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CN-122010053-A - Preparation method for rapidly preparing low-oxygen-content titanium hydride powder

CN122010053ACN 122010053 ACN122010053 ACN 122010053ACN-122010053-A

Abstract

The invention provides a preparation method of titanium hydride powder with low oxygen content, which relates to the technical field of metal chemical industry and sequentially comprises the steps of preparing Sp1 raw materials, crushing and screening titanium or titanium alloy ingots, residues or cuttings to obtain particle raw materials, carrying out vacuum rolling desorption and drying on Sp2, carrying out vacuum preheating and activation to 300-450 ℃ for 5-30 min at the vacuum degree of less than or equal to 10Pa at the temperature of 120-180 ℃, carrying out primary intensified hydrogenation on Sp3, carrying out downward spraying or permeation on hydrogen through a distributed hydrogen supply structure under the condition of 500-650 ℃ and 10-100 kPa, enabling the hydrogen and settled particles to be in parallel flow or countercurrent contact to generate hydrogenation products, carrying out vacuum dehydration and dehydrogenation on Sp5, introducing magnesium steam/calcium steam for steam deoxidation at the temperature of 700-850 ℃ and 0.1-50 Pa, carrying out secondary hydrogenation phasing on Sp6, carrying out cyclone separation and airtight filtration after Sp7 argon replacement and cooling to be less than or equal to 150 ℃ and collecting finished products. The method realizes the continuous closed production with determinable hydrogenation end point, stable deoxidation and low oxygen powder.

Inventors

  • WANG YUAN
  • GAO LIANG
  • HU YU

Assignees

  • 贵州钛科新材料有限公司

Dates

Publication Date
20260512
Application Date
20260210

Claims (10)

