An aluminium trichloride generator

Abstract

The present application relates to a kind of aluminium trichloride generator, comprising: tank body, tank body has metal shell, heat preservation layer and refractory layer are sequentially laid in metal shell;Raw material access hole, raw material access hole is arranged at the side of tank body lower side;Setting at the upper side of tank body one side place of discharge port, setting at the top of tank body aluminium particle feeding port, aluminium particle feeding port is formed by elastic heat-resistant material;Thermocouple temperature measuring component is arranged at one side or both sides of the middle position of aluminium trichloride generator vertical direction;Bottom tray assembly is arranged in the lower part of the tank body of aluminium trichloride generator, and bottom tray assembly includes gas distribution disc, and there are small holes on distribution disc;Ceramic microbead is distributed on the gas distribution disc of bottom tray assembly, and the diameter of ceramic microbead is greater than the diameter of small hole on distribution disc.

Description

Technical Field

[0001] This invention relates to the chemical industry and manufacturing processes. Specifically, it relates to an apparatus for producing raw material gases, a gas transport and manufacturing apparatus combining the characteristics of both solid-bed and fluidized-bed systems. More specifically, it relates to an aluminum trichloride generator with an improved structure and configuration. Background Technology

[0002] In the chlorination process, purified titanium tetrachloride undergoes a gas-phase oxidation reaction with oxygen at high temperatures to produce titanium dioxide particles. The resulting titanium dioxide particles have anatase and rutile crystal structures. At low temperatures, the primary titanium dioxide particles are predominantly anatase. To increase the rutile content, further heating is required, but the crystal transformation time is also relatively long. To reduce the conversion energy for rutile titanium dioxide formation, an appropriate amount of aluminum trichloride is added to the titanium tetrachloride gas, thus achieving a rutile content of over 99.9% in the produced titanium dioxide. The titanium tetrachloride gas-phase oxidation reactor is a pipeline reactor, and the trace aluminum trichloride content in the titanium tetrachloride must be uniform; therefore, the amount of aluminum trichloride produced must be stable and controllable.

[0003] There are generally two ways to add aluminum chloride to titanium tetrachloride gas. One is to add pre-made aluminum trichloride (e.g., purchased externally); the other is to react metallic aluminum with chlorine gas and then add it directly to the titanium tetrachloride gas.

[0004] While using pre-prepared aluminum trichloride eliminates the need for expensive on-site preparation equipment—aluminum trichloride can be directly added to the gaseous phase of titanium tetrachloride—this process requires first dissolving aluminum trichloride in liquid titanium tetrachloride, then heating the titanium tetrachloride before mixing it into the aluminum trichloride, a time-consuming process. Furthermore, pre-prepared aluminum trichloride suffers from purity issues; impurities can affect dye quality, and there are also problems such as hydrolysis of aluminum trichloride during mixing and severe corrosion of equipment. These issues limit the applicability of this method.

[0005] In alternative solutions, aluminum trichloride can be generated by reacting pure aluminum with chlorine and then directly added to the gas phase of titanium tetrachloride. Production experience tells us that the aluminum trichloride generated in this way has better activity than pre-made aluminum trichloride, which can improve product quality and save production steps, eliminating the need for waiting and pre-making aluminum trichloride.

[0006] In the manufacturing process of aluminum trichloride, a fluidized bed reactor can be used. Inert materials such as alumina, zirconium oxide, and quartz sand form a reaction bed. A mixture of chlorine and titanium tetrachloride enters from the bottom of the reactor, passing through the inert sand to create a boiling state. Because of the use of inert materials, the fluidized bed reactor avoids the localized sintering problem caused by the violent exothermic reaction of aluminum particles. Simultaneously, the added titanium tetrachloride dilutes the concentration of chlorine, allowing the reaction to proceed smoothly. A disadvantage is that if the particles are too fine, they may be carried into the oxidation furnace.

[0007] Fixed-bed reactors use chlorine nozzles installed at the bottom to distribute the feedstock onto a distribution plate. However, this method suffers from severe equipment corrosion, and nozzle blockage can cause localized overheating.

