CN105290409B - The preparation method of hydrogenation and dehydrogenization stove and low oxygen content titanium valve - Google Patents

Abstract

The invention provides a hydrogenation dehydrogenation furnace, which includes a horizontal heating furnace, a reactor, and a gas storage tank. The heating furnace includes a first heating furnace and a second heating furnace, and the reactor includes a first reactor and a second heating furnace. The reactor has a thermocouple on the heating furnace. Both the first reactor and the second reactor are cylinders with closed ends. One end of the cylinder is provided with a material inlet and outlet, and a sealing cover is provided at the material inlet and outlet. The cylinder body of the sealing cover is provided with a water cooling jacket, the cylinder body is provided with a gas inlet and outlet, and the gas storage tank is provided with a pressure gauge, a reactor joint, a vacuum joint, and a hydrogen source joint; the first reactor and the second reaction The reaction section of the reactor is respectively located in the hearth of the first heating furnace and the second heating furnace, and the reactor joint of the gas storage tank is respectively communicated with the gas inlet and outlet of the first reactor and the second reactor through pipe fittings. The invention also provides a method for preparing titanium powder with low oxygen content. The oxygen content of the titanium powder prepared by the method is not more than 0.15wt%.

Description

Hydrodehydrogenation furnace and preparation method of titanium powder with low oxygen content

technical field

The invention belongs to the production field of hydrogenation dehydrogenation process of titanium powder, and relates to a hydrogenation dehydrogenation furnace and a preparation method of titanium powder with low oxygen content.

Background technique

Titanium powder is an important raw material for preparing titanium alloys. The mechanical properties of titanium alloys decrease significantly with the increase of oxygen content. For example, for titanium alloy TC4, when the oxygen content exceeds 0.3%, its elongation after fracture will decrease. If it is lower than 8%, when the oxygen content in it reaches 1%, its elongation after breaking will be lower than 1%, and TC4 will be brittle at this time. Since the oxygen content of powder metallurgy sintered products is generally higher than that of the original powder matrix, the application of titanium powder produced by the existing hydrogenation dehydrogenation process in the field of powder molding is limited. If you want to prepare titanium alloys with better mechanical properties , the premise is to prepare titanium powder with low oxygen content.

Among the many methods for preparing titanium powder, the hydrodehydrogenation process is a common process for preparing titanium powder. This process has the advantages of simple operation, low requirements for raw materials, low production cost and easy realization of large-scale production. The production process of titanium powder by hydrogenation dehydrogenation process is as follows: the raw material sponge titanium is heated and activated in a hydrogen atmosphere and converted into titanium hydride by absorbing hydrogen at 400-500 ° C, grinding the cooled titanium hydride to the required particle size, and grinding The final titanium hydride is dehydrogenated at 600-700°C under vacuum to obtain titanium powder, which is then ground to the required particle size under the protection of argon. At present, the hydrodehydrogenation furnace used in the above process includes a heating furnace and a reactor for placing sponge titanium or titanium hydride in the heating furnace. The reactor is a cylinder with both ends closed, and the end of one end of the cylinder is There is a material inlet and outlet, and a sealing cover is provided at the material inlet and outlet. The hydrogen source interface for connecting the hydrogen source and the vacuum pumping interface of the vacuum pump are provided on the cylinder close to the sealing cover. The hydrogen purification equipment is not included. When in use, the The hydrogen source and the vacuum pump are connected with the reactor, and high-purity hydrogen is directly used as the hydrogen source when the titanium sponge is hydrogenated.

The production process of the hydrodehydrogenation process is relatively lengthy, and each process may introduce unnecessary oxygen impurities into the intermediate product or the final product. Among them, the hydrogen absorption process of sponge titanium is most seriously polluted by oxygen. Since the hydrogenation reaction is carried out at a high temperature of 400-500 ° C, and the hydrogen absorption capacity of sponge titanium is extremely large, and under high temperature conditions, the solid solution of oxygen in sponge titanium and the oxidation of sponge titanium will increase sharply. As a hydrogen source, but it inevitably contains oxygen, the hydrogenation process will cause a large amount of oxygen in the hydrogen source and the gas path to be enriched in the sponge titanium; at the same time, during the hydrogenation reaction, the phase change volume of titanium changes suddenly and titanium The embrittlement of the material will cause cracks on the material, which will cause a sharp increase in the surface area of the material, which also increases the probability of the material being polluted by impurity oxygen. The above factors will reduce the purity of the final product titanium powder. In addition, the raw material sponge titanium itself is polluted by oxygen, and the grinding process is polluted by oxygen. The oxygen content of the titanium powder prepared by the existing hydrodehydrogenation process is usually higher than 0.3wt%.

