An apparatus for producing high-porosity titanium sponge and a method of using the same

Abstract

The application relates to a device for producing high-porosity titanium sponge and a method for using the same, and belongs to the technical field of titanium industry. A detachable distillation channel frame is fixed to the middle and lower part of a vertical reaction container. In use, the channel frame is first installed in the reaction container, liquid magnesium is added and heated, and after the titanium sponge is reduced and vacuum distilled, the channel frame is detached together with the titanium sponge for slicing, and after the slicing and crushing are completed, the channel frame fragments are separated from the titanium sponge particles. The titanium sponge has a distillation channel formed in the center of the titanium sponge, the distillation cycle of a single furnace can be shortened by 14-17%, the impurities in the finished titanium sponge can meet the requirements of 0.030%-0.055% of Cl impurities in the national standard, the porosity of the finished titanium sponge is significantly improved, the packaging density of the finished product is as low as 1.45-1.50 g / cm3, and the efficiency of the vacuum distillation stage of the titanium sponge can be significantly improved by using the device. A The product requires that the content of Cl impurities is 0.030%-0.055%. The porosity of the obtained finished titanium sponge is significantly improved, and the packaging density of the finished product is as low as 1.45-1.50 g / cm 3 . The efficiency of the vacuum distillation stage of the titanium sponge can be significantly improved by using the device.

Description

TECHNICAL FIELD

[0001] The present application belongs to the production technology field of titanium industry, and particularly relates to a device for producing high-porosity sponge titanium and a use method thereof. BACKGROUND

[0002] Titanium and titanium alloy have the characteristics of high specific strength, corrosion resistance, and good high-temperature performance, and are widely used in the fields of aerospace, deep-sea exploration, chemical industry, medical treatment, etc. Sponge titanium, as a raw material for the preparation of titanium and titanium alloy, is only prepared by the magnesium thermal method in industry. The sponge titanium is obtained by vacuum self-consumption smelting and cold bed electron beam smelting method to obtain titanium and titanium alloy ingots. Before vacuum self-consumption smelting, the sponge titanium needs to be pressed into a self-consumption electrode. When the sponge titanium has poor porosity or the pressure of the press is low, the pressed electrode is prone to abnormal conditions such as material falling off and breaking during smelting, which eventually leads to interruption of smelting. Therefore, sponge titanium with better porosity is more favored by smelting enterprises.

[0003] The existing problem of the sponge titanium industrial production is that the mass transfer capacity of Mg and MgCl2 in the center of the titanium lump is poor in the vacuum distillation stage, the distillation period is prolonged, and the pore structure of the sponge titanium is dense.

[0004] In order to obtain sponge titanium with better porosity, various enterprises in the reduction process adopt measures such as adding TiCl4 dispersedly and improving the heat dissipation capacity of the reactor to prevent the pore structure of the sponge titanium from being dense due to excessively high temperature. For example, the document with the patent application number CN200920125595.8 is a reduction reaction device for producing sponge titanium, which solves the problem of excessively high temperature in the center of the reactor caused by the centralized addition of TiCl4 by uniformly and symmetrically arranging multiple feeding devices on the reaction furnace cover plate; the document with the patent application number CN200710011744.3 is a device for internal heat exchange of a magnesium method sponge titanium production reactor, which cools the sponge titanium in the reactor by inserting a heat exchanger into the reactor and passing a wind cooling medium into the heat exchanger. In the vacuum distillation process, various enterprises mainly improve the Mg and MgCl2 distillation efficiency to shorten the distillation period and improve the shrinkage degree of the titanium lump in the vacuum distillation stage. For another example, the document with the patent application number CN202123417024.1 is a large-scale hollow sponge titanium production device, which solves the problems of long diffusion path of Mg and MgCl2 in the center of the titanium lump and long distillation period by adding a conical barrel in the reactor; the document with the patent application number CN202210358466.3 is a sponge titanium production titanium lump supporting and pore forming device, which improves the kinetic conditions of Mg / MgCl2 distillation in the pores of titanium sponge by adding a cylindrical supporting device in the reactor to support and form pores for the titanium lump. SUMMARY

[0005] The present application aims to provide a device for producing high-porosity titanium sponge and a method for using the same, so as to solve the problems of poor mass transfer capacity of Mg and MgCl2 in the center of titanium lump in the vacuum distillation stage, prolonged distillation period, and dense pore structure of the titanium sponge, and solve the problem of dense surface of the titanium sponge due to the reaction of TiCl4 on the surface of the titanium lump.