  1. 1. A preparation method for rapidly preparing titanium hydride powder with low oxygen content, which is characterized by comprising the following steps: Sp1, preparing a raw material, namely crushing titanium or titanium alloy cast ingots, scraps or cuttings and screening to obtain a particle raw material; sp2, vacuum rolling desorption drying, namely placing the particle raw materials into a pretreatment tank, turning and rolling and heating, and treating for 1-2 hours under the conditions that the temperature is 120-180 ℃ and the vacuum degree is less than or equal to 10 Pa; Sp3, preheating and activating, namely feeding the particle raw material treated by Sp2 into a preheating section through gas locking, heating to 300-450 ℃ under vacuum atmosphere, and keeping the residence time for 5-30 min; Sp4, carrying out primary intensified hydrogenation, conveying the particle raw material preheated and activated by Sp3 to a primary hydrogenation section, and carrying out hydrogenation reaction under the conditions of 500-650 ℃ and 10-100 kPa of hydrogen pressure, wherein the hydrogen is sprayed downwards or permeated downwards through a distributed hydrogen supply structure, so that the hydrogen and the particle raw material settled from top to bottom form parallel flow contact or countercurrent contact to generate titanium hydride or titanium hydride alloy; Sp5, carrying out dehydrogenation-deoxidation coupling, conveying the material hydrogenated by Sp4 to a dehydrogenation and deoxidation section, vacuumizing to remove redundant hydrogen at the temperature of 700-850 ℃ and the vacuum degree of 0.1-50 Pa, and introducing deoxidizer steam into the dehydrogenation and deoxidation section, wherein the deoxidizer steam is magnesium steam, calcium steam or mixed steam of the magnesium steam and the calcium steam so as to reduce the oxygen content of the material; sp6, carrying out secondary hydrogenation phasing, namely conveying the material treated by Sp5 to a secondary hydrogenation section, and carrying out secondary hydrogenation under the conditions of 450-600 ℃ and 5-60 kPa of hydrogen pressure so as to regulate the composition and hydrogen content of the hydrogenation phase; Sp7, inert displacement cooling and airtight collection, introducing argon to displace hydrogen after secondary hydrogenation is completed, cooling to the material temperature of less than or equal to 150 ℃ under the argon atmosphere, and adopting cyclone separation and airtight filtration collection to obtain titanium hydride powder or titanium hydride alloy powder with low oxygen content.
  2. 2. The method for rapidly preparing titanium hydride powder with low oxygen content according to claim 1, wherein the particle size of the particle raw material in Sp1 is 0.2-3 mm, the raw material purity is more than or equal to 99.5%, when the raw material is cuttings, a degreasing step is added before Sp2, and the cuttings are heated to 200-350 ℃ under inert atmosphere and kept for 0.5-2 h to remove greasy dirt and organic residues.
  3. 3. The method for rapidly preparing titanium hydride powder with low oxygen content according to claim 1, wherein hydrogen in Sp4 is provided by an active hydrogen generation step, the active hydrogen generation step is carried out according to the following steps of introducing hydrogen into an active hydrogen generator, carrying out thermal cracking or catalytic cracking at the temperature of 650-900 ℃ to obtain hot hydrogen containing active hydrogen components, and conveying the hot hydrogen to an inlet of a primary hydrogenation section through a heat preservation conveying pipe, wherein the length of the heat preservation conveying pipe is less than or equal to 1.5m, and the pipe wall temperature is more than or equal to 450 ℃.
  4. 4. The method for rapidly preparing titanium hydride powder with low oxygen content according to claim 1, wherein the primary hydrogenation section of Sp4 adopts a cyclone sedimentation bed operation mode, hydrogen enters the primary hydrogenation section through a tangential inlet to form a cyclone air curtain, materials are settled along the axial direction, and the pressure drop delta P in the primary hydrogenation section is measured and the feeding rate is adjusted to keep the delta P at 50-400 Pa.
  5. 5. The method for rapidly preparing titanium hydride powder with low oxygen content according to claim 1, wherein the Sp4 distributed hydrogen supplying structure satisfies one of the following conditions: The distributed hydrogen supply structure is a micro-nozzle array, the aperture of the nozzle is 0.3-1.2 mm, the spraying direction is downward, and the spraying angle is 5-30 degrees; The distributed hydrogen supply structure is a porous metal permeation plate, the pore diameter is 5-50 mu m, and the permeation direction is from outside to inside and downwards forms a hydrogen permeation curtain.
  6. 6. The method for rapidly preparing titanium hydride powder with low oxygen content according to claim 1, wherein the primary intensified hydrogenation of Sp4 adopts a pulse hydrogen supply mode, pulse hydrogen supply is performed by superposing pulse flow on the basis of continuous baseline hydrogen supply flow, the pulse period is 10-60 s, the pulse duration is 1-5 s, and the pulse peak flow is 1.05-1.30 times of the baseline flow.
  7. 7. The method for rapidly preparing titanium hydride powder with low oxygen content according to claim 6, wherein the dehydrogenation and deoxidation section of Sp5 is divided into three sections along the flow direction and respectively meets the following conditions: The temperature of the first-stage dehydrogenation main zone is 700-760 ℃ and the vacuum degree is 5-20 Pa; the temperature of the second stage deoxidization reaction zone is 760-830 ℃ and the vacuum degree is 0.5-5 Pa, and deoxidizer steam is introduced into the second stage deoxidization reaction zone; the temperature of the third section cleaning stable region is 720-780 ℃ and the vacuum degree is 0.5-3 Pa.
  8. 8. The method for rapidly preparing the titanium hydride powder with low oxygen content according to claim 6, wherein deoxidizing agent steam in Sp5 is generated by an independent evaporator and is introduced into a dehydrogenation deoxidization section through a heat preservation conveying channel, when the deoxidizing agent steam is magnesium steam, the temperature of the evaporator is 650-780 ℃, when the deoxidizing agent steam is calcium steam, the temperature of the evaporator is 750-900 ℃, the temperature of the pipe wall of the heat preservation conveying channel is more than or equal to 450 ℃, and an introducing port is positioned in a deoxidization reaction zone.
  9. 9. The method for rapidly preparing titanium hydride powder with low oxygen content according to claim 6, wherein a high-temperature filtering and trapping step and a condensation and trapping step are sequentially arranged at the downstream of the dehydrogenation and deoxidation section of Sp5, mgO and CaO particles are trapped by a sintered metal filter core in the high-temperature filtering and trapping step at 600-850 ℃, metal steam condensate is trapped by the condensation and trapping step at 50-250 ℃, and the oxygen content of an argon inlet for replacement in Sp7 is less than or equal to 20ppm and the dew point is less than or equal to-60 ℃.
  10. 10. The control method for the preparation method of the titanium hydride powder with low oxygen content according to any one of claims 1 to 9, wherein the control method is carried out according to the following steps: Sp1, solid phase flux closed-loop control, namely collecting pressure drop delta P in a primary hydrogenation section, collecting the rotating speed or the opening of a feeding mechanism, comparing the delta P with a target pressure drop interval of 50-400 Pa, and keeping the delta P at 50-400 Pa by adjusting the rotating speed or the opening of the feeding mechanism; Sp2, primary hydrogenation end point criterion and cut-off control, collecting an inlet hydrogen volume fraction C_in and an outlet hydrogen volume fraction C_out of a primary hydrogenation section, calculating delta C=C_in-C_out, and collecting hydrogen mass flow And calculate the relative rate of change over 180 seconds of succession When delta C is less than or equal to 0.30vol% and R is less than or equal to 0.02, controlling the material to be switched into a dehydrogenation and deoxidation section; sp3, carrying out closed-loop control on dehydrogenation and deoxidation steam supply, collecting the vacuum degree and the temperature of a dehydrogenation main zone, a deoxidation reaction zone and a sweeping stable zone, respectively controlling the vacuum degree and the temperature to be within the limit of claim 7, and collecting the oxygen content O_tail and the dew point D_tail of the tail gas of the dehydrogenation and deoxidation zone, wherein when the O_tail is more than 20ppm or D_tail is more than 60 ℃, the oxygen-removing agent steam supply rate is increased and the feeding rate is reduced, and when the O_tail is less than or equal to 20ppm and the D_tail is less than or equal to-60 ℃ for 300 seconds, the current oxygen-removing agent steam supply rate and the feeding rate are maintained; sp4, replacement, cooling and collection interlocking control, namely collecting the volume fraction C_H2 in the system after secondary hydrogenation is finished, introducing argon for replacement, enabling C_H2 to be less than or equal to 1.0vol%, starting cooling, collecting the temperature T_m of the material, and allowing the airtight cyclone separation and airtight filtering collection step to be started under the condition that T_m is less than or equal to 150 ℃.