[0008] For example, patent publication CN103896319A discloses an aluminum trichloride generator and a method for preparing aluminum trichloride. The aluminum trichloride generator includes: a body having a reaction chamber; a first inlet for injecting aluminum powder into the reaction chamber along its axial direction on the upper surface of the body; a second inlet on the circumferential surface of the body; and an outlet at the bottom of the body. Each of the first inlet, the second inlet, and the outlet is connected to the reaction chamber. At least one of the first inlet and the second inlet is used to inject chlorine gas into the reaction chamber along its axial and radial directions.

[0009] However, the use of aluminum powder causes reactants to scatter randomly, resulting in uneven airflow and nozzle clogging. The related technology still has shortcomings.

[0010] Meanwhile, existing methods and equipment still fail to achieve controllability, continuity, and convenience in the reaction of aluminum and chlorine under specific conditions. They also fail to overcome the shortcomings of the aforementioned equipment. Summary of the Invention

[0011] The first aspect of the present invention provides an aluminum trichloride generator that solves one or more of the above-mentioned technical problems.

[0012] According to a first aspect of the present invention, an aluminum trichloride generator is provided, the aluminum trichloride generator comprising:

[0013] The tank body has a metal outer shell, and an insulation layer and a fire-resistant layer are sequentially laid inside the metal outer shell;

[0014] Raw material inlet hole, which is located on one side below the main body of the tank;

[0015] The discharge port is located on the upper side of the main body of the tank.

[0016] An aluminum granule inlet is provided at the top of the main body of the tank, and the aluminum granule inlet is formed of an elastic heat-resistant material;

[0017] Thermocouple temperature measuring components are installed on one or both sides of the middle position in the vertical direction of the aluminum chloride generator.

[0018] A bottom tray assembly is provided at the lower part of the main body of the aluminum trichloride generator tank. The bottom tray assembly includes a gas distribution plate with small holes.

[0019] Ceramic microspheres are distributed on the gas distribution disk of the bottom tray assembly, and the diameter of the ceramic microspheres is larger than the diameter of the holes on the distribution disk.

[0020] In an optional embodiment, the aluminum granule feed inlet includes an outer edge of the feed inlet, a feed inlet contraction section extending vertically along the aluminum trichloride generator, and a feed inlet expansion section that connects to the feed inlet contraction section and gradually expands in diameter, wherein...

[0021] The ratio (H1:H2) of the widest diameter H1 at the top of the feed inlet constriction section to the narrowest width H2 at the feed inlet constriction section is 10:(8-9.5).

[0022] In a further preferred embodiment, the aluminum granule inlet is made of a heat-resistant rubber material, preferably, the aluminum granule inlet is made of hydrogenated nitrile butadiene rubber (HNBR).

[0023] In a further preferred embodiment, the aluminum trichloride generator also includes aluminum granules.

[0024] The diameter D of the aluminum particles and the diameter H2 of the narrowest part of the feed port expansion section 203 of the aluminum particle feed port 2 are D:H2=1:(0.90-0.95), and the diameter of the aluminum particles is preferably 13 mm to 16 mm.

[0025] In an optional embodiment, the ceramic microspheres are alumina microspheres or zirconia microspheres, wherein the diameter of the ceramic microspheres is 10 to 15 mm, and the number of layers of ceramic microspheres stacked in the lower part of the tank body of the aluminum trichloride generator is approximately 8 to 12 layers.

[0026] Furthermore, the aluminum trichloride generator provided in this application may also include one or more of the following components:

[0027] An observation window is located on one side of the upper part of the main body of the aluminum trichloride generator tank. An upper temperature measuring device is attached to the observation window to detect the temperature near the discharge port and the aluminum particle inlet.

[0028] A ceramic bead replenishment port extends in an inclined direction and is located on one side of the middle part of the main body of the tank to add or replenish the ceramic microbeads;

[0029] A pressure testing tube is installed on one side of the lower part of the main body of the tank;

[0030] The material discharge port is located at the bottom of the main body of the tank and extends vertically.

[0031] Furthermore, the aluminum trichloride generator also meets one or more of the following structural requirements:

[0032] The distance from the aluminum granule feed inlet extending into the aluminum trichloride generator is 60-80cm.

