powder and CaCl 2 -KCl co-molten salt, the molar ratio of calcium to aluminium powder in the calcium-containing titanium source being 1.5:1, the molar ratio of aluminium powder to titanium in the calcium-containing titanium source being 1.1:1, cacl 2 KCl eutectic salt and calcium-titanium-containing source titanium in TiO 2 The weight ratio of the catalyst to the catalyst is 0.5:1, and the catalyst is subjected to first reduction for 6 hours at 1000 ℃ in sequence in helium atmosphere to obtain a first reduced product;
slurrying the first reduced product with water, wherein the liquid-solid ratio is 70:1mL/g, so as to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 2.0, and the slurry is filtered, and the obtained solid phase is washed at normal temperature and dried at 40 ℃ in sequence to obtain first reduction powder;
titanium dioxide is prepared from magnesium powder and MgCl 2 Performing second reduction on KCl eutectic salt in helium atmosphere at 700 ℃ for 24 hours, wherein the molar ratio of magnesium powder to titanium dioxide is 2.0:1, and MgCl is used for preparing the magnesium powder-titanium dioxide composite material 2 -the weight ratio of KCl co-molten salt to titanium dioxide is 2.5:1, yielding a second reduced product;
slurrying the second reduced product with water, wherein the liquid-solid ratio is 20:1mL/g, so as to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 1.2, and the slurry is filtered, and the obtained solid phase is washed at normal temperature and dried at 48 ℃ in sequence to obtain second reducing powder;
(2) Mixing the first reducing powder and the second reducing powder according to the mass ratio of 1:1, and sintering for 12 hours at 1000 ℃ under vacuum condition to obtain a titanium oxide solid solution;
(3) The titanium oxide solid solution is prepared by magnesium powder and MgCl 2 Performing third reduction for 18h at 650 ℃ in a hydrogen-argon mixed atmosphere (the volume fraction of hydrogen is 95 percent), wherein the mass ratio of magnesium powder to titanium oxide solid solution is 0.15:1, and MgCl is adopted 2 The weight ratio of KCl eutectic salt to titanyl solid solution is 2.0:1, and a third reduction product is obtained;
slurrying the third reduced product by hydrochloric acid solution with the pH value of 0.5 and the liquid-solid ratio of 25:1mL/g to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 2.5, and the obtained solid phase is washed at 25 ℃ and dried at 40 ℃ in sequence through filtration, so that the low-oxygen metal titanium powder is obtained.
Example 2
The embodiment provides a preparation method of low-oxygen metal titanium powder, which comprises the following steps:
(1) Mixing a calcium-containing titanium source (according to CaTiO) 3 The mixture of calcined product and calcium oxide after mixing calcium oxide and titanium dioxide), aluminum powder and anhydrous CaCl 2 The molar ratio of the calcium in the calcium-containing titanium source to the aluminum powder is 0.6:1, and the molar ratio of the aluminum powder to the titanium in the calcium-containing titanium source is 1.0:1, and the anhydrous CaCl is prepared by the method of the preparation method 2 TiO with titanium in a calcium-containing titanium source 2 The weight ratio is 3:1, and the first reduction is carried out for 24 hours at 1200 ℃ under vacuum condition in sequence to obtain a first reduced product;
slurrying the first reduced product by hydrochloric acid solution with the pH value of 2.5 and the liquid-solid ratio of 100:1mL/g to obtain slurry; the slurry is subjected to pH adjustment in sequence, the pH of the slurry is controlled to be more than or equal to 1.0 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 1.5, and the slurry is filtered, and the obtained solid phase is subjected to washing at 45 ℃ and drying at 60 ℃ in sequence to obtain first reduction powder;
titanium dioxide is prepared from magnesium powder and MgCl 2 -CaCl 2 The eutectic salt is subjected to second reduction for 48 hours at 600 ℃ in argon atmosphere, the molar ratio of magnesium powder to titanium dioxide is 2:1, and MgCl is used for preparing the alloy powder 2 -CaCl 2 The weight ratio of the eutectic salt to the titanium dioxide is 3:1, and a second reduced product is obtained;
