Method for removing organic impurities from refined titanium tetrachloride

Abstract

The present application belongs to the field of mixed metallurgy, and discloses a method for removing organic impurities in refined titanium tetrachloride, comprising the following steps: opening a titanium tetrachloride valve, and introducing refined titanium tetrachloride after vanadium removal into a mixing tank; opening a reagent valve, and introducing a reagent into the mixing tank, wherein the reagent comprises at least one of the following: alkali metal chlorides and their hydrated chlorides, alkaline earth metal chlorides and their hydrated chlorides, aluminum trichloride and its hydrated chloride, and iron trichloride and its hydrated chloride; opening a stirrer in the mixing tank to stir, so that the reagent and the refined titanium tetrachloride are fully mixed and reacted; and introducing the reaction liquid into a distillation device, and obtaining refined titanium tetrachloride with an organic impurity content of <0.0001% through distillation. The method of the present application has a high removal rate of organic impurities in refined titanium tetrachloride, reaching 99.99%, and the process of the present application is simple, the equipment investment is small, and the energy consumption is low.

Description

A method for removing organic impurities from purified titanium tetrachloride Technical Field

[0001] This invention relates to a process for refining vanadium-removing slurry from organic matter, belonging to the field of mixed metallurgy, and more specifically, to a method for removing organic impurities from refined titanium tetrachloride. Background Technology

[0002] The main impurities in industrial titanium tetrachloride include SiCl4, AlCl3, FeCl3, and VOCl3. Based on the difference in boiling point between these impurities and TiCl4, they are classified into high-boiling-point impurities, low-boiling-point impurities, and impurities with similar boiling points. All these impurities are detrimental to TiCl4 and affect the performance of titanium tetrachloride.

[0003] The Chinese patent database contains numerous patent applications related to the production and purification of titanium tetrachloride. Examples include: Chinese Patent No. 200910220312.2, entitled "Method for Recovering and Purifying Titanium Tetrachloride for Preparing Olefin Polymerization Catalysts"; Chinese Patent No. 201210572866.0, entitled "Titanium Tetrachloride Purification System and Method"; Chinese Patent No. 201210588402.9, entitled "A Process and System for Purifying and Removing Vanadium from Titanium Tetrachloride"; Chinese Patent No. 201410075517.7, entitled "Method for Removing Vanadium Impurities from Crude Titanium Tetrachloride and Method for Refining Crude Titanium Tetrachloride"; and Chinese Patent No. 201510053934.6, entitled "Method and System for Preparing Refined Titanium Tetrachloride," etc. These patents effectively remove impurities such as SiCl4, AlCl3, FeCl3, and VOCl3.

[0004] However, organic impurities such as acyl chlorides, carbon, oxygen, and sulfur, generated (or remaining) during the production or refining of titanium tetrachloride to remove vanadium, can enter sponge titanium products at four times their normal concentration, severely affecting the quality of sponge titanium. Although Chinese patent document No. 201810120467.8, entitled "A Method for Producing Ultra-High Purity Titanium Tetrachloride," provides a method for producing titanium tetrachloride with a purity of 99.99999%, this method removes low-boiling-point impurities through purely physical means (sub-boiling distillation and rectification) to produce semiconductor-grade refined titanium tetrachloride. This method suffers from low efficiency and high energy consumption, and cannot meet the actual production needs of sponge titanium.

[0005] Therefore, existing technologies need to be improved. Summary of the Invention

[0006] The purpose of this invention is to provide a method for removing organic impurities from purified titanium tetrachloride. The residual organic matter in purified titanium tetrachloride undergoes a complexation reaction with the provided reagent to form a precipitate, which is then precipitated from the purified titanium tetrachloride. The content of organic impurities in the purified titanium tetrachloride is <0.0001%.

[0007] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0008] According to one aspect of the present invention, a method for removing organic impurities from purified titanium tetrachloride is provided, comprising the following steps:

[0009] 1) Open the titanium tetrachloride valve and introduce the vanadium-removed refined titanium tetrachloride into the mixing tank;

[0010] 2) Open the reagent valve and introduce the reagent into the mixing tank. The reagent includes, but is not limited to: alkali metal chlorides and their hydