CN110158049B - System and method for producing Ti powder or Ti coating through fluidized bed - Google Patents

System and method for producing Ti powder or Ti coating through fluidized bed Download PDF

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CN110158049B
CN110158049B CN201810456041.XA CN201810456041A CN110158049B CN 110158049 B CN110158049 B CN 110158049B CN 201810456041 A CN201810456041 A CN 201810456041A CN 110158049 B CN110158049 B CN 110158049B
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powder
fluidized bed
pipeline
ticl
deposition reaction
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CN110158049A (en
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朱庆山
向茂乔
宋淼
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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
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • C23C16/14—Deposition of only one other metal element
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/442—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using fluidised bed process

Abstract

The invention discloses a fluidized bed for producing Ti powder and Ti coatingSystems and methods of layers. Adding titanium seed powder in fluidized bed, fluidizing with inert gas, and adding gaseous TiCl at certain temperature range4Reacting with hydrogen in a fluidized bed to synthesize Ti powder and a Ti coating. The method obviously shortens the process of preparing the Ti powder by the traditional process, improves the efficiency of preparing the Ti powder and the Ti coating by the traditional process, has no other metal by-products in the reaction process, has simple process flow, does not need high-cost equipment, can realize continuous mass production of the Ti powder and the Ti coating, and has good economic benefit and social benefit.

Description

System and method for producing Ti powder or Ti coating through fluidized bed
Technical Field
The invention belongs to the field of chemical engineering and materials, and particularly relates to a system and a method for producing Ti powder and a Ti coating.
Background
Titanium metal has the characteristics of small density, good processing performance, high strength and excellent corrosion resistance, and plays an increasingly important role in the fields of high-end automobile manufacturing and aerospace. However, titanium metal is difficult to smelt, resulting in expensive metallic Ti powder. In addition, the processing cost of titanium is high, and the price of titanium parts is very expensive, so that the application of the titanium parts in the traditional field is greatly limited.
At present, titanium powder on the market is mainly developed based on Hunter (Na reduction) or Kroll (Mg reduction) reduction process (J.Am.chem.Soc.,32(1910)330, U.S. patent 2,205,854(1937)), namely TiO is prepared2Chlorination to TiCl4Subsequent reduction of TiCl with Na or Mg4Obtaining titanium sponge, refining the titanium sponge to obtain high-purity titanium ingots, and finally processing the titanium ingots into parent materials in different forms such as titanium rods, titanium wires and the like. Finally, powders with different properties are prepared by adopting different processes based on the titanium base material. At present, the metal titanium powder is prepared by the following three main processes: (1) hydrogenation dehydrogenation process for preparing powder, i.e. hydrogenating parent metal into TiH2And then mechanically crushed into fine particles, followed by dehydrogenation to obtain hydrogenated dehydrogenated powder. For example, in US6475428B1, to produce ultra-fine titanium powder, the parent material is first hydrogenated to TiH2Then broken into small pieces, and rapidly added in vacuumHeating to 450 ℃ and 500 ℃ and preserving heat for 2h and 6h respectively, preserving heat for 4-5 days at 650 ℃ and 700 ℃ for dehydrogenation, cooling the dehydrogenated powder, crushing again, and screening out ultrafine titanium powder with proper particle size. Although the process has high powder yield and high yield, the process is complex, the powder has irregular shape and high impurity content. (2) The powder is prepared by the gas atomization powder process, namely, the titanium base material is subjected to gas atomization in inert atmosphere to obtain spherical titanium powder. For example, chinese patent CN201410687649.5 discloses a device and method for preparing spherical titanium powder by gas atomization, wherein a titanium rod is heated in an inert atmosphere to be changed into a liquid state, and then an inert gas is used to atomize the liquid into fine particles, and the prepared powder is spherical powder due to the action of surface tension. However, the process has low powder yield, low productivity and high powder price ($ 165- & gt, 330- & gt/kg). (3) The powder is made by a rotary electrode process, namely, a self-rotating titanium rod is heated, and liquid drops leave a base material and are solidified into spherical powder under the centrifugal action. For example, the American Nuclear corporation (Atomization of cultures M]Oxford: Oxford University Press,1994,207) in vacuum or inert gas protective atmosphere, using plasma thermal arc to heat and melt the self-rotating titanium rod, diverging into small droplets along the tangential direction under the action of centrifugal force, and finally solidifying into spherical powder. But the process has extremely low powder yield, small production energy and very expensive powder price (407- & gt $ 1210/kg).