In order to solve the problem of oxygen pollution, some researchers have proposed to operate all the steps of the hydrodehydrogenation process under a protective atmosphere or to carry out integrated operations under a protective atmosphere to reduce the oxygen-increasing link, but this method will lead to high production costs , and cannot fundamentally solve the problem of oxygen pollution during the high-temperature hydrogenation of sponge titanium, so the control effect of this type of method on the oxygen content in titanium powder is also relatively limited. Therefore, if the preparation method of titanium powder with low oxygen content and the supporting hydrodehydrogenation furnace can be developed based on the low-cost hydrodehydrogenation process, it will have important significance for expanding the application of hydrodehydrogenation titanium powder in the field of powder molding.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art, to provide a hydrodehydrogenation furnace and a method for preparing titanium powder with low oxygen content, to reduce the oxygen content of titanium powder prepared by the hydrodehydrogenation process, and to improve the hydrodehydrogenation process The quality of the prepared titanium powder.

The hydrogenation dehydrogenation furnace provided by the present invention includes a heating furnace and a reactor placed horizontally, a gas storage tank, a first support, a second support, a movable third support and a mobile fourth support, and the heating furnace includes The first heating furnace and the second heating furnace, the reactor includes the first reactor and the second reactor,

Both the first heating furnace and the second heating furnace are equipped with thermocouples, the first reactor and the second reactor are cylinders with both ends closed, one end of the cylinder is provided with a material inlet and outlet, and the material inlet and outlet A sealing cover is provided, and a water cooling jacket is provided on the cylinder close to the sealing cover. The cylinder is also provided with a gas inlet and outlet, and the gas inlet and outlet of the first reactor and the second reactor are respectively provided with first valves. and the second valve; the gas storage tank is provided with a pressure gauge, a reactor joint equipped with the third valve, a vacuum joint equipped with the fourth valve, and a hydrogen source joint equipped with the fifth valve;

The first heating furnace and the second heating furnace are respectively installed on the first support and the second support, and the first reactor and the second reactor are respectively installed on the mobile third support and the mobile fourth support, and the first reactor The reaction section of the second reactor is located in the furnace of the first heating furnace, and the reaction section of the second reactor is located in the furnace of the second heating furnace. The reactor joint of the gas storage tank is respectively connected with the first reactor and the second reaction chamber through pipe fittings. The gas inlet and outlet of the device are connected.

In the above-mentioned hydrodehydrogenation furnace, fans for cooling the first reactor and the second reactor are installed on the third movable support and the fourth movable support. When the first reactor or the second reactor needs to be cooled during the production process, the fan can speed up the cooling speed and save production time.

In the above-mentioned hydrodehydrogenation furnace, the first reactor and the second reactor are provided with hooks to facilitate loading and unloading of the reactors with lifting equipment.

The preparation method of titanium powder with low oxygen content according to the present invention, the method uses the above-mentioned hydrodehydrogenation furnace and is equipped with a vacuum pump and a storage tank storing high-purity hydrogen, and the vacuum pump and the storage tank storing high-purity hydrogen are respectively connected to the vacuum pump and the storage tank containing high-purity hydrogen through pipe fittings The vacuum joint of the gas storage tank of the hydrodehydrogenation furnace is connected with the hydrogen source joint, and the steps are as follows:

① Loading

The hydrogen storage alloy and the titanium sponge are respectively placed in the reaction section of the first reactor and the reaction section of the second reactor, close the sealing cover and the first valve to the fifth valve, then start the vacuum pump and open the first valve to the fifth valve. The fourth valve, evacuate until the pressure in the first reactor, the second reactor and the gas storage tank is 100-1000Pa, close the first valve to the fourth valve and the vacuum pump;

②Hydrogen storage alloy activates and purifies the atmosphere in the furnace

Turn on the first heating furnace to raise the furnace temperature of the first heating furnace to 200-300°C and maintain the temperature, open the fifth valve, pass hydrogen gas into the gas storage tank until the pressure is 0.1-0.5 MPa, close the fifth valve, Then open the first valve to the third valve, start the vacuum pump after the indication of the pressure gauge on the gas storage tank remains unchanged, and open the fourth valve to evacuate to the first reactor, the second reactor and the gas storage tank The pressure is 100～1000Pa, close the first valve to the fourth valve and the vacuum pump; repeat the aforementioned operation of passing hydrogen and vacuuming for 3 to 5 times, then close the first heating furnace, and drop the temperature of the first reactor to room temperature;

③Hydrogen storage alloy hydrogen absorption

Open the fifth valve, pass hydrogen gas into the gas storage tank until the pressure is 1-1.5MPa, close the fifth valve, then open the first valve and the third valve to make the hydrogen storage alloy in the first reactor absorb hydrogen, and wait for the gas After the indication of the pressure gauge on the storage tank remains unchanged, close the first valve and the third valve; repeat the aforementioned hydrogen flow and hydrogen absorption operations until the hydrogen storage alloy reaches hydrogen absorption saturation, then start the vacuum pump and open the first valve, The third valve and the fourth valve are evacuated until the pressure in the first reactor and the gas storage tank is 100-1000Pa, and the first valve, the third valve and the fourth valve and the vacuum pump are closed;

④Hydrogenation reaction of sponge titanium

Turn on the first heating furnace and the second heating furnace, raise the furnace temperature of the first heating furnace and the second heating furnace to 300-350°C and 400-425°C respectively and maintain the aforementioned temperature, open the first valve to the third valve, Carry out the hydrogenation reaction of the hydrogen storage alloy and the hydrogenation reaction of the sponge titanium. After the hydrogenation reaction of the sponge titanium is completed, titanium hydride is obtained. The first heating furnace and the second heating furnace and the first valve to the third valve are closed, and the first reactor and the temperature of the second reactor is lowered to room temperature;