[0033] The apparent flow rate of the reaction gas in the aluminum trichloride reactor is set at 200-1000 mm / s;

[0034] The overall height of the reactor generator is 5 to 8 meters;

[0035] The distance between the thermocouple temperature measuring component at the middle position of the aluminum chloride generator and the top of the aluminum chloride generator is 3 to 4 meters;

[0036] The diameter of the holes on the distribution plate is 80%-90% of the diameter of the ball;

[0037] The total area of ​​the small holes in the distribution plate is greater than 50% of the cross-sectional area of ​​the raw material inlet hole.

[0038] In a second aspect of the invention, a method for producing titanium tetrachloride feedstock gas and aluminum trichloride using an aluminum trichloride generator is also provided, the method comprising the following steps:

[0039] A mixture of TiCl4 and Cl2 is transported at a molar mass ratio of 100:(2-5), wherein the total flow rate of the mixture is controlled to be an apparent gas velocity of 200-1000 mm / s;

[0040] The temperature in the middle of the reactor was measured and controlled between 410℃ and 420℃.

[0041] Aluminum granules are fed into the aluminum trichloride generator by controlling the narrowest point of the feed inlet contraction section through the feeding device at uniform intervals.

[0042] The gas discharged from the outlet after the reaction is completed is collected, and the molar ratio of titanium tetrachloride (TiCl4) to aluminum trichloride (AlCl3) is determined.

[0043] According to the method, optionally, an upper temperature measuring device is used to detect the temperature near the lower end of the discharge port and the aluminum particle feed port, so that the temperature is maintained at 170°C to 190°C.

[0044] The gas discharged from the outlet after the reaction is completed is collected, and the molar ratio of titanium tetrachloride (TiCl4) to aluminum trichloride (AlCl3) is determined to be between 100:(1.5-2.5).

[0045] Non-limitingly, according to the technical solution provided by the present invention, a certain thickness of non-metallic oxide microspheres are spread on the reaction plate. The diameter of the microspheres is large enough to prevent them from being blown away by the gas. There are sufficient gaps between the microspheres, which serve as channels for the rising reactive gas, similar to the chlorine nozzles in a fixed-bed reactor. The uniformly distributed microspheres also resemble the inert medium in a fluidized bed reactor. The non-metallic oxide microspheres here can be alumina beads, zirconium oxide beads, etc., which will not be blown away by the reactive gas. Therefore, the present invention possesses the dual characteristics of a fixed bed and a fluidized bed.

[0046] Furthermore, this invention optimizes the structure to address the reaction and transport characteristics between aluminum trichloride, chlorine, and titanium tetrachloride. Specifically, the tray microspheres, aluminum particles, and raw material inlet are optimized to ensure an effective, continuous, and stable reaction between the raw material gas (including chlorine) and elemental Al, facilitating continuous and damage-free operation of the equipment. These improvements will be further described in detail in the embodiments.

[0047] The technical solutions and advantages of the present invention will be explained and described in more detail below with reference to specific embodiments. It should be understood that the content presented in the specification and specific embodiments is only for the purpose of more clearly illustrating the technical solutions and advantages of the present invention, and does not constitute a limitation on the scope of protection of the present invention. Those skilled in the art can obtain modified technical solutions based on the disclosure in the specification through various reasonable modifications. As long as these modifications do not depart from the spirit of the present invention, all modified technical solutions should be understood to be included within the scope of protection of the present invention. Attached Figure Description

[0048] The accompanying drawings are provided to further understand the technical solutions of this disclosure and constitute a part of the specification. They are used together with the specific embodiments of this application to explain the technical solutions of this disclosure and do not constitute a limitation on the technical solutions of this disclosure.

[0049] Figure 1 This is a cross-sectional schematic diagram of a fixed-bed aluminum trichloride generator according to an embodiment of the present invention.

[0050] Figure 2 It shows Figure 1 The "A" part is a partial cross-sectional diagram of the aluminum granule feed inlet;

[0051] Figure 3 yes Figure 1 The "B" part is a schematic diagram of the stacking of ceramic microspheres;

[0052] Figure 4 This is a schematic diagram showing the relationship between the diameter of the ceramic microsphere stack and the average pore diameter it forms.