slurrying the second reduced product by hydrochloric acid solution with the pH value of 0.5 and the liquid-solid ratio of 100:1mL/g to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 1.5, and the slurry is filtered, and the obtained solid phase is washed at 0 ℃ and dried at 30 ℃ in sequence to obtain second reducing powder;
(2) Mixing the first reducing powder and the second reducing powder according to the mass ratio of 1:10, and sintering at 800 ℃ for 24 hours under the argon atmosphere to obtain a titanium oxide solid solution;
(3) The titanium oxide solid solution is prepared by calcium powder and anhydrous CaCl 2 Deep deoxidizing at 1000 deg.c in argon atmosphere for 24 hr with the mass ratio of calcium powder to titania solid solution of 0.09 to 1 and anhydrous CaCl 2 The weight ratio of the catalyst to the titanium oxide solid solution is 0.05:1, and a third reduction product is obtained;
slurrying the third reduced product with water, wherein the liquid-solid ratio is 100:1mL/g, so as to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 3.0, and the obtained solid phase is washed at 0 ℃ and dried at 45 ℃ in sequence through filtration, so that the low-oxygen metal titanium powder is obtained.
Example 3
The embodiment provides a preparation method of low-oxygen metal titanium powder, which comprises the following steps:
(1) Mixing calcium-containing titanium source (mixture of calcium oxide and calcined titanium dioxide), aluminum powder and CaCl 2 -LiCl co-molten salt, the molar ratio of calcium to aluminum powder in the calcium-containing titanium source being 2.0:1, the molar ratio of aluminum powder to titanium in the calcium-containing titanium source being 1.22:1, cacl 2 LiCl Co-ordinatesTiO based on titanium in molten salt and calcium-containing titanium source 2 The weight ratio of the catalyst to the catalyst is 0.05:1, and the catalyst is subjected to first reduction for 12 hours at 800 ℃ in sequence in helium atmosphere to obtain a first reduced product;
Slurrying the first reduced product by hydrochloric acid solution with the pH value of 1.0 and the liquid-solid ratio of 80:1mL/g to obtain slurry; the slurry is subjected to pH adjustment in sequence, the pH of the slurry is controlled to be more than or equal to 1.0 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 3.0, and the slurry is filtered, and the obtained solid phase is subjected to washing at 10 ℃ and drying at 50 ℃ in sequence to obtain first reduction powder;
titanium dioxide is prepared from magnesium powder and MgCl 2 Performing second reduction on KCl eutectic salt in hydrogen atmosphere at 900 ℃ for 0.25h, wherein the molar ratio of magnesium powder to titanium dioxide is 2.05:1, and MgCl is formed 2 -the weight ratio of KCl co-molten salt to titanium dioxide is 0.05:1, yielding a second reduced product;
slurrying the second reduced product by hydrochloric acid solution with the pH value of 0.8 and the liquid-solid ratio of 20:1mL/g to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 2.5, and the slurry is filtered, and the obtained solid phase is washed at 15 ℃ and dried at 20 ℃ in sequence to obtain second reducing powder;
(2) Mixing the first reducing powder and the second reducing powder according to the mass ratio of 1:0.267, and sintering for 0.25h at 1200 ℃ in helium atmosphere to obtain a titanium oxide solid solution;
(3) The titanium oxide solid solution is prepared by calcium powder and CaCl 2 -MgCl 2 Deep deoxidizing the eutectic salt for 48 hours at 700 ℃ in a hydrogen atmosphere, wherein the mass ratio of the calcium powder to the titanium oxide solid solution is 0.25:1, and CaCl is as follows 2 -MgCl 2 The weight ratio of the eutectic salt to the titanium oxide solid solution is 3:1, and a third reduced product is obtained;
slurrying the third reduced product with aqueous hydrochloric acid solution, wherein the liquid-solid ratio is 80:1mL/g, so as to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 1.5, and the obtained solid phase is washed at 0 ℃ and dried at 30 ℃ in sequence through filtration, so that the low-oxygen metal titanium powder is obtained.