⑤ Pulverization and dehydrogenation

Take titanium hydride out of the second reactor, place it in the reaction section of the second reactor after pulverization under the argon atmosphere, then close the sealing cover of the second reactor, turn on the vacuum pump and open the second valve to the fourth Valve, vacuumize to keep the pressure in the second reactor and gas storage tank at 100-1000Pa, then open the second heating furnace to raise the furnace temperature of the second heating furnace to 600-650°C and maintain this temperature for titanium hydride After the dehydrogenation reaction is completed, the second heating furnace, the second valve to the fourth valve and the vacuum pump are closed to obtain titanium powder with an oxygen content of no more than 0.15wt%.

In step ① of the above method, the mass ratio of the hydrogen storage alloy in the first reactor to the titanium sponge in the second reactor is (2-2.5):1.

In the above method, the hydrogen storage alloy is vanadium-titanium-chromium-iron.

In the above method, the titanium sponge is grade 0 titanium sponge, that is, grade 0 titanium sponge conforming to the GB/T 2524-2010 "Titanium Sponge" standard.

In step ⑤ of the above method, the pulverization degree of titanium hydride is determined according to actual application requirements, and the titanium hydride is usually pulverized to be below 250 μm.

In step ⑤ of the above method, after the dehydrogenation reaction is completed, the second valve to the fourth valve and the vacuum pump are closed, the temperature of the reactor is lowered to room temperature, and the obtained titanium powder is taken out, ground and sieved under an argon atmosphere, specifically The grinding and sieving conditions are determined according to the requirements for the particle size of titanium powder in practical applications. Usually, grinding and sieving can be carried out according to the particle size requirements in the YS/T 654-2007 "Titanium Powder" standard.

In step ② in the above method, it is preferred to use a fan to reduce the temperature of the first reactor to room temperature, and in step ④ it is preferred to use a fan to reduce the temperature of the first reactor and the second reactor to room temperature.

In the above method, the high-purity hydrogen refers to hydrogen with a purity equal to or higher than 99.999%.

In step ③ of the above method, when the reading on the pressure gauge on the gas storage tank is higher than the atmospheric pressure and does not change anymore, the hydrogen storage alloy reaches hydrogen absorption saturation.

In step ④ of the above method, the method for judging whether the hydrogenation reaction of sponge titanium is completed is as follows: make the first valve, the fourth valve and the fifth valve in the closed state, the second valve and the third valve in the open state, and wait for the gas to be stored When the reading on the pressure gauge on the tank is higher than the atmospheric pressure and does not change, the hydrogenation reaction of sponge titanium is completed.

In the step ⑤ of the above-mentioned method, the judging method of whether the dehydrogenation reaction of titanium hydride is completed is: make the first valve, the fourth valve and the fifth valve be in the closed state, the second valve and the third valve are in the open state, wait for the gas storage When the indication of the pressure gauge on the container tank no longer changes, the dehydrogenation reaction of titanium hydride is completed.

Compared with the prior art, the present invention has the following beneficial effects:

1. The present invention provides a kind of hydrodehydrogenation furnace of novel structure, because this hydrodehydrogenation furnace is provided with two groups of heating furnaces, two groups of reactors and gas storage tank, wherein one group of heating furnaces and reactors and gas storage tanks The combination of the tank, the hydrogen storage alloy and the hydrogen source can realize the purification of the hydrogen source by the hydrogen storage alloy, reduce the oxygen content of the hydrogen source, and cooperate with another set of heating furnace, reactor and gas storage tank to realize the hydrogenation of sponge titanium And titanium hydride and titanium powder with low oxygen content are prepared during the dehydrogenation process of titanium hydride, which is suitable for the production of titanium hydride and titanium powder with low oxygen content.

2. Since the hydrogenation dehydrogenation furnace of the present invention sets the supports supporting the first reactor and the second reactor into a mobile type, and a blower fan is also set on the mobile support, when the first reactor is used in the production process When the temperature of the first reactor or the second reactor needs to be lowered, the movable support is used to push the reactor out of the hearth of the heating furnace and start the fan to cool the reactor, which is beneficial to speed up the cooling speed of the reactor and improve the production efficiency.

3. The present invention provides a new method for producing titanium powder by hydrodehydrogenation process. The method uses hydrogen purified by hydrogen storage alloy to produce titanium hydride. Since the hydrogen storage alloy absorbs hydrogen, impurity gases other than hydrogen cannot be stored. Hydrogen alloy absorption, after the hydrogen storage alloy is saturated with hydrogen, the impurity gas, especially impurity oxygen, which is enriched in the atmosphere outside the hydrogen storage alloy can be effectively removed by vacuuming. Therefore, when the hydrogen storage alloy is subsequently heated, the storage The hydrogen alloy can emit extremely high-purity hydrogen, and the use of the hydrogen to prepare titanium hydride can effectively reduce the oxygen content in the titanium hydride, and then effectively reduce the oxygen content in the titanium powder.