The powder prepared by the hydrogenation and dehydrogenation process is low in price, but high in impurity content. The gas atomization process and the rotary electrode process have high powder quality and low impurity content, but the powder yield is low, the price is extremely high, and the industrial acceptance is difficult. Therefore, how to use inexpensive TiO2Or TiCl4The method is a focus of developing a new process in the industry at present for preparing titanium powder directly at low cost without a parent metal preparation process as a raw material.
At present, based on TiO2Or TiCl4The direct preparation of titanium powder from raw materials mainly comprises the following three new processes: (1) molten salt electrolysis process, i.e. direct incorporation of TiO in molten salt2Or TiCl4Directly preparing Ti powder by electrolysis. For example, researchers at Cambridge university in England (Nature,407(2000)361) in CaCl2In molten salt, adding TiO2By electrolysis intoTitanium powder. Although the process greatly shortens the traditional process flow, the prepared powder has low purity, high oxygen content and low production efficiency. (2) The magnesium thermal reaction process is to adopt gaseous metal Mg to directly react TiCl4Reducing the Ti into Ti. For example, U.S. Pat. No. 6,5032176 discloses a method of introducing Mg vapor and TiCl in a fluidized bed4The fluidized gas phase reaction of gas can directly prepare titanium powder. Despite the high process efficiency, MgCl will form2By-product, followed by MgCl2The distillation process can cause the oxygen content in the titanium to be sharply increased and the powder to be internally porous. (3) Sodium thermal reaction process, similar to magnesium thermal reaction, directly reacting TiCl with gaseous metallic Na4Reducing the Ti into Ti. For example, International Titanium Powder (ITP) LLC of the united states (int.j. Powder metal, 46(2010)19.) will TiCl4The gas is injected into the Na melt and reduced to loose titanium, and then crushed to produce titanium powder. Similar to the Mg thermal reduction process, the thermal reduction reaction of sodium to form titanium also forms MgCl2The NaCl by-product which is more difficult to remove, the chlorine and oxygen content in the finally prepared titanium powder is extremely high, and the powder is loose and porous, so far, the titanium powder is not applied.
Based on the problems of difficult preparation, high price and the like of the titanium powder, the titanium coating technology is expected to replace metal titanium materials in partial fields, and the application field of titanium is expanded. At present, the preparation method of the titanium coating mainly comprises the following steps:
(1) physical deposition methods, such as physical spraying: chinese patent CN 103695834B discloses a method for spraying a titanium coating on a substrate, which changes titanium powder into a molten or semi-molten state by a plasma spraying method, and sprays the titanium coating on a steel or aluminum material. However, the method cannot be applied to workpieces with complex shapes, the coating is usually not compact enough, and the bonding force with the substrate is poor due to the existence of thermal stress.
(2) Molten salt electroplating method: chinese patent CN 103060862B discloses a method for immersing a substrate material containing K2TiF6A titanium coating is deposited on a substrate by electroplating in a molten salt medium of a eutectic salt. Such methods can achieve cladding of complex shaped parts. However, titanium is easily formed in the electrolyteThe complex compound causes low utilization efficiency of raw materials, and simultaneously equipment is complex, a large amount of chloride and fluoride are needed, so that the environment is polluted, and equipment and substrate materials are corroded. In addition, other metals need to be added into the molten salt, so that the molten salt is polluted and cannot be reused. For these reasons, the molten salt plating method has not been able to realize industrial mass production.
(3) Chemical vapor deposition method: chinese patent CN105525272A discloses a new type of medicine2And TiCl4SiC fibers are put in a tubular furnace as raw materials, are filled with mercury, and react at 1000-1200 ℃ to prepare a titanium coating with a certain thickness. However, the process has low efficiency, mercury is toxic, pollutes the environment and is not suitable for large-scale mass production of titanium coatings in industry.
In summary, although there are many methods for preparing metallic titanium powder or titanium coating, there is no new process for preparing metallic titanium powder or titanium coating with low cost and high efficiency in industry.