Description

Preparation method for rapidly preparing low-oxygen-content titanium hydride powder Technical Field The invention relates to the technical field of metalization, in particular to a preparation method for rapidly preparing titanium hydride powder with low oxygen content. Background Titanium hydride powder and titanium hydride alloy powder are widely applied to the fields of powder metallurgy, metal injection molding and additive manufacturing, and the common preparation route is based on a hydrogenation-dehydrogenation method, and target powder is obtained by carrying out hydrogenation embrittlement treatment on titanium or titanium alloy raw materials, and then carrying out dehydrogenation, crushing and classification. The prior industrial hydrogenation process mainly adopts an intermittent vacuum hydrogenation furnace or a continuous vacuum atmosphere rotary kiln. Batch vacuum hydrogenators typically employ a tray or cartridge charge that is heated and contacted with hydrogen in stacked layers. The gas-solid contact area of the mode is limited by the thickness of the material layer, the diffusion path of hydrogen in the material layer is long, the local heat and mass transfer are uneven, the hydrogenation induction period is long, the hydrogenation rate is low, the consistency among batches is poor, and the problems of frequent loading and unloading, high labor intensity and limited production beat exist. The continuous vacuum atmosphere rotary kiln depends on the rotation of a cylinder body to form a material curtain to roll so as to realize contact, but the gas-solid contact fluctuates along with the shape of the material curtain, the residence time distribution is wide, micro leakage and secondary oxygen inhalation caused by end sealing and high-temperature movement of materials are difficult to avoid, the oxygen content of a finished product fluctuates, and particularly low-oxygen powder is difficult to stably obtain under continuous production conditions. Meanwhile, the traditional process mostly uses fixed heat preservation time as a terminal control basis, and lacks on-line criterion and closed-loop adjustment based on gas composition, flow and pressure drop, so that excessive reaction or insufficient reaction is caused, and the rise of energy consumption, the dispersion of powder quality and low oxygen failure are caused. Therefore, there is a need for a preparation method capable of achieving efficient uniform hydrogenation, low oxygen deoxidation, end point determinable and full-flow closed low oxygen guarantee under continuous production conditions, so as to improve the preparation efficiency and stably obtain titanium hydride powder or titanium hydride alloy powder with low oxygen content. Disclosure of Invention Technical problem to be solved Aiming at the defects of the prior art, the invention provides a preparation method for rapidly preparing titanium hydride powder with low oxygen content, which solves the problems of the prior art. Technical proposal The preparation method for rapidly preparing the titanium hydride powder with low oxygen content is realized by the following steps: Sp1, preparing a raw material, namely crushing titanium or titanium alloy cast ingots, scraps or cuttings and screening to obtain a particle raw material; sp2, vacuum rolling desorption drying, namely placing the particle raw materials into a pretreatment tank, turning and rolling and heating, and treating for 1-2 hours under the conditions that the temperature is 120-180 ℃ and the vacuum degree is less than or equal to 10 Pa; Sp3, preheating and activating, namely feeding the particle raw material treated by Sp2 into a preheating section through gas locking, heating to 300-450 ℃ under vacuum atmosphere, and keeping the residence time for 5-30 min; Sp4, carrying out primary intensified hydrogenation, conveying the particle raw material preheated and activated by Sp3 to a primary hydrogenation section, and carrying out hydrogenation reaction under the conditions of 500-650 ℃ and 10-100 kPa of hydrogen pressure, wherein the hydrogen is sprayed downwards or permeated downwards through a distributed hydrogen supply structure, so that the hydrogen and the particle raw material settled from top to bottom form parallel flow contact or countercurrent contact to generate titanium hydride or titanium hydride alloy; Sp5, carrying out dehydrogenation-deoxidation coupling, conveying the material hydrogenated by Sp4 to a dehydrogenation and deoxidation section, vacuumizing to remove redundant hydrogen at the temperature of 700-850 ℃ and the vacuum degree of 0.1-50 Pa, and introducing deoxidizer steam into the dehydrogenation and deoxidation section, wherein the deoxidizer steam is magnesium steam, calcium steam or mixed steam of the magnesium steam and the calcium steam so as to reduce the oxygen content of the material; sp6, carrying out secondary hydrogenation phasing, namely conveying the material treated by Sp5 to a seco