[0053] 1-Discharge port; 2-Aluminum granule inlet; 3-Insulation layer; 4-Pressure test hole; 5-Material discharge port; 6-Raw material inlet; 7-Ceramic bead replenishment port; 8-Observation window; 9-Metal shell; 10-Ceramic microspheres; 11-Refractory layer; 12-Dike tray assembly; 13-Thermocouple temperature measuring component; 201-Outer edge of inlet; 202-Inlet contraction section; 203-Inlet expansion section. Detailed Implementation

[0054] The invention is described in more detail below to aid in understanding it.

[0055] Before describing the specific implementation scheme, it should be noted that the sources of raw materials described in the specific embodiments of this specification are not limiting. Those skilled in the art can select appropriate raw materials and testing equipment to conduct relevant tests and obtain corresponding results based on the teachings and guidance of this invention. For raw materials for which specific manufacturers or methods are not specified, those skilled in the art can select raw materials that meet the corresponding requirements as reaction starting materials based on the disclosure and needs of this specification. The reaction raw materials for synthesizing some compounds are derived from the initial products synthesized in the preceding steps of this invention, which is also understandable based on the disclosure of this specification.

[0056] Example 1

[0057] This embodiment describes the structure and function of each component of the fixed-bed aluminum trichloride generator of the present invention.

[0058] refer to Figure 1 As shown, the aluminum trichloride generator has a metal outer shell 9, and an insulation layer 3 and a refractory layer 11 are laid inside the metal outer shell 9 in sequence, thus forming the main body of the aluminum trichloride generator tank.

[0059] A raw material inlet 6 is located diagonally below the main body of the tank (in this embodiment, it is shown as the lower right side of the main body). The raw material inlet 6 is located on one side below the main body and can be connected to a titanium tetrachloride preheater. A predetermined amount of chlorine gas (not shown) is simultaneously added to the inlet pipe. An aluminum granule inlet 2 is located at the top center of the main body. The structure of the aluminum granule inlet 2 will be described in detail later. After Al reacts with chlorine gas, the product is discharged through the outlet 1 of the main body (in this embodiment, it is located at the upper left side of the main body).

[0060] A pressure test port 4 is provided on the lower side of the aluminum trichloride generator (tank body). Thermocouple temperature measuring components 13 are provided on both sides of the middle position in the vertical direction of the aluminum trichloride generator. Ceramic bead replenishment ports 7 can also be provided on one or both sides of the middle position, extending in the inclined direction and located on one side of the middle of the tank body. The replenishment ports are equipped with shut-off valves for sealing. A bottom tray assembly 12 is provided at the lower part of the aluminum trichloride generator. The bottom tray assembly 12 includes a gas distribution plate with small holes (not shown in the figure) and a support at the bottom. In this embodiment, zirconia beads, which are ceramic microbeads 10, are distributed on the distribution plate. Alumina microbeads can also be selected according to the needs of use. In order to support the ceramic microbeads, the diameter of the microbeads is larger than the diameter of the small holes on the distribution plate.

[0061] In the device setup of this invention, the gravity of the ceramic microspheres 10 is greater than the upward force provided by the raw material gas (TiCl4 and Cl2) blown in through the raw material inlet hole 6, so that the ceramic microspheres 10 distributed on the bottom tray assembly 12 will not be blown away by the raw material gas blown in through the raw material inlet hole 6. Therefore, the aluminum trichloride generator of this embodiment can have the dual characteristics of a fixed bed and a fluidized bed. When the microspheres are not blown away, the large diameter of the microspheres (5-20 mm, preferably 8-15 mm, 15 mm in this embodiment) provides sufficient and uniformly distributed voids, similar to the inert medium of a fluidized bed. These voids serve as channels for the rising reaction gas, similar to the chlorine nozzle in a fixed bed reactor, which can effectively transport the gaseous raw materials without clogging the nozzle or introducing impurities into the reactants as easily as in a fluidized bed reactor.