4. Experiments show that the oxygen content of the titanium powder prepared by the hydrodehydrogenation process in the method of the present invention is no more than 0.15wt%, which is obviously lower than that of the titanium powder prepared by the existing hydrodehydrogenation process, and the quality is higher.

5. The process of the method of the present invention is simple, multiple second reactors can be used alternately in the production process, thereby realizing the efficient production of titanium powder, and the hydrogen storage alloy in the first reactor can be used repeatedly, which is conducive to saving production cost, thus the method of the present invention is conducive to popularization and application and the realization of industrialized production.

Description of drawings

Fig. 1 is a kind of structural representation of hydrodehydrogenation furnace of the present invention;

Fig. 2 is another kind of structural representation of hydrodehydrogenation furnace of the present invention;

Fig. 3 is the schematic diagram that adopts the hydrogenation dehydrogenation furnace of the present invention to cooperate vacuum pump, the storage tank that stores high-purity hydrogen to prepare titanium powder;

In the figure, 1—first valve, 2—second valve, 3—third valve, 4—fourth valve, 5—fifth valve, 6—gas storage tank, 7—first heating furnace, 8—the first Two heating furnaces, 9—the first reactor, 9-1—the reaction section of the first reactor, 10-1—the reaction section of the second reactor, 10—the second reactor, 11—the sealing cover, 12 —Water cooling jacket, 13—Thermocouple, 14—First bracket, 15—Second bracket, 16—Mobile third bracket, 17—Mobile fourth bracket, 18—Pressure gauge, 19—Hook, 20—Fan , 21—vacuum pump, 22—storage tank with high-purity hydrogen.

detailed description

The preparation method of the hydrodehydrogenation furnace and the low-oxygen content titanium powder of the present invention will be further described through examples and in conjunction with the accompanying drawings. The purity of the high-purity hydrogen used in the following examples is ≥99.999%.

Example 1

In this embodiment, the structure of the hydrogenation dehydrogenation furnace is shown in Figure 1, including a horizontally placed heating furnace, a horizontally placed reactor, a gas storage tank 6, a first support 14, a second support 15, a mobile The third support 16 and the fourth mobile support 17, the heating furnace includes the first heating furnace 7 and the second heating furnace 8, and the reactor includes the first reactor 9 and the second reactor 10,

The first heating furnace 7 and the second heating furnace 8 are equipped with thermocouples 13, and the first reactor 9 and the second reactor 10 are cylinders with both ends closed, and one end of the cylinder is provided with a material Inlet and outlet, there is a sealing cover 11 at the material inlet and outlet, and a water cooling jacket 12 is provided on the cylinder close to the sealing cover. The water cooling jacket is used to reduce the temperature at the sealing cover during the use of the reactor to avoid the sealing cover The sealing gasket of the reactor is aged and deformed due to the influence of high temperature. The cylinder body is provided with a hook 19 to facilitate loading and unloading of the reactor with the lifting equipment. The cylinder body is also provided with a gas inlet and outlet. The gas inlet and outlet of the first reactor and the second reactor are respectively provided with a first valve 1 and a second valve 2; the gas storage tank 6 is provided with a pressure gauge 18, a reactor joint equipped with a third valve 3, The vacuum joint equipped with the fourth valve 4 and the hydrogen source joint equipped with the fifth valve 5;

The first heating furnace and the second heating furnace are installed on the first support 14 and the second support 15 respectively, and the first reactor 9 and the second reactor 10 are respectively installed on the movable third support 16 of the band roller and the third support of the band roller. On the mobile fourth support 17, the reaction section 9-1 of the first reactor is located in the hearth of the first heating furnace 7, and the reaction section 10-1 of the second reactor is located in the hearth of the second heating furnace 8 . The first reactor and the second reactor are arranged on the movable third support 16 and the fourth movable support 17 with rollers in order to facilitate the first reactor and the second reactor from the first heating furnace and the second Pushing in and out of the heating furnace is convenient for loading and unloading. At the same time, when the first reactor and the second reactor need to be cooled, pushing them out of the heating furnace can speed up the cooling speed. The reactor joint of the gas storage tank 6 communicates with the gas inlet and outlet of the first reactor and the second reactor respectively through pipe fittings.