[0006] The device for producing high-porosity titanium sponge is a hollow vertical reaction container, the upper opening of the container is provided with a cover, the lower part of the container is provided with a perforated partition plate, and the lower end of the container is provided with a MgCl2 discharge mechanism.

[0007] The central part of the middle and lower part of the reaction container is detachably fastened with a tubular, one-time-use distillation channel frame in the longitudinal direction, the upper end and the lower end of the channel frame are open, the upper end of the channel frame is provided with a titanium particle blocking cap, and the pipe wall of the channel frame is uniformly provided with 4-10 longitudinal distillation through holes with a diameter of 10-15 mm;

[0008] The straight section height (H4) of the reactor is the sum of the reaction interface height (H3) and the argon space height (H5) of the reactor, wherein the argon space height is 0.5-1.5 m, and preferably 1.2 m;

[0009] The ratio of the reaction interface height (H3) to the straight section height (H4) of the reactor is 0.75-0.85, and preferably the ratio is 0.8;

[0010] The ratio of the titanium lump height (H2) to the straight section height (H4) of the reactor at the end of TiCl4 feeding is 0.6-0.7 m, and preferably the ratio is 0.68 m;

[0011] The ratio of the channel frame height (H1) to the straight section height (H4) of the reactor is 0.3-0.5, and preferably the ratio is 0.4;

[0012] The channel frame height (H1) is always less than the titanium lump height (H2), and the titanium lump height (H2) is always less than the reaction stage height (H3);

[0013] The ratio of the straight section height (H4) of the reactor to the reactor diameter (D1) is 2.0-2.5, and preferably the ratio is 2.2; the reactor diameter is 1.4-2.3 m, and preferably the reactor diameter is 1.9 m;

[0014] The channel frame functions to form a distillation channel in the center of the titanium lump.

[0015] The channel frame is preferably made of pure titanium, and the grade thereof is preferably TA1.

[0016] The channel frame is preferably fastened to the perforated baffle plate at the lower part of the reactor by means of bolts, and the open lower end of the channel frame is in communication with the holes in the perforated baffle plate after fastening.

[0017] The diameter of the channel frame is preferably 100-150 mm, and the wall thickness is preferably 0.5-1.5 mm, and the optimal diameter is 150 mm and the optimal wall thickness is 0.5 mm.

[0018] A method for using the device for producing high-porosity titanium sponge, characterized by the following steps:

[0019] (1) installing the channel frame in the reactor;

[0020] (2) adding liquid magnesium into the reactor and heating, and when the temperature reaches the set temperature value, adding TiCl4 into the reactor, and the ratio of the total amount of TiCl4 to the total amount of Mg is 2.0-2.3, and the optimal ratio is 2.2;

[0021] (3) installing a condenser above the reactor after the amount of TiCl4 reaches the set value;

[0022] (4) in the vacuum distillation stage, the distillation cycle is determined in the following manner: the pressure drop speed of the distiller is less than 0.5 Pa / h, and the ratio of the distillation cycle to the furnace weight is 15.0-19.0 (h / ton), and the optimal ratio is 17.0 h / ton;

[0023] (5) the furnace weight of the titanium sponge is calculated according to the following formula: W = {(M1 / 189.68) x 47.87} / 1000, wherein the weight unit of TiCl4 is kg, and the unit of the furnace weight W is ton;

[0024] (6) in the titanium sponge reduction and vacuum distillation stage, the channel frame is removed when the titanium lump is sliced, and is sliced together with the titanium lump, and after the slicing and crushing are completed, the channel frame fragments are separated from the titanium sponge particles;

[0025] When the device is used, a thermocouple is used to monitor the outer wall of the reactor, wherein the control temperature of the titanium lump height (H2) section is 840-890℃, and the optimal control temperature is 850℃; the control temperature of the titanium lump height to the reaction interface (H3-H2) section is 800-850, and the optimal control temperature is 840℃; and the control temperature of the argon upper space (H5) section is 720-750℃, and the optimal control temperature is 730℃.

[0026] The beneficial effects of the present application are as follows: when the device and the use method thereof are used for industrial production, a distillation channel with a diameter of 100-150 mm is formed in the center of the titanium sponge lump, the single-furnace distillation cycle can be shortened by 14-17%, and the impurities in the finished titanium sponge can meet the requirements of the national standard GB / T 2524-2019 "Titanium Sponge".A The product requirement is that the Cl impurity content is 0.030%-0.055%. The porosity of the titanium sponge product produced is significantly improved, and the packaging density of the finished product can be increased from 1.65-1.75g / cm 3 Reduced to 1.45-1.50g / cm 3 During the reduction production process, the titanium sponge lump is always immersed below the surface of liquid magnesium, and the weight of the bright titanium shell of the titanium sponge cap can be reduced by 150-350kg. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic diagram of the main structure of the embodiment.