Example 4
The embodiment provides a preparation method of low-oxygen metal titanium powder, which comprises the following steps:
(1) Mixing a calcium-containing titanium source (exceeding CaTiO) 3 The calcined product after mixing calcium oxide and titanium dioxide), aluminum powder and CaCl 2 -KCl co-molten salt, the molar ratio of calcium to aluminium powder in the calcium-containing titanium source being 1.5:1, the molar ratio of aluminium powder to titanium in the calcium-containing titanium source being 1.15:1, cacl 2 KCl eutectic salt and calcium-titanium-containing source titanium in TiO 2 The weight ratio is 2.2:1, and the first reduction is carried out for 20 hours at 1000 ℃ under vacuum condition in sequence to obtain a first reduced product;
slurrying the first reduced product by hydrochloric acid solution with the pH value of 1.0 and the liquid-solid ratio of 40:1mL/g to obtain slurry; the slurry is subjected to pH adjustment in sequence, the pH of the slurry is controlled to be more than or equal to 1.0 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 2.5, and the slurry is filtered, and the obtained solid phase is subjected to washing at 20 ℃ and drying at 45 ℃ in sequence to obtain first reduction powder;
Titanium dioxide is prepared from magnesium powder and MgCl 2 Performing second reduction on KCl eutectic salt in hydrogen atmosphere at 700 ℃ for 3h, wherein the molar ratio of magnesium powder to titanium dioxide is 2.1:1, and MgCl is used for preparing the magnesium powder-titanium dioxide composite material 2 The weight ratio of KCl eutectic salt to titanium dioxide is 1.5:1, obtaining a second reduced product;
slurrying the second reduced product by hydrochloric acid solution with the pH value of 1.0 and the liquid-solid ratio of 15:1mL/g to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 2.8, and the slurry is filtered, and the obtained solid phase is washed at 25 ℃ and dried at 20 ℃ in sequence to obtain second reducing powder;
(2) Mixing the first reducing powder and the second reducing powder according to the mass ratio of 1:3, and sintering for 12 hours at 900 ℃ in an argon atmosphere to obtain a titanium oxide solid solution;
(3) The titanium oxide solid solution is prepared by magnesium powder and MgCl 2 Performing third reduction on KCl eutectic salt in pure hydrogen atmosphere at 900 ℃ for 3h, wherein the mass ratio of magnesium powder to titanium oxide solid solution is 0.1:1, and MgCl is formed 2 The weight ratio of KCl eutectic salt to titanyl solid solution is 3:1, and a third reduction product is obtained;
slurrying the third reduced product with aqueous hydrochloric acid solution, wherein the liquid-solid ratio is 80:1mL/g, so as to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 2.0, and the obtained solid phase is washed at 0 ℃ and dried at 55 ℃ in sequence through filtration, so that the low-oxygen metal titanium powder is obtained.
Example 5
This example provides a method for preparing a low oxygen metallic titanium powder, which removes CaCl in the first reduction of step (1) 2 -KCl eutectic salt substitution with AlCl 3 The remainder was the same as in example 1, except for the KCl co-molten salt.
Example 6
This example provides a method for preparing a low oxygen metallic titanium powder, which removes CaCl in the first reduction of step (1) 2 KCl eutectic salt and calcium-titanium-containing source titanium in TiO 2 The weight ratio was 3.5:1, the remainder being the same as in example 1.
Example 7
This example provides a method for preparing a low oxygen metallic titanium powder, which removes CaCl in the first reduction of step (1) 2 KCl eutectic salt and calcium-titanium-containing source titanium in TiO 2 The weight ratio was 0.01:1, and the rest was the same as in example 1.
Example 8
This example provides a method for preparing a low oxygen metallic titanium powder, which removes MgCl in the second reduction of step (1) 2 -KCl eutectic salt substitution with CaCl 2 The remainder was the same as in example 1, except for the KCl co-molten salt.