Disclosure of Invention
Aiming at the problems, the invention provides a system and a method for producing Ti powder and a Ti coating by a fluidized bed, and aims to solve the key problems of shortening the traditional process flow for preparing the Ti powder, improving the efficiency of preparing the Ti powder and the Ti coating by the existing new process and providing the method for preparing the Ti powder and the Ti coating by TiCl4Titanium powder seeds are introduced into a fluidized bed with high heat transfer and mass transfer efficiency as a raw material, and a novel process for preparing Ti powder and a Ti coating with high efficiency and low cost is based on chemical vapor deposition.
In order to achieve the purposes, the invention adopts the following technical scheme:
the invention provides a system and a method for producing Ti powder and a Ti coating by a fluidized bed, wherein the system comprises a powder feeding device 1 and TiCl4An evaporation device 2, a heating device 2-1, a deposition reaction fluidized bed 3, a cyclone separation device 4, a high-temperature dust removal device 5, a fine powder collection device 6, a water cooling device 7, TiCl4 A recovery device 8, a tail gas treatment device 9, a powder collecting device 10 and a base material 11;
the gas inlet at the bottom of the powder feeding device 1 is connected with an inert gas pipeline through a gas valve and a pipeline; a discharge port at the bottom of the powder feeding device 1 is connected with a feed port at the bottom of the deposition reaction fluidized bed 3 through a material valve and a pipeline;
the TiCl4The evaporation device 2 is provided with the heating device 2-1; the TiCl4The air inlet of the evaporation device 2 is connected with an inert gas pipeline and a hydrogen pipeline through an air valve and a pipeline; the TiCl4The exhaust port of the evaporation device 2 is connected with the air inlet at the lower part of the deposition reaction fluidized bed 3 through a pipeline;
the gas inlet at the bottom of the deposition reaction fluidized bed 3 is connected with an inert gas pipeline through a gas valve and a pipeline; an exhaust port at the upper part of the deposition reaction fluidized bed 3 is connected with an air inlet at the upper part of the cyclone separation device 4 through a pipeline; the discharge outlet at the lower part of the deposition reaction fluidized bed 3 is connected with the powder collecting device 10 through a material valve and a pipeline; a feed inlet at the lower part of the deposition reaction fluidized bed 3 is connected with a discharge outlet at the lower part of the cyclone separation device 4 and a discharge outlet of the fine powder collection device 6 through pipelines; the base material 11 is suspended in the deposition reaction fluidized bed 3;
an exhaust port at the upper part of the cyclone separation device 4 is connected with a feed inlet of the high-temperature dust removal device 5 through a pipeline; the discharge port of the high-temperature dust removal device 5 is connected with the feed port of the fine powder collection device 6 through a pipeline; the exhaust port of the high-temperature dust removal device 5 is connected with the air inlet of the water cooling device 7 through a pipeline; the discharge opening of the water cooling device 7 and the TiCl4The feed inlets of the recovery device 8 are connected through a pipeline; and the exhaust port of the water cooling device 7 is connected with the air inlet of the tail gas treatment device 9 through a pipeline.
The method for producing the Ti powder and the Ti coating based on the system comprises the following steps:
titanium powder seeds are cleaned by inert gas in the powder feeding device 1, and conveyed into the deposition reaction fluidized bed 3 after air impurities of physical or chemical adsorption are removed; passing hydrogen and an inert gas through the TiCl4An evaporation device 2 removes TiCl4Loading into the deposition reaction fluidized bed 3; inert gas enters the deposition reaction flow through a gas valve and a pipelineThe fluidized bed 3 makes the titanium powder seeds in a fluidized state, and a metallic titanium coating or synthesized powder is deposited on the base material 11 and attached to the titanium seed powder to form new powder or form new fine titanium powder by self-nucleation;
the powder synthesized in the deposition reaction fluidized bed 3 is collected in the powder collecting device 10 through a material valve and a pipeline; part of the synthetic powder enters the cyclone separation device 4 through an exhaust port at the upper part of the deposition reaction fluidized bed 3 along with tail gas, and returns to the deposition reaction fluidized bed 3 through a pipeline for further deposition after gas-solid separation; the tail gas further recovers fine powder in the tail gas through the high-temperature dust removal device 5, and the fine powder returns to the deposition reaction fluidized bed 3 through the fine powder collection device 6 to continue growing; the tail gas after dust removal enters the water cooling device 7, and residual TiCl in the tail gas4After being cooled by circulating water, the TiCl becomes liquid4Into the TiCl4A recovery device 8 realizes TiCl4And the tail gas enters the tail gas treatment device 9 to treat the tail gas such as HCl and the like.