Example 2

In this embodiment, the structure of the hydrodehydrogenation furnace is shown in Figure 2, including a horizontally placed heating furnace, a horizontally placed reactor, a gas storage tank 6, a first support 14, a second support 15, a mobile The third support 16, the fourth mobile support 17 and the fan 20, the heating furnace includes the first heating furnace 7 and the second heating furnace 8, and the reactor includes the first reactor 9 and the second reactor 10,

The first heating furnace 7 and the second heating furnace 8 are equipped with thermocouples 13, and the first reactor 9 and the second reactor 10 are cylinders with both ends closed, and one end of the cylinder is provided with a material Inlet and outlet, there is a sealing cover 11 at the material inlet and outlet, and a water cooling jacket 12 is provided on the cylinder close to the sealing cover. The water cooling jacket is used to reduce the temperature at the sealing cover during the use of the reactor to avoid the sealing cover The sealing gasket of the reactor is aged and deformed due to the influence of high temperature. The cylinder body is provided with a hook 19 to facilitate loading and unloading of the reactor with the lifting equipment. The cylinder body is also provided with a gas inlet and outlet. The gas inlet and outlet of the first reactor and the second reactor are respectively provided with a first valve 1 and a second valve 2; the gas storage tank 6 is provided with a pressure gauge 18, a reactor joint equipped with a third valve 3, The vacuum joint equipped with the fourth valve 4 and the hydrogen source joint equipped with the fifth valve 5;

The first heating furnace and the second heating furnace are installed on the first support 14 and the second support 15 respectively, and the first reactor 9 and the second reactor 10 are respectively installed on the movable third support 16 of the band roller and the third support of the band roller. On the mobile fourth support 17, the reaction section 9-1 of the first reactor is located in the hearth of the first heating furnace 7, and the reaction section 10-1 of the second reactor is located in the hearth of the second heating furnace 8 , the mobile third support 16 and the fourth mobile support 17 are all provided with fans 20 for cooling the first reactor and the second reactor, and the first reactor and the second reactor are arranged on the mobile first The three supports 16 and the movable fourth support 17 with rollers are used to push the first reactor and the second reactor in and out from the first heating furnace and the second heating furnace conveniently, so as to facilitate loading and unloading. At the same time, when the first reactor and the second reactor need to be cooled, they can be pushed out from the heating furnace to speed up the cooling speed, and the blower fan 20 can be started during cooling, which can further speed up the cooling speed and improve production efficiency. The reactor joint of the container tank 6 communicates with the gas inlet and outlet of the first reactor and the second reactor respectively through pipe fittings.

Example 3

The present embodiment improves the preparation method of titanium powder with low oxygen content, as shown in Figure 3, the method uses the hydrodehydrogenation furnace described in Example 2 and is equipped with a vacuum pump 21 and a storage tank 22 storing high-purity hydrogen, and the vacuum pump 21 The storage tank 22 that stores high-purity hydrogen is communicated with the vacuum joint and the hydrogen source joint of the gas storage tank 6 of the hydrodehydrogenation furnace respectively through pipe fittings, and the steps are as follows:

① Loading

The hydrogen storage alloy vanadium titanium chromium iron is placed in the reaction section 9-1 of the first reactor, and the 0-grade sponge titanium with a particle size of no more than 25 mm is placed in the reaction section 10-1 of the second reactor. The mass ratio of hydrogen alloy vanadium-titanium-chromium-iron to 0-grade sponge titanium is 2:1, close the sealing cover 11 of the first reactor and the second reactor, close the first valve to the fifth valve, then start the vacuum pump 21 and open the second From one valve to the fourth valve, vacuumize until the pressure in the first reactor, the second reactor and the gas storage tank is 1000 Pa, and close the first valve to the fourth valve and the vacuum pump 21 .

②Hydrogen storage alloy activates and purifies the atmosphere in the furnace

Open the first heating furnace 7 to raise the temperature of the hearth of the first heating furnace to 200°C and keep this temperature; open the fifth valve, pass hydrogen to the gas storage tank 6 to a pressure of 0.1MPa, close the fifth valve, and then Open the first valve to the third valve, until the indication of the pressure gauge 18 on the gas storage tank no longer changes (this process is the operation of passing hydrogen), start the vacuum pump and open the fourth valve to evacuate to the first reactor, the second The pressure in the second reactor and the gas storage tank is 1000Pa, close the first valve to the fourth valve and the vacuum pump (this process is a vacuum operation); repeat the aforementioned hydrogen and vacuum operation 5 times, then close the first heating Furnace, the first reactor 9 is released from the first heating furnace 7, the fan on the mobile third support 16 is started to reduce the temperature of the first reactor to room temperature, and then the first reactor is pushed into the first heating furnace middle.

③Hydrogen storage alloy hydrogen absorption

Open the fifth valve, pass hydrogen to the gas storage tank until the pressure is 1MPa, close the fifth valve (this process is the operation of passing hydrogen), then open the first valve and the third valve to make the hydrogen storage alloy in the first reactor Inhale hydrogen, after the indication of the pressure gauge 18 on the gas storage tank remains unchanged, close the first valve and the third valve (this process is hydrogen absorption operation); The reading on the pressure gauge on the container tank is higher than the atmospheric pressure and does not change, and the hydrogen storage alloy reaches hydrogen absorption saturation; then start the vacuum pump and open the first valve, the third valve and the fourth valve to evacuate to the first reactor And the pressure in the gas storage tank is 1000Pa, close the first valve, the third valve and the fourth valve and the vacuum pump.