[0028] Figure 2 It is a schematic diagram of the main structure of the channel frame in the embodiment.

[0029] Figure 3 It is a schematic diagram showing the meaning of each dimension in the embodiment.

[0030] Figure 4 Schematic top view of the porous partition in the embodiment. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0032] See also Figures 1-4 .

[0033] It is a hollow vertical reaction vessel 1 with a cover 6 at the top, a porous partition 8 at the lower part of the container 1, and a MgCl2 discharge mechanism 9 at the lower end of the container.

[0034] A tubular, disposable distillation channel holder 2 is detachably fastened longitudinally in the center of the lower middle portion of the reaction vessel 1. The upper end of the channel holder 2 is open and the lower end is closed. The open end of the channel holder 2 is provided with a titanium particle clogging prevention cap 4. Nine longitudinally arranged distillation through-holes 3 are evenly distributed on the tube wall of the channel holder 2. The diameter of the through-holes 3 is 50 mm, and the spacing between the holes is 20 mm.

[0035] The straight section height H4 of reactor 1 is the sum of the reaction interface height H3 and the argon-filled space height H5 of the reactor, where the Ar gas space height is 1.2 m.

[0036] The ratio of the reaction interface height H3 to the reactor straight section height H4 is 0.8.

[0037] At the end of TiC14 feeding, the ratio of the titanium lump height H2 to the reactor straight section height H4 was 0.68m.

[0038] The ratio of the channel frame height H1 to the reactor straight section height H4 is 0.4.

[0039] The height H1 of the channel frame is always smaller than the height H2 of the titanium lump; the height H2 of the titanium lump is always smaller than the height H3 of the reaction stage.

[0040] The ratio of the reactor straight section height H4 to the reactor diameter is 2.2; the reactor diameter is 1.9 m.

[0041] The material of the channel frame 2 is TA1 pure titanium tube, the pure titanium tube has a diameter of 150mm and a wall thickness of 0.5mm.

[0042] The channel frame 2 is fastened to the porous partition 8 at the lower part of the reaction container 1 by bolts 5.

[0043] In the figure, numeral 7 represents titanium particles.

[0044] How to use this device:

[0045] (1) Fixing the distillation channel bracket (2) in an empty reaction vessel (1) by means of bolts (5); adding 14 tons of liquid magnesium into the reaction vessel (1) and heating it; when the temperature reaches 750°C, adding TiCl4 into the reaction vessel, wherein the total amount of TiCl4 added is 18 tons.

[0046] (2) The amount of TiCl4 added reached 30.8 tons, and a condenser was installed above the reactor to form an I-type structure by distiller and condensation;

[0047] (3) The outer wall of the reactor was monitored using thermocouples, with the temperature of the H2 section controlled at 850°C; the temperature of the section from the titanium lump height to the reaction interface (H3-H2) controlled at 840°C; and the temperature of the section above the argon gas (H5) controlled at 730°C.

[0048] (4) heating the distillation furnace to 800-900° C. and performing vacuum distillation on the titanium sponge in the distiller;

[0049] (5) When the pressure drop rate of the distiller is less than 0.5Pa / h, and the pressure of the distiller reaches below 10Pa, the pressure (absolute pressure) at the bottom of the distiller is less than 10Pa for 30h, and the total distillation time reaches 135.0h, the distillation operation is carried out; argon is introduced into the distiller, and the argon pressure is controlled at 5-25kPa; when the wall temperature of the distiller drops to 40℃, the titanium lump in the reactor is taken out.

[0050] (6) The distillation channel support and the titanium lump are sliced ​​at the same time. After the slicing is completed, the distillation channel fragments are separated from the sponge titanium particles.

[0051] Comparison of distillation cycles before and after using this device

[0052]

[0053] The device is used for producing 7.5 tons of titanium sponge in a furnace. The time consumed for reducing the pressure (absolute pressure) in the lower part of the distiller to 4 Pa during vacuum distillation is 39.1-96.8 h, and the average time is 61.5 h. The pressure (absolute pressure) in the lower part of the distiller at the end of vacuum distillation is 1.7-3.3 Pa, and the average pressure is 2.5 Pa. The vacuum distillation cycle is reduced from 157-160 h to 130.1-137.9 h, and the average distillation cycle is 133.5 h. The efficiency of vacuum distillation stage of titanium sponge is significantly improved after using the device.