Preferably, the titanium powder particle size of the titanium seed powder in the powder feeding device 1 is 30 to 500 μm.
Preferably, the TiCl4The temperature of the evaporation device 2 is 25-100 ℃, H2With evaporated TiCl4Is greater than 0.5.
Preferably, the temperature of the deposition reaction fluidized bed 3 is 950 ℃ to 1200 ℃, and the average powder residence time is 30min to 180 min.
Compared with the prior art, the invention has the following advantages: (1) the raw material cost is low, and TiCl with low raw material cost is adopted in the process4Is a titanium source and can realize TiCl4The recovery and reuse of the raw materials improve the utilization rate of the raw materials; (2) no other metal by-products are generated, and because no other metals such as Na/Mg and the like are added in the process, no by-products are generated in the process of preparing the powder, so that the impurity content in the powder is obviously reduced; (3) the process flow is simple, and the efficiency is high: the process adopts a fluidized bed with high heat transfer and mass transfer as a reactor and introduces a method of titanium seed powder, so that the powder obtaining rate is obviously improved; (4) can be used in complex shapesDepositing a titanium coating with good binding force on the substrate; (5) the continuous mass production of the Ti powder and the Ti coating can be realized, so that the prices of the Ti powder and the Ti coating can be greatly reduced, and the application range of the Ti powder and the Ti coating is expanded.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a schematic view of the configuration of a system for producing Ti powder and Ti coating according to the present invention;
FIG. 2 is an SEM micrograph of the Ti coating prepared in example 3;
FIG. 3 is an SEM micrograph of the surface of the coarse Ti powder prepared in example 4;
FIG. 4 is an SEM micrograph of the Ti coating prepared in example 5.
Reference numerals:
1. a powder feeding device; 2. TiCl (titanium dioxide)4An evaporation device; 2-1, a heating device; 3. depositing a reaction fluidized bed; 4. a cyclonic separating apparatus; 5. a high temperature dust removal device; 6. a fine powder collection device; 7. a water cooling device; 8. TiCl (titanium dioxide)4A recovery device; 9. a tail gas treatment device; 10. a powder collecting device; 11. a base material.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
The invention is described in further detail below with reference to the figures and the detailed description.
Example 1
Referring to FIG. 1, the system for producing Ti powder and Ti coating used in this example comprises a powder feeder 1 and TiCl4 An evaporation device 2, a heating device 2-1, a deposition reaction fluidized bed 3, a cyclone separation device 4 and a high-pressure separatorA warm dust removal device 5, a fine powder collection device 6, a water cooling device 7 and TiCl4 A recovery device 8, a tail gas treatment device 9, a powder collecting device 10 and a base material 11;
the gas inlet at the bottom of the powder feeding device 1 is connected with an inert gas pipeline through a gas valve and a pipeline; a discharge port at the bottom of the powder feeding device 1 is connected with a feed port at the bottom of the deposition reaction fluidized bed 3 through a material valve and a pipeline;
the TiCl4The evaporation device 2 is provided with the heating device 2-1; the TiCl4The air inlet of the evaporation device 2 is connected with an inert gas pipeline and a hydrogen pipeline through an air valve and a pipeline; the TiCl4The exhaust port of the evaporation device 2 is connected with the air inlet at the lower part of the deposition reaction fluidized bed 3 through a pipeline;
the gas inlet at the bottom of the deposition reaction fluidized bed 3 is connected with an inert gas pipeline through a gas valve and a pipeline; an exhaust port at the upper part of the deposition reaction fluidized bed 3 is connected with an air inlet at the upper part of the cyclone separation device 4 through a pipeline; the discharge outlet at the lower part of the deposition reaction fluidized bed 3 is connected with the powder collecting device 10 through a material valve and a pipeline; a feed inlet at the lower part of the deposition reaction fluidized bed 3 is connected with a discharge outlet at the lower part of the cyclone separation device 4 and a discharge outlet of the fine powder collection device 6 through pipelines; the base material 11 is suspended in the deposition reaction fluidized bed 3;
an exhaust port at the upper part of the cyclone separation device 4 is connected with a feed inlet of the high-temperature dust removal device 5 through a pipeline; the discharge port of the high-temperature dust removal device 5 is connected with the feed port of the fine powder collection device 6 through a pipeline; the exhaust port of the high-temperature dust removal device 5 is connected with the air inlet of the water cooling device 7 through a pipeline; the discharge opening of the water cooling device 7 and the TiCl4The feed inlets of the recovery device 8 are connected through a pipeline; and the exhaust port of the water cooling device 7 is connected with the air inlet of the tail gas treatment device 9 through a pipeline.