[0062] This application will now describe the aluminum granule feed inlet 2 used in more detail. (See reference...) Figure 2 In this embodiment, the aluminum granule feed inlet 2 is barrel-shaped, comprising an outer edge 201 extending horizontally along the cross-sectional view of the aluminum trichloride generator, a feed inlet contraction section 202 (upper section) arranged vertically along the aluminum trichloride generator, and a feed inlet expansion section 203 (lower section, only partially shown) connecting to the feed inlet contraction section 202 and extending along the diameter expansion direction. The length ratio of the feed inlet contraction section 202 to the feed inlet expansion section 203 along the vertical direction of the aluminum trichloride generator is 1:1. The angle formed by the feed inlet contraction section 202 and the vertical direction is 10°.

[0063] Still referencing Figure 2 ( Figure 2 yes Figure 1(Enlarged cross-sectional view of part A) In this embodiment, the diameter (width) at the widest point of the upper part of the feed inlet contraction section 202 of the aluminum granule feed inlet 2 is H1, and the width at the narrowest point of the feed inlet contraction section 202 (i.e., the narrowest point of the feed inlet expansion section 203) is H2, H1:H2=10:9.

[0064] In this embodiment, the aluminum granule inlet 2 is made of heat-resistant rubber. This allows the rate at which aluminum granules are released into the aluminum trichloride generator (tank body) to be controlled by the slope set by H1 and H2 when aluminum granules are stacked at the aluminum granule inlet 2. In this embodiment, the heat-resistant rubber used for the aluminum granule inlet 2 is hydrogenated nitrile butadiene rubber (HNBR). Other similar heat-resistant rubber materials can also be used to manufacture the aluminum granule inlet 2 using existing molding and cutting processes. In this embodiment, the hydrogenated nitrile butadiene rubber, as the inlet portion, can withstand a certain high temperature at the outlet of the reactor, while also possessing a certain degree of elasticity and resilience, and resistance to permanent deformation.

[0065] In this application, the feeding speed of aluminum particles can be simply and effectively controlled by combining a simple screw feed conveyor mechanism (not shown) with an aluminum particle feed inlet 2 made of hydrogenated nitrile butadiene rubber (HNBR). A sealing device that is combined with or cooperates with the feed conveyor mechanism can be provided at the outer edge 201 of the feed inlet. The sealing measures for the aluminum particle feed inlet 2 can adopt existing sealing technologies for rubber cylinders or rubber sealing rings.

[0066] In the aluminum trichloride generator of this invention, only a small amount of aluminum trichloride is required to combine with a larger amount of titanium tetrachloride. Therefore, the aluminum particles do not need to be fed continuously and rapidly, but rather intermittently according to a certain pattern, or intermittently supplied according to experimental needs. Therefore, the aluminum particle inlet 2 of this embodiment can be easily and practically combined with a conventional conveying mechanism, allowing for simple and effective control of the falling frequency and speed of the aluminum particles.

[0067] In this embodiment, the diameter (D) of the aluminum granules (when the aluminum granules are not perfectly circular, it can refer to the dimension in the direction of the maximum width of the aluminum granules) and the diameter H2 of the narrowest point of the inlet expansion section 203 of the aluminum granule inlet 2 are used at a ratio of D:H2 = 1:0.95. With this diameter ratio, the aluminum granules can be controlled to fall uniformly at a rate of one (or several) granules at a time. In this embodiment, aluminum granules with a diameter of 15 mm are selected. Combined with the size and number of layers of ceramic microspheres in the equipment, this facilitates the reaction with the rising chlorine gas at the bottom in the middle section of the equipment, allowing aluminum trichloride to be supplied in a stable, minute quantity. This will be described in detail below. The technical solution using aluminum granules of a specific size is superior to the related technical solution of manufacturing aluminum trichloride using aluminum powder in terms of controllability, production cost, and stable gas flow rate.

[0068] According to the configuration of this embodiment, when a large number of aluminum particles (more than two or three) gather on the shrinking ramp formed by the feed inlet shrinkage section 202 and the feed inlet expansion section 203, the aluminum particles can be appropriately compressed by the feeding mechanism, which can cause the aluminum particle feed inlet 2 made of hydrogenated nitrile butadiene rubber (HNBR) to undergo slight deformation and expand, so that the aluminum particles can fall to the middle of the reactor individually or in a predetermined number.