Example 9
The present embodiment provides a method for preparing low oxygen metal titanium powder, which is the same as that of embodiment 1 except that the first reducing powder and the second reducing powder are mixed in the mass ratio of 1:0.1 in the step (2).
Example 10
The present embodiment provides a method for preparing low-oxygen metal titanium powder, which is the same as that of embodiment 1 except that the first reducing powder and the second reducing powder are mixed in the mass ratio of 1:14 in step (2).
Example 11
This example provides a method for producing a low-oxygen metallic titanium powder, which is the same as example 1 except that the atmosphere for the third reduction in step (3) is replaced with helium atmosphere.
Example 12
The present example provides a method for producing a low oxygen metal titanium powder, which is the same as example 1 except that the molar ratio of calcium to aluminum powder in the calcium-titanium-containing source in step (1) is 0.2:1.
Example 13
The present example provides a method for producing a low oxygen metal titanium powder, which is the same as example 1 except that the molar ratio of calcium to aluminum powder in the calcium-titanium-containing source in step (1) is 2.5:1.
Comparative example 1
This comparative example provides a method for preparing a low oxygen metal titanium powder, which is the same as example 1 except that the calcium-titanium-containing source of step (1) is replaced with a non-calcium-titanium-containing source, i.e., calcined titanium dioxide is directly used.
Method for measuring content of other elements by ICP-OES and method for measuring TiO by X-ray diffraction x The value of x in the intermediate powder was measured for the oxygen content of the second reduced powder and the final metallic titanium powder using an ONH analyzer, and the cost of the reducing agent consumed per ton of metallic titanium powder was calculated, wherein in accordance with the current market price of magnesium, aluminum was in the form of 4 ten thousand yuan per ton, and calcium consumed in step (3) was in the form of 4.5 ten thousand yuan per ton.
The test, calculation results and effects of the above examples and comparative examples are shown in tables 1 and 2.
TABLE 1
TABLE 2
In the table "/" indicates that there is no relevant data.
From tables 1 and 2, the following points can be seen:
(1) It can be seen from comprehensive examples 1-4 that the preparation method of the metal titanium powder provided by the invention can prepare the metal titanium powder with the oxygen content less than 0.2%, the simple reduction of titanium dioxide and magnesium is difficult to achieve the low oxygen content, and the cost of the reducing agent is reduced by more than 20% compared with that of the original full magnesium reduction process;
(2) As can be seen from a combination of example 1 and examples 6 to 7, the present invention is carried out by combining a first auxiliary agent with titanium in a calcium-containing titanium source as TiO 2 The weight ratio of the meter is controlled in a specific range, so that the waste of the first auxiliary agent can be reduced, the formation of weak acid insoluble aluminum phase can be avoided, and the subsequent wet separation is facilitated;
(3) As can be seen from a combination of examples 1 and 8, the magnesium reduction in example 1 uses a second auxiliary agent containing magnesium, as compared to CaCl in example 8 2 The KCl eutectic salt as a second auxiliary agent, the oxygen content in the second reduced powder of example 1 was 2.10wt% and the oxygen content in example 8 exceeded the expected 3wt%, thus indicating that the present invention improves the effect of the second reduction by using the second auxiliary agent containing magnesium;
(4) It can be seen from the combination of example 1 and examples 9 to 10 that the mass ratio of the first reducing powder to the second reducing powder in example 9 is 1:0.1, which results in the oxygen content in the titanium oxide solid solution exceeding the expected 8wt%, and the subsequent sintering effect is poor, which results in the reduction of the low-oxygen metallic titanium powder which is not expected; in the embodiment 10, the amount of Mg in the reducing agent is significantly increased due to the higher amount of the second reducing powder, so that the effect of saving the cost of the reducing agent is not achieved, and therefore, the invention can achieve the effects of better controlling the oxygen content and reducing the cost of the reducing agent by controlling the mass ratio of the first reducing powder to the second reducing powder within a specific range;
(5) As can be seen from the combination of example 1 and example 11, when the third reduction in example 1 is performed in a hydrogen-containing atmosphere using magnesium as a reducing agent, the oxygen content of the metallic titanium powder in example 11 is as high as 3.1wt% and far as low as that in example 1, as compared with the case of performing in an atmosphere containing no hydrogen in example 11, thereby showing that the present invention improves the effect of the third reduction by using magnesium as a reducing agent in combination with the hydrogen-containing atmosphere;
(6) It can be seen from a combination of examples 1 and 12-13 and comparative example 1 that the molar ratio of calcium to aluminum powder in the calcium-titanium-containing source in example 1 is 1.5:1, and that the first reduced product in example 1 can give TiO with x=0.38 after wet treatment, compared with 0.2:1 and 2.5:1 in examples 10-11, respectively, without calcium in comparative example 1 x The powder, while in comparative example 1 and example 12, the subsequent wet separation was difficult due to the formation of the weakly acid insoluble aluminum phase, and in example 13, there was an ineffective consumption of excess CaO, thus indicating that the present invention can effectively secure the solubility of the reduction by-products in the weakly acid by controlling the molar ratio of calcium to aluminum powder within a specific range.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.