Claims

1. A method for producing highly porous titanium sponge, characterized in that: (1) The equipment used is a hollow vertical reaction vessel with a lid on the top of the vessel, a porous partition at the bottom of the vessel, a MgCl2 discharge mechanism at the bottom of the vessel, a tubular, disposable distillation channel rack detachably fastened longitudinally to the center of the lower middle portion of the reaction vessel, the upper and lower ends of the channel rack are open, the upper end of the channel rack is provided with a titanium particle clogging prevention cap, 4-10 longitudinally arranged distillation through holes are uniformly distributed on the tube wall of the channel rack, and the diameter of the through holes is 10-15 mm; the height of the straight section of the reactor is the sum of the height of the reaction interface and the height of the argon-filled space of the reactor, wherein the height of the Ar gas space is 0.5-1.5 m; the height of the reaction interface is 1.5 m higher than the height of the straight section of the reactor. The ratio of the height of the titanium tube to the height of the straight section of the reactor is 0.75-0.85; the ratio of the height of the titanium tube to the height of the straight section of the reactor at the end of the TiCl4 addition is 0.68; the ratio of the height of the channel rack to the height of the straight section of the reactor is 0.3-0.5; the height of the channel rack is always less than the height of the titanium tube; the height of the titanium tube is always less than the height of the reaction stage; the ratio of the height of the straight section of the reactor to the diameter of the reactor is 2.0-2.5; the diameter of the reactor is 1.4-2.3m; the diameter of the channel rack is 100-150mm, and the wall thickness is 0.5-1.5mm; the channel rack is fastened to the porous baffle at the lower part of the reaction vessel with bolts, and after fastening, the lower end opening of the channel rack is connected to the holes on the porous baffle; (2) The operation steps are as follows: (a) Installing a channel rack in a reaction vessel; (b) adding liquid magnesium to the reaction vessel and heating it, and when the temperature reaches a set temperature, adding TiCl4 to the reaction vessel, wherein the ratio of the total amount of TiCl4 added to the total amount of Mg added is 2.0-2.3; (c) After the amount of TiCl4 added reaches the set value, a condenser is installed above the reactor; (d) During the vacuum distillation stage, the distillation cycle was determined as follows: the rate of pressure drop in the distiller was less than 0.5 Pa / h, and the ratio of the distillation cycle to the furnace weight was controlled to be 15.0-19.0 h / ton; (e) The furnace weight of titanium sponge is calculated according to the following formula: W = {(M1 / 189.68) × 47.87} / 1000, where the TiCl4 weight M1 is in kg and the furnace weight W is in tons; (f) During the titanium sponge reduction and vacuum distillation stages, when the titanium lump is sliced, the channel frame is removed and sliced ​​together with the titanium lump. After the slicing is completed, the channel frame fragments are separated from the titanium sponge particles. When the equipment is in use, a thermocouple is used to monitor the outer wall of the reactor, wherein the temperature of the titanium lump height section is controlled at 840-890°C; the temperature of the titanium lump height to the reaction interface section is controlled at 800-850; and the temperature of the argon-filled space height section of the reactor is controlled at 720-750°C.

2. The method for producing highly porous titanium sponge according to claim 1, wherein: The height of the Ar gas space is 1.2m, the ratio of the reaction interface height to the reactor straight section height is 0.8, the ratio of the titanium lump height to the reactor straight section height at the end of TiCl4 addition is 0.68, the ratio of the channel rack height to the reactor straight section height is 0.4, and the ratio of the reactor straight section height to the reactor diameter is 2.

2.

3. The method for producing highly porous titanium sponge according to claim 1, wherein: The channel frame is made of TA1 titanium tube.

4. The method for producing highly porous titanium sponge according to claim 1, wherein: In step (b), the ratio of the total amount of TiCl4 added to the total amount of Mg added is 2.2; In step (d), the ratio of the distillation cycle to the furnace weight is controlled to be 17.0 h / ton.

5. The method for producing highly porous titanium sponge according to claim 1, wherein: The outer wall of the reactor was monitored using a thermocouple. The temperature at the titanium lump height section was controlled at 850°C, and the temperature at the titanium lump height to the reaction interface section was controlled at 840°C. The temperature at the argon-filled space height section of the reactor was controlled at 730°C.

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