[0069] Another feature of the technical solution according to the present invention is that it combines the characteristics of both a fluidized bed and a fixed bed reactor. Formally, the aluminum trichloride generator of this embodiment has a bottom tray assembly 12. However, this embodiment also has a certain thickness of non-metallic oxide microspheres (ceramic microspheres 10) spread on the bottom tray assembly 12. The diameter of the microspheres must be large enough to prevent them from falling into the holes on the tray assembly. In this embodiment, the diameter of the ceramic microspheres 10 is selected as 12 mm. The reactant gas permeates upwards from the holes (not shown) of the bottom tray assembly 12, passing through the layer of ceramic microspheres 10. Because there are sufficient gaps between the ceramic microspheres 10, and the microspheres do not completely block the holes of the tray and the gas escape channels, these gaps serve as channels for the rising reactant gas, acting similarly to the chlorine nozzles of a fixed bed reactor. The uniformly distributed microspheres also resemble the inert medium of a fluidized bed.

[0070] In an ideal situation, reference Figure 3 and Figure 4 It shows the layer of ceramic microbeads 10 and the gaps formed between multiple ceramic microbeads 10. Figure 3 The ceramic microspheres 10 are layered on the bottom tray assembly 12 (the small holes at the bottom are not shown for ease of illustration), which constitutes... Figure 4 The gap shown. In Figure 4 In the figure, virtual small circles (virtual radius r) that are tangent to three closely adjacent ceramic microspheres 10 (radius R) constitute the gaps between the three closely adjacent ceramic microspheres 10. r is called the "average pore radius" (virtual small circle in the figure) formed when the three microspheres of this layer are arranged tangentially to each other on a plane. Due to the irregular shape of the tray assembly 12 and the presence of pores at the bottom of the tray during actual stacking, the average pore radius r between the actually stacked single-layer ceramic microspheres 10 is approximately 0.14R to 0.16R. In this embodiment, r is approximately 0.154R to 0.156R. In this embodiment of the invention, r is 2.20 mm to 2.50 mm, preferably 2.31 mm to 2.35 mm. The number of ceramic microspheres 10 stacked is approximately 9 to 10 layers.

[0071] The inventors discovered that when the diameter of the ceramic microspheres 10 is controlled between 8-20 mm, preferably between 10-15 mm, and the number of stacked layers is 8-12, the fluid form of the gas flow injected into the generator is similar to that of a gas flow formed by a gas nozzle, without the drawback of nozzle clogging. When the number of ceramic microspheres 10 layers is too large, the upward thrust of the raw gas through the ceramic microspheres is insufficient. When the number of layers is too small or the diameter of a single layer of ceramic microspheres 10 is too large, an effective chlorine-containing raw material injection cannot be formed.

[0072] In this embodiment of the invention, the thermocouple temperature measuring component 13 mainly detects the temperature of the reaction between aluminum particles and chlorine gas. To ensure the effective reaction of the two, the temperature in the middle of the equipment is preferably set between 400°C and 410°C. Simultaneously, considering the special heat-resistant rubber material at the bottom of the top aluminum particle inlet 2, the distance between the thermocouple temperature measuring component 13 and the bottom of the aluminum particle inlet 2, as well as the distance between the thermocouple temperature measuring component 13 and the top of the aluminum trichloride generator, should be controlled. In this invention, the distance between the thermocouple temperature measuring component 13 at the middle position of the aluminum trichloride generator and the top of the aluminum trichloride generator is set to 3-4 meters. This facilitates the uniform reaction of falling aluminum particles of a specific size with rising chlorine gas and also protects the durability of the special heat-resistant rubber material at the bottom of the aluminum particle inlet 2. Advantageously, an upper temperature measuring device is added at the observation window 8 to monitor the temperature near the bottom of the outlet 1 and the aluminum particle inlet 2. In this embodiment, the aforementioned distance setting allows the temperature at the lower end of the aluminum granule inlet 2 to be controlled below 200°C, preferably below 180°C, to ensure the durability of the hydrogenated nitrile butadiene rubber (HNBR). Simultaneously, in this embodiment, the distance by which the aluminum granule inlet 2 extends into the aluminum trichloride generator is 60-80 cm.