④Hydrogenation reaction of sponge titanium

Turn on the first heating furnace 7 and the second heating furnace 8, respectively raise the furnace temperature of the first heating furnace and the second heating furnace to 300°C and 400°C to maintain the aforementioned temperature, and open the first valve to the third valve for hydrogen storage Alloy hydrogenation reaction and hydrogenation reaction of sponge titanium, after 1h, make the first valve, the fourth valve and the fifth valve be in closed state, the second valve and the third valve are in open state, the pressure gauge on the gas storage tank The reading is higher than the atmospheric pressure and does not change, indicating that the hydrogenation reaction of the sponge titanium has been completed to obtain titanium hydride. Close the first heating furnace and the second heating furnace and the first valve to the third valve, push the first reactor out of the first heating furnace, push the second reactor out of the second heating furnace, start the mobile third The fan 20 on the frame 16 and the mobile fourth frame 17 reduces the temperature of the first reactor and the second reactor to room temperature.

⑤ Pulverization and dehydrogenation

The titanium hydride is quickly taken out from the second reactor, sealed in a ball mill jar in the glove box and ball-milled until the particle size does not exceed 100 μm. No balls are used during ball milling to avoid contamination of the titanium hydride by the balls. The atmosphere in the glove box is Argon gas with oxygen content <1000ppm, quickly transfer the ball-milled titanium hydride to the reaction section 10-1 of the second reactor, then close the sealing cover of the second reactor, and push the second reactor into the second heating In the furnace, turn on the vacuum pump and open the second valve to the fourth valve, evacuate to keep the pressure in the second reactor and the gas storage tank at 100-1000Pa, and at the same time turn on the second heating furnace to heat the hearth of the second heating furnace To 600 ℃ and keep the temperature, carry out the dehydrogenation reaction of titanium hydride, the dehydrogenation reaction time is 2h, after the dehydrogenation is completed, close the second heating furnace, the second valve to the fourth valve and the vacuum pump to obtain low oxygen content Titanium powder.

Use the mobile fourth support 17 to push the second reactor out of the second heating furnace, cool the temperature of the second reactor to room temperature, quickly take out the obtained titanium powder, pulverize and sieve under an argon atmosphere to obtain the particle size A titanium powder sample of no more than 80 μm was packaged in an argon atmosphere, and the oxygen content of the titanium powder was measured using a LECO TCH-600 nitrogen, oxygen and hydrogen analyzer, and the result was 0.15 wt%. And adopt existing hydrodehydrogenation method, adopt the sponge titanium identical with present embodiment, identical hydrogenation reaction temperature and time, the oxygen content of the titanium powder prepared by identical ball milling condition and identical dehydrogenation reaction temperature and time is 0.31wt %. It shows that the method of the present invention can effectively reduce the oxygen content in the titanium powder and improve the quality of the titanium powder.

Example 4

The present embodiment improves the preparation method of titanium powder with low oxygen content, as shown in Figure 3, the method uses the hydrodehydrogenation furnace described in Example 2 and is equipped with a vacuum pump 21 and a storage tank 22 storing high-purity hydrogen, and the vacuum pump 21 The storage tank 22 that stores high-purity hydrogen is communicated with the vacuum joint and the hydrogen source joint of the gas storage tank 6 of the hydrodehydrogenation furnace respectively through pipe fittings, and the steps are as follows:

① Loading

The hydrogen storage alloy vanadium titanium chromium iron is placed in the reaction section 9-1 of the first reactor, and the 0-grade sponge titanium with a particle size of no more than 25mm is placed in the reaction section 10-1 of the second reactor, The mass ratio of the hydrogen storage alloy vanadium-titanium-chromium-iron to 0-grade sponge titanium is 2.5:1, close the sealing cover 11 of the first reactor and the second reactor, close the first valve to the fifth valve, then start the vacuum pump 21 and open The first valve to the fourth valve are vacuumed until the pressure in the first reactor, the second reactor and the gas storage tank is 100 Pa, and the first valve to the fourth valve and the vacuum pump 21 are closed.

②Hydrogen storage alloy activates and purifies the atmosphere in the furnace

Open the first heating furnace 7 to raise the furnace temperature of the first heating furnace to 300°C and keep the temperature; open the fifth valve, pass hydrogen to the gas storage tank 6 until the pressure is 0.5MPa, close the fifth valve, and then open From the first valve to the third valve, when the indication of the pressure gauge 18 on the gas storage tank no longer changes (this process is hydrogen operation), start the vacuum pump and open the fourth valve to evacuate to the first reactor, the second The pressure in the reactor and the gas storage tank is 100Pa, close the first valve to the fourth valve and the vacuum pump (this process is a vacuum pumping operation); repeat the aforementioned hydrogen gas and vacuum pumping operations for 3 times, then close the first heating furnace , the first reactor 9 is released from the first heating furnace 7, the fan on the mobile third support 16 is started to reduce the temperature of the first reactor to room temperature, and then the first reactor is pushed into the first heating furnace .