Claims (10)

1. The preparation method of the low-oxygen metal titanium powder is characterized by comprising the following steps of:
(1) Performing first reduction and first wet treatment on a calcium-titanium-containing source through the action of a first reducing agent and a first auxiliary agent to obtain first reduction powder, wherein the first reduction powder is TiO x Powder, wherein x is more than or equal to 0.333 and less than or equal to 0.5, and the first reducing agent comprises aluminum; sequentially carrying out second reduction and second wet treatment on the titanium dioxide by a second reducing agent to obtain second reduction powder, wherein the oxygen content in the second reduction powder is less than or equal to 3wt%, and the second reducing agent comprises magnesium;
(2) Mixing the first reducing powder and the second reducing powder, and sintering to obtain a titanium oxide solid solution with the oxygen content less than or equal to 8 wt%;
(3) And carrying out third reduction and third wet treatment on the titanyl solid solution by a third reducing agent to obtain low-oxygen metal titanium powder, wherein the third reducing agent comprises magnesium and/or calcium.
2. The method according to claim 1, wherein the molar ratio of calcium in the calcium-titanium-containing source to the first reducing agent in step (1) is 0.6 to 2:1;
preferably, the molar ratio of the first reducing agent to titanium in the calcareous titanium source is 1-1.22:1.
3. The method of claim 1 or 2, wherein the first adjuvant in step (1) comprises anhydrous CaCl 2 、CaCl 2 KCl eutectic salt and CaCl 2 NaCl eutectic salt or CaCl 2 -any one or a combination of at least two of LiCl co-molten salts;
preferably, the first auxiliary agent and the titanium in the calcium-containing titanium source are mixed with TiO 2 The weight ratio of the components is 0.05-3:1;
preferably, the temperature of the first reduction is 700-1200 ℃;
preferably, the time of the first reduction is 0.3 to 24 hours;
preferably, the atmosphere of the first reduction comprises a vacuum or a protective atmosphere;
preferably, the protective atmosphere for the first reduction comprises any one or a combination of at least two of argon, hydrogen or helium.
4. A method according to any one of claims 1 to 3, wherein the temperature of the second reduction in step (1) is 600 to 900 ℃;
preferably, the time of the second reduction is 0.25 to 48 hours;
preferably, the molar ratio of the second reducing agent to the titanium dioxide is 2-4:1;
preferably, the second reducing atmosphere is any one or a combination of at least two of argon, hydrogen or helium.
5. The process according to any one of claims 1 to 4, wherein a second auxiliary is added to the second reduction in step (1);
preferably, the weight ratio of the second auxiliary agent to the titanium dioxide is 0.05-3:1;
Preferably, the second auxiliary comprises anhydrous MgCl 2 、MgCl 2 -CaCl 2 Eutectic salt, mgCl 2 -NaCl co-molten salt or MgCl 2 -any one or a combination of at least two of KCl co-molten salts.