Example 2
The method for producing the Ti powder and the Ti coating by using the system in the embodiment 1 specifically comprises the following steps: titanium powder seeds are in the powder feeding deviceAfter being cleaned by inert gas in the device 1, the air impurities which are physically or chemically adsorbed are removed and then are conveyed into the deposition reaction fluidized bed 3; passing hydrogen and an inert gas through the TiCl4 An evaporation device 2 removes TiCl4Loading into the deposition reaction fluidized bed 3; inert gas enters the deposition reaction fluidized bed 3 through a gas valve and a pipeline to enable titanium powder seeds to be in a fluidized state, a metal titanium coating or synthetic powder is deposited on the base material 11, and the synthetic powder is attached to the titanium seed powder to form new powder or form new fine titanium powder by self-nucleation;
the powder synthesized in the deposition reaction fluidized bed 3 is collected in the powder collecting device 10 through a material valve and a pipeline; part of the synthetic powder enters the cyclone separation device 4 through an exhaust port at the upper part of the deposition reaction fluidized bed 3 along with tail gas, and returns to the deposition reaction fluidized bed 3 through a pipeline for further deposition after gas-solid separation; the tail gas further recovers fine powder in the tail gas through the high-temperature dust removal device 5, and the fine powder returns to the deposition reaction fluidized bed 3 through the fine powder collection device 6 to continue growing; the tail gas after dust removal enters the water cooling device 7, and residual TiCl in the tail gas4After being cooled by circulating water, the TiCl becomes liquid4Into the TiCl4 A recovery device 8 realizes TiCl4And the tail gas enters the tail gas treatment device 9 to treat the tail gas such as HCl and the like.
Example 3
In this example, the particle size of the titanium powder was 100 μm based on example 2, and the TiCl powder was formed by sintering4The temperature of the evaporator 2 was 30 ℃ and H2With evaporated TiCl4The molar ratio of (3) is equal to 0.6, the temperature of the deposition reaction fluidized bed 3 is 1000 ℃, the average residence time of powder is 30min, and the base material is SiO2. FIG. 2 is an SEM microscopic morphology of the prepared Ti coating, and it can be seen that the surface is smooth and flat, and the average grain size is about 100 nm.
Example 4
This example is based on the above example 2, the titanium powder particle size is 30 μm, the TiCl4The temperature of the evaporation device 2 is 65 c,H2with evaporated TiCl4The molar ratio of (3) is equal to 1, the temperature of the deposition reaction fluidized bed 3 is 1050 ℃, and the average powder residence time is 80 min. FIG. 3 is an SEM microscopic morphology of the surface of the prepared coarse Ti powder, and it can be seen that many small titanium particles with a particle size of about 400nm are formed on the surface of the powder.
Example 5
In this example, the particle size of the titanium powder was 420 μm based on example 2, and the TiCl powder was formed by TiCl4The temperature of the evaporator 2 is 90 ℃ and H2With evaporated TiCl4The molar ratio of (3) is equal to 4, the temperature of the deposition reaction fluidized bed 3 is 980 ℃, the average powder residence time is 160min, and the matrix material is Al2O3. FIG. 4 is an SEM microscopic morphology of the prepared Ti coating, and it can be seen that the surface is smooth and flat, and the average grain size is about 80 nm.