[0073] Example 2

[0074] This embodiment briefly describes the process of preparing titanium tetrachloride containing a small amount of aluminum trichloride using the equipment of Example 1.

[0075] In this embodiment, a mixture of TiCl4 and Cl2 gas is supplied at a molar mass ratio of 100:3, and the total flow rate is controlled to an apparent gas velocity of 500 mm / s. The temperature measured by the thermocouple temperature measuring component 13 is controlled at 410°C. Al particles are fed into the aluminum trichloride generator by the feeding device, which compresses the narrowest part of the feed port contraction section 202 of the aluminum particle feed port 2 at a rate of one particle every 2 seconds. At this time, the temperature detected by the upper temperature measuring device is 180°C. After the reaction stabilizes, the molar ratio of titanium tetrachloride (TiCl4) to aluminum trichloride (AlCl3) obtained at the discharge port 1 is detected to be 100:1.9.

[0076] Under ideal high-temperature oxidation conditions for titanium tetrachloride, the molar content of aluminum trichloride required in the oxidation stage is approximately 2% of the total molar amount of titanium tetrachloride (TiCl4) and aluminum trichloride (AlCl3). Therefore, using the aluminum trichloride generator of Example 1 in Example 2, the raw material gas can be produced smoothly, continuously, and stably at a near-ideal content at a lower cost, allowing the raw material gas to be easily transported to the next stage (e.g., the rutile phase preparation stage).

[0077] Comparative Example 1

[0078] In Comparative Example 1, while keeping other equipment structures and experimental parameters unchanged from Examples 1 and 2, the number of stacked layers of ceramic microspheres 10 was varied. The test results are shown in Table 1.

[0079] Table 1

[0080]

[0081] As can be seen from Table 1, in the embodiments of the present invention, a three-layer aluminum chloride generator containing 9 to 10 microbead layers is preferred, so that the reaction of chlorine gas with Al, which is specific to aluminum trichloride, is continuous, uniform, and controllable.

[0082] Comparative Example 2

[0083] In Comparative Example 1, the other equipment structures and experimental parameters in Examples 1 and 2 were kept unchanged, but the size of the ceramic microspheres 10 was changed.

[0084]

[0085] Here, the applicant does not wish to be constrained by any theory. However, when the size of the ceramic microspheres 10 is determined to be around 15mm, a stacking size of 9-10 layers makes the stacking gaps between the ceramic microspheres most similar to the gas flow achieved by a gas nozzle. Thus, it achieves an effect similar to a gas nozzle in a fixed bed while effectively avoiding the problem of nozzle clogging. At the same time, the gas flow rate and lift set in this invention will not blow the ceramic microspheres 10 upwards, but the properties of the inert microspheres are similar to the structure and mechanism of a fluidized bed.

[0086] Comparative Example 3

[0087] In Comparative Example 1, the other equipment structures and experimental parameters in Examples 1 and 2 were kept unchanged, but the size of the aluminum particles was changed.

[0088]

[0089]

[0090] As can be seen from the above comparative examples, when the diameter of the aluminum particles in this invention is too small, the aluminum particles are blown away by the rising gas and cannot reach the optimal central region of the reactor. When the aluminum particles are blown away to the upper part of the reactor, the reaction temperature is insufficient, and the reaction between the Al particles and chlorine cannot be fully realized. In the embodiments of this invention, the diameter of the Al particles is preferably 13-16 mm.

[0091] Comparative Example 4

[0092] In Comparative Example 1, the other equipment structures and experimental parameters in Examples 1 and 2 were kept unchanged, but the diameter of the aluminum particle inlet 2 was changed.

[0093]

[0094] Furthermore, in this embodiment of the invention, considering the deformability of hydrogenated nitrile butadiene rubber (HNBR), the diameter (width) at the widest point of the upper part of the feed inlet contraction section 202 of the aluminum granule feed inlet 2 is H1, and the width at the narrowest point of the feed inlet contraction section 202 (i.e., the narrowest point of the feed inlet expansion section 203) is H2, with H1:H2 = 10:(8-9.5), preferably 10:9. The inclination angle of the sidewall of the aluminum granule feed inlet 2 is preferably 5-10 degrees relative to the vertical direction.