③Hydrogen storage alloy hydrogen absorption

Open the fifth valve, pass hydrogen to the gas storage tank until the pressure is 1.5MPa, close the fifth valve (this process is the operation of passing hydrogen), then open the first valve and the third valve to make the hydrogen storage in the first reactor Alloy hydrogen absorption, after the indication of the pressure gauge 18 on the gas storage tank remains unchanged, close the first valve and the third valve (this process is the hydrogen absorption operation); repeat the aforementioned hydrogen flow and hydrogen absorption operations, when the gas The indication of the pressure gauge on the storage tank is higher than the atmospheric pressure and does not change, and the hydrogen storage alloy reaches hydrogen absorption saturation; then start the vacuum pump and open the first valve, the third valve and the fourth valve, and vacuumize to the first reaction The pressure in the device and the gas storage tank is 100Pa, and the first valve, the third valve and the fourth valve and the vacuum pump are closed.

④Hydrogenation reaction of sponge titanium

Turn on the first heating furnace 7 and the second heating furnace 8, respectively raise the furnace temperature of the first heating furnace and the second heating furnace to 350°C and 425°C to maintain the aforementioned temperature, and open the first valve to the third valve for hydrogen storage Alloy hydrogenation reaction and hydrogenation reaction of sponge titanium, after 1h, make the first valve, the fourth valve and the fifth valve be in closed state, the second valve and the third valve are in open state, the pressure gauge on the gas storage tank The reading is higher than the atmospheric pressure and does not change, indicating that the hydrogenation reaction of the sponge titanium has been completed to obtain titanium hydride. Close the first heating furnace and the second heating furnace and the first valve to the third valve, push the first reactor out of the first heating furnace, push the second reactor out of the second heating furnace, start the mobile third The fan 20 on the frame 16 and the mobile fourth frame 17 reduces the temperature of the first reactor and the second reactor to room temperature.

⑤ Pulverization and dehydrogenation

The titanium hydride is quickly taken out from the second reactor, sealed in a ball mill jar in the glove box and ball-milled until the particle size does not exceed 100 μm. No balls are used during ball milling to avoid contamination of the titanium hydride by the balls. The atmosphere in the glove box is Argon gas with oxygen content <1000ppm, quickly transfer the ball-milled titanium hydride to the reaction section 10-1 of the second reactor, then close the sealing cover of the second reactor, and push the second reactor into the second heating In the furnace, turn on the vacuum pump and open the second valve to the fourth valve, evacuate to keep the pressure in the second reactor and the gas storage tank at 100-1000Pa, and at the same time turn on the second heating furnace to heat the hearth of the second heating furnace To 650 ℃ and keep the temperature, carry out the dehydrogenation reaction of titanium hydride, the dehydrogenation reaction time is 2h, after the dehydrogenation is completed, close the second heating furnace, the second valve to the fourth valve and the vacuum pump to obtain low oxygen content Titanium powder.

Use the mobile fourth support 17 to push the second reactor out of the second heating furnace, turn on the fan 20 to lower the temperature of the second reactor to room temperature, and then quickly take out the obtained titanium powder, crush and sieve it under an argon atmosphere to obtain A titanium powder sample with a particle size of no more than 75 μm was packaged under an argon atmosphere, and the oxygen content of the titanium powder was measured using a LECO TCH-600 nitrogen, oxygen and hydrogen analyzer, and the result was 0.12 wt%.

Claims (10)

1. a kind of hydrogenation and dehydrogenization stove, includes the heating furnace and reactor of horizontal placement, it is characterised in that is also stored including gas and holds tank (6), first support (14), second support (15), portable 3rd support (16) and portable 4th support (17), the heating Stove includes the first heating furnace (7) and the second heating furnace (8), and reactor includes first reactor (9) and second reactor (10),

Thermocouple (13), first reactor (9) and second reactor are equipped with first heating furnace (7) and the second heating furnace (8) (10) cylinder closed at both ends is, one end of the cylinder, which is provided with material import and export, material import and export, is provided with closure (11), it is provided with the cylinder of close closure on water collar (12), the cylinder and is additionally provided with gas inlet and outlet, first reactor With the first valve (1) and the second valve (2) are respectively equipped with the gas inlet and outlet of second reactor；Gas, which stores to be held, set on tank (6) There are pressure gauge (18), the vacuumizing joint for being configured with the reactor joint of the 3rd valve (3), being configured with the 4th valve (4), configuration The hydrogen source joint of 5th valve (5)；

First heating furnace and the second heating furnace are separately mounted in first support (14) and second support (15), first reactor (9) it is separately mounted to second reactor (10) on portable 3rd support (16) and portable 4th support (17), first is anti- The reaction section (9-1) of device is answered to be located in the burner hearth of the first heating furnace (7), the reaction section (10-1) of second reactor is located at the In the burner hearth of two heating furnaces (8), the reactor joint that gas stores appearance tank (6) is anti-with first reactor and second respectively by pipe fitting The gas inlet and outlet of device is answered to connect.

2. hydrogenation and dehydrogenization stove according to claim 1, it is characterised in that portable 3rd support (16) and portable the Four supports (17) are provided with the blower fan (20) for being used for cooling down first reactor and second reactor.

3. hydrogenation and dehydrogenization stove according to claim 1 or claim 2, it is characterised in that set in the first reactor and second reactor There is suspension hook (19).