The invention has not been described in detail and is within the skill of the art.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (5)

1. A system for producing Ti powder or Ti coating by a fluidized bed is characterized by comprising a powder feeding device (1) and TiCl4An evaporation device (2), a heating device (2-1), a deposition reaction fluidized bed (3), a cyclone separation device (4), a high-temperature dust removal device (5), a fine powder collection device (6), a water cooling device (7), TiCl4A recovery device (8), a tail gas treatment device (9), a powder collecting device (10) and a base material (11);
the gas inlet at the bottom of the powder feeding device (1) is connected with an inert gas pipeline through a gas valve and a pipeline; a discharge port at the bottom of the powder feeding device (1) is connected with a feed port at the bottom of the deposition reaction fluidized bed (3) through a material valve and a pipeline;
the TiCl4The evaporation device (2) is provided with the heating device (2-1); the TiCl4The air inlet of the evaporation device (2) is connected with the inert gas pipeline and the hydrogen pipeline through the air valve and the pipeline; the TiCl4The exhaust port of the evaporation device (2) is connected with the air inlet at the lower part of the deposition reaction fluidized bed (3) through a pipeline;
the gas inlet at the bottom of the deposition reaction fluidized bed (3) is connected with an inert gas pipeline through a gas valve and a pipeline; an exhaust port at the upper part of the deposition reaction fluidized bed (3) is connected with an air inlet at the upper part of the cyclone separation device (4) through a pipeline; a discharge port at the lower part of the deposition reaction fluidized bed (3) is connected with the powder collecting device (10) through a material valve and a pipeline; a feed inlet at the lower part of the deposition reaction fluidized bed (3) is connected with a discharge outlet at the lower part of the cyclone separation device (4) and a discharge outlet of the fine powder collection device (6) through pipelines; the base material (11) is suspended in the deposition reaction fluidized bed (3);
an exhaust port at the upper part of the cyclone separation device (4) is connected with a feed inlet of the high-temperature dust removal device (5) through a pipeline; the discharge outlet of the high-temperature dust removal device (5) is connected with the feed inlet of the fine powder collection device (6) through a pipeline; an exhaust port of the high-temperature dust removal device (5) is connected with an air inlet of the water cooling device (7) through a pipeline; the discharge opening of the water cooling device (7) is connected with the TiCl4The feed inlets of the recovery device (8) are connected through a pipeline; and the exhaust port of the water cooling device (7) is connected with the air inlet of the tail gas treatment device (9) through a pipeline.
2. A method for producing Ti powder or Ti coating based on the system of claim 1, the method comprising the steps of:
titanium seed powder is cleaned by inert gas in the powder feeding device (1), and is conveyed into the deposition reaction fluidized bed (3) after air impurities of physical or chemical adsorption are removed; passing hydrogen and an inert gas through the TiCl4The evaporation device (2) is used for removing TiCl4Loading into the deposition reaction fluidized bed (3); inert gas throughThe gas valve and the pipeline enter the deposition reaction fluidized bed (3) to enable the titanium powder seeds to be in a fluidized state, powder is synthesized or a metal titanium coating is deposited on the base material (11), and the synthesized powder is attached to the titanium seed powder to form new powder or form new fine titanium powder by self-nucleation;
the powder synthesized in the deposition reaction fluidized bed (3) is collected in the powder collecting device (10) through a material valve and a pipeline; part of the synthetic powder enters the cyclone separation device (4) through an exhaust port at the upper part of the deposition reaction fluidized bed (3) along with tail gas, and returns to the deposition reaction fluidized bed (3) through a pipeline for further deposition after gas-solid separation; fine powder in the tail gas is further recovered by the high-temperature dust removal device (5), and the fine powder is returned to the deposition reaction fluidized bed (3) for continuous growth by the fine powder collection device (6); the tail gas after dust removal enters the water cooling device (7), and residual TiCl in the tail gas4After being cooled by circulating water, the TiCl becomes liquid4Into the TiCl4A recovery device (8) for realizing TiCl4Recycling and reusing, and treating the tail gas in the tail gas treatment device (9).
3. The method for producing Ti powder or Ti coating according to claim 1, wherein the titanium seed powder in the powder feeding device (1) is titanium powder, and the particle size of the titanium powder is 30 μm to 500 μm.
4. The method of claim 2 for producing Ti powder or Ti coating based on the system of claim 1 wherein the TiCl is4The temperature of the evaporation device (2) ranges from 25 ℃ to 100 ℃, and H2With evaporated TiCl4The molar ratio is greater than 0.5.
5. The method for producing Ti powder or Ti coating according to claim 2, wherein the temperature of the deposition reaction fluidized bed (3) is 950 ℃ to 1200 ℃ and the average powder residence time is 30min to 180 min.
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