[0095] Based on the embodiments and technical content described in this specification, the present invention can provide at least the following technical solutions: Although this disclosure includes specific embodiments, it will be apparent to those skilled in the art that various substitutions or changes in form and detail can be made to these embodiments without departing from the inventive spirit and scope of the claims and their equivalents. The embodiments described herein should be considered illustrative only and not for limiting purposes. The description of features and aspects in each embodiment is considered applicable to similar features and aspects in other embodiments. Therefore, the scope of this disclosure should not be limited by the specific description, but rather by the technical solutions of the claims, and all variations within the scope of the claims and their equivalents are to be interpreted as included within the technical solutions of this disclosure.

Claims

1. An aluminum trichloride generator, the aluminum trichloride generator comprising: The tank body has a metal outer shell, and an insulation layer and a fire-resistant layer are sequentially laid inside the metal outer shell; Raw material inlet hole, which is located on one side below the main body of the tank; The discharge port is located on the upper side of the main body of the tank. An aluminum granule inlet is located at the top of the main body of the tank; Thermocouple temperature measuring components are installed on one or both sides of the middle position in the vertical direction of the aluminum chloride generator. A bottom tray assembly is provided at the lower part of the main body of the aluminum trichloride generator tank. The bottom tray assembly includes a gas distribution plate with small holes. And ceramic microspheres distributed on the gas distribution disk of the bottom tray assembly, the diameter of the ceramic microspheres being larger than the diameter of the orifices on the distribution disk, and the ceramic microspheres being configured such that the weight of the ceramic microspheres is greater than the upward force provided by the raw material gas blown in through the raw material inlet orifice, and The aluminum granule feed inlet includes an outer edge of the feed inlet, a feed inlet contraction section extending vertically along the aluminum trichloride generator, and a feed inlet expansion section that connects to the feed inlet contraction section and gradually expands in diameter. The ratio H1:H2 of the widest diameter H1 at the upper part of the feed inlet constriction section of the aluminum granule feed inlet to the narrowest width H2 at the feed inlet constriction section is 10:(8-9.5). The aluminum granule feed inlet is made of heat-resistant rubber material; The aluminum trichloride generator also includes aluminum granules. The ratio of the diameter D of the aluminum particle to the diameter H2 of the narrowest part of the expansion section of the aluminum particle feed inlet is D:H2=1:(0.90-0.95), and the diameter of the aluminum particle is 13 mm to 15 mm.

2. The aluminum trichloride generator according to claim 1, wherein... The ceramic microspheres are alumina microspheres or zirconium oxide microspheres, wherein the diameter of the ceramic microspheres is 10 to 15 mm, and the number of layers of ceramic microspheres stacked in the lower part of the tank body of the aluminum trichloride generator is 8 to 12.

3. The aluminum trichloride generator according to claim 1, The aluminum trichloride generator further includes one or more of the following components: An observation window is located on one side of the upper part of the main body of the aluminum trichloride generator tank. An upper temperature measuring device is attached to the observation window to detect the temperature near the discharge port and the aluminum particle inlet. A ceramic bead replenishment port extends in an inclined direction and is located on one side of the middle part of the main body of the tank to add or replenish the ceramic microbeads; A pressure testing tube is installed on one side of the lower part of the main body of the tank; The material discharge port is located at the bottom of the main body of the tank and extends vertically.

4. The aluminum trichloride generator according to claim 1, The aluminum trichloride generator described therein also meets one or more of the following structural requirements: The distance from the aluminum granule feed inlet extending into the aluminum trichloride generator is 60-80cm. The apparent flow rate of the reaction gas in the aluminum trichloride generator is set at 200-1000 mm / s; The overall height of the generator is 5 to 8 meters; The distance between the thermocouple temperature measuring component at the middle position of the aluminum chloride generator and the top of the aluminum chloride generator is 3 to 4 meters; The diameter of the small holes on the distribution disk is 80%-90% of the diameter of the ceramic microspheres; The total area of ​​the small holes in the distribution plate is greater than 50% of the cross-sectional area of ​​the raw material inlet hole.

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