4. a kind of preparation method of low oxygen content titanium valve, it is characterised in that any right will in this method usage right requirement 1 to 3 Seek the hydrogenation and dehydrogenization stove and equipped with vavuum pump (21) and contain the storage tank (22) of high-purity hydrogen, by vavuum pump (21) and contain The vacuumizing joint and hydrogen source that the storage tank (22) of high-purity hydrogen stores appearance tank (6) with the gas of hydrogenation and dehydrogenization stove respectively by pipe fitting connect Head connection, step is as follows：

1. feed

Hydrogen bearing alloy and titanium sponge are respectively placed in the reaction section (9-1) of first reactor and the reaction section of second reactor In (10-1), closure (11) and the first valve to the 5th valve are closed, then starts vavuum pump (21) and opens the first valve The valves of Men Zhi tetra-, be evacuated to first reactor, second reactor and gas store hold the pressure in tank for 100~ 1000Pa, closes the first valve to the 4th valve and vavuum pump；

2. hydrogen bearing alloy activates and purifies furnace atmosphere

Opening the first heating furnace makes the fire box temperature of the first heating furnace rise to 200~300 DEG C and keeps the temperature, opens the 5th valve Door, it is 0.1~0.5MPa to be stored to gas and lead in appearance tank (6) hydrogen to pressure, closes the 5th valve, then opens the first valve extremely 3rd valve, starts vavuum pump after the registration that gas stores the pressure gauge (18) on appearance tank is constant and the 4th valve of opening is vacuumized It is 100~1000Pa that the pressure held in tank is stored to first reactor, second reactor and gas, closes the first valve to the 4th Valve and vavuum pump；Foregoing logical hydrogen and the operation vacuumized 3~5 times are repeated, the first heating furnace is then shut off, by the first reaction The temperature of device is down to room temperature；

3. hydrogen bearing alloy inhales hydrogen

The 5th valve is opened, it is 1~1.5MPa to store logical hydrogen to pressure in appearance tank to gas, closes the 5th valve, then opens First valve and the 3rd valve make the hydrogen bearing alloy in first reactor inhale hydrogen, treat that gas stores showing for pressure gauge (18) on appearance tank After number is constant, the first valve and the 3rd valve are closed；Repeat foregoing logical hydrogen and inhale the operation of hydrogen until hydrogen bearing alloy reaches suction Hydrogen saturation, then starts vavuum pump and opens the first valve, the 3rd valve and the 4th valve, be evacuated to first reactor gentle It is 100~1000Pa that body, which stores the pressure held in tank, closes the first valve, the 3rd valve and the 4th valve and vavuum pump；

4. the hydrogenation of titanium sponge

The first heating furnace and the second heating furnace are opened, the fire box temperature of the first heating furnace and the second heating furnace is risen to 300 respectively ~350 DEG C, 400~425 DEG C and aforementioned temperature is kept, open the first valve to the 3rd valve, carry out hydrogen bearing alloy hydrogen discharge reaction With the hydrogenation of titanium sponge, titantium hydride is produced after the completion of the hydrogenation of titanium sponge, the first heating furnace and the second heating is closed Stove and the first valve to the 3rd valve, room temperature is down to by the temperature of first reactor and second reactor；

5. crush and dehydrogenation

Titantium hydride is taken out from second reactor, is placed in after being crushed under argon atmosphere in the reaction section of second reactor, Be then shut off the closure of second reactor, open vavuum pump and simultaneously open the second valve to the 4th valve, vacuumize make it is second anti- Answer device and gas to store the pressure held in tank and be maintained at 100~1000Pa, be then turned on the second heating furnace by the burner hearth of the second heating furnace Temperature is risen to after the completion of 600~650 DEG C and the dehydrogenation reaction for keeping the temperature to carry out titantium hydride, dehydrogenation reaction, is closed second and is added Hot stove, the second valve produce the titanium valve that oxygen content is no more than 0.15wt% to the 4th valve and vavuum pump.

5. the preparation method of low oxygen content titanium valve according to claim 4, it is characterised in that step 1. in, in first reactor Hydrogen bearing alloy and second reactor in titanium sponge mass ratio be (2~2.5):1.

6. the preparation method of low oxygen content titanium valve according to claim 4 or 5, it is characterised in that the hydrogen bearing alloy is vanadium titanium Ferrochrome.

7. the preparation method of low oxygen content titanium valve according to claim 4 or 5, it is characterised in that the titanium sponge is 0 grade of sea Continuous titanium.

8. the preparation method of low oxygen content titanium valve according to claim 6, it is characterised in that the titanium sponge is 0 grade of sponge Titanium.

9. the preparation method of low oxygen content titanium valve according to claim 4 or 5, it is characterised in that step 5. in dehydrogenation reaction After the completion of, the second heating furnace, the second valve to the 4th valve and vavuum pump are closed, the temperature of second reactor is down to after room temperature Gained titanium valve is taken out, grinds, sieve under argon atmosphere.

10. the preparation method of low oxygen content titanium valve according to claim 8, it is characterised in that step 5. in completed in dehydrogenation Afterwards, the second heating furnace, the second valve to the 4th valve and vavuum pump are closed, the temperature of second reactor is down to after room temperature and taken out Gained titanium valve, grinds under argon atmosphere, sieves.