6. The method of any one of claims 1 to 5, wherein the mixing in step (2) comprises dry powder mixing, or the mixing comprises mixing, crushing and granulating a first reducing powder and a second reducing powder;
preferably, the dry powder mixing comprises any one or a combination of at least two of three-dimensional mixing, V-type mixing or roller mixing;
preferably, the crushing mode comprises any one or a combination of at least two of ball milling, barreling, stirring milling or air flow milling;
preferably, the granulating mode comprises any one of spray granulating, roller granulating or compression granulating;
preferably, the mass ratio of the first reducing powder to the second reducing powder is 1:0.267-10.
7. The method according to any one of claims 1 to 6, wherein the sintering temperature in step (2) is 800 to 1200 ℃;
preferably, the sintering time is 0.25-24 hours;
preferably, the sintering atmosphere is vacuum or protective atmosphere;
Preferably, the protective atmosphere for sintering comprises any one or a combination of at least two of hydrogen, argon or helium.
8. The method according to any one of claims 1 to 7, wherein a third auxiliary agent is added to the third reduction in step (3);
preferably, when the third reducing agent contains magnesium, the mass ratio of magnesium to titanyl solid solution is 0.033-0.6:1;
preferably, when the third reducing agent contains magnesium, the third auxiliary comprises anhydrous MgCl 2 、MgCl 2 -CaCl 2 Eutectic salt, mgCl 2 -NaCl co-molten salt or MgCl 2 -any one or a combination of at least two of KCl co-molten salts;
preferably, when the third reducing agent contains magnesium, the weight ratio of the third auxiliary agent to the titanium oxide solid solution is 0.05-3:1;
preferably, when the third reducing agent contains magnesium, the temperature of the third reduction is 650-900 ℃;
preferably, when the third reducing agent contains magnesium, the time of the third reduction is 0.25-48 h;
preferably, when the third reducing agent contains magnesium, the third reducing atmosphere includes a hydrogen-argon mixed atmosphere or a pure hydrogen atmosphere;
preferably, the volume fraction of hydrogen in the hydrogen-argon mixed atmosphere is 5-100%;
preferably, when the third reducing agent contains calcium, the mass ratio of the calcium to the titanyl solid solution is 0.033-0.8:1;
Preferably, the third auxiliary agent comprises anhydrous CaCl when the third reducing agent contains calcium 2 、CaCl 2 -MgCl 2 Eutectic salt, caCl 2 NaCl eutectic salt, caCl 2 KCl co-fused salt or CaCl 2 -any one or a combination of at least two of LiCl co-molten salts;
preferably, when the third reducing agent contains calcium, the weight ratio of the third auxiliary agent to the titanium oxide solid solution is 0.05-3:1;
preferably, when the third reducing agent contains calcium, the temperature of the third reduction is 700-1100 ℃;
preferably, when the third reducing agent contains calcium, the time of the third reduction is 0.25-48 h;
preferably, when the third reducing agent contains calcium, the third reducing atmosphere comprises a vacuum or a protective atmosphere;
preferably, the protective atmosphere for the third reduction comprises any one or a combination of at least two of argon, hydrogen or helium.
9. The method according to any one of claims 1 to 8, wherein the first wet treatment in step (1) comprises: slurrying the first reduced product with water and/or acid liquor to obtain slurry; the slurry is subjected to pH adjustment and solid-liquid separation in sequence, and the obtained solid phase is washed and dried in sequence to obtain first reduction powder;
preferably, the second wet treatment in step (1) comprises: slurrying the second reduced product with water and/or acid liquor to obtain slurry; the slurry is subjected to pH adjustment and solid-liquid separation in sequence, and the obtained solid phase is washed and dried in sequence to obtain second reduction powder;
Preferably, the third wet treatment in step (3) comprises: pulping the third reduced product by water and/or acid liquor to obtain slurry; the slurry is subjected to pH adjustment and solid-liquid separation in sequence, and the obtained solid phase is washed and dried in sequence to obtain low-oxygen metal titanium powder;
preferably, the pH of the acid liquor in the first wet process, the second wet process and the third wet process is each independently ≡0.5;
preferably, the slurried liquid-to-solid ratios in the first wet process, the second wet process, and the third wet process are each independently 1 to 100:1ml/g;
preferably, the acids employed for pH adjustment in the first wet process, the second wet process and the third wet process are each independently hydrochloric acid;
preferably, the pH of the slurry is independently controlled to be more than or equal to 0.8 in the pH adjustment in the first wet treatment, the second wet treatment and the third wet treatment;
preferably, the pH of the pH-adjusted slurry in the first wet process, the second wet process, and the third wet process is each independently 1.5 to 3.0;
preferably, the temperature of the washing in the first wet process, the second wet process and the third wet process is each independently 0 to 60 ℃;
preferably, the drying temperatures in the first wet process, the second wet process and the third wet process are each independently equal to or less than 60 ℃.
10. The preparation method according to any one of claims 1 to 9, characterized in that the preparation method comprises the steps of:
(1) Mixing a calcium-containing titanium source, a first reducing agent and a first auxiliary agent, wherein the molar ratio of calcium in the calcium-containing titanium source to the first reducing agent is 0.6-2:1, the molar ratio of the first reducing agent to titanium in the calcium-containing titanium source is 1-1.22:1, and the first auxiliary agent and the titanium in the calcium-containing titanium source are prepared by adopting TiO (titanium oxide) 2 The weight ratio is 0.05-3:1, and the first reduction is carried out for 0.3-24 h at 700-1200 ℃ sequentially through vacuum or protective atmosphere, thus obtaining a first reduction product;
slurrying the first reduced product by water and/or acid liquor with the pH value of more than or equal to 0.5, wherein the liquid-solid ratio is 1-100:1 mL/g, so as to obtain slurry; the slurry is subjected to pH adjustment in sequence, the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized to be 1.5-3.0, and solid-liquid separation is carried out, and the obtained solid phase is washed at 0-60 ℃ and dried at less than or equal to 60 ℃ in sequence to obtain first reduction powder;
carrying out second reduction on the titanium dioxide for 0.25-48 h in a protective atmosphere at 600-900 ℃ by using a second reducing agent and a second auxiliary agent, wherein the molar ratio of the second reducing agent to the titanium dioxide is 2-4:1, and the weight ratio of the second auxiliary agent to the titanium dioxide is 0.05-3:1, so as to obtain a second reduced product;
Slurrying the second reduced product by water and/or acid liquor with the pH value of more than or equal to 0.5, wherein the liquid-solid ratio is 1-100:1 mL/g, so as to obtain slurry; the slurry is subjected to pH adjustment in sequence, the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized at 1.5-3.0, and the obtained solid phase is subjected to solid-liquid separation, washing at 0-60 ℃ and drying at less than or equal to 60 ℃ in sequence, so that second reduction powder is obtained;
(2) Mixing the first reducing powder and the second reducing powder according to the mass ratio of 1:0.267-10, and sintering for 0.25-24 hours at 800-1200 ℃ under vacuum or protective atmosphere to obtain a titanium oxide solid solution with the oxygen content less than or equal to 8 wt%;
(3) The titanium oxide solid solution is subjected to third reduction under the action of a third reducing agent and a third auxiliary agent to obtain a third reduction product;
slurrying the third reduced product by water and/or acid liquor with the pH value of more than or equal to 0.5, wherein the liquid-solid ratio is 1-100:1 mL/g, so as to obtain slurry; the pH of the slurry is controlled to be more than or equal to 0.8 in the pH adjustment, the pH of the slurry after the pH adjustment is stabilized to be 1.5-3.0, and the solid phase obtained through solid-liquid separation is washed at 0-60 ℃ and dried at less than or equal to 60 ℃ in sequence, so that the low-oxygen metal titanium powder is obtained.
CN202210516759.XA 2022-05-12 2022-05-12 Preparation method of low-oxygen metal titanium powder Pending CN117086318A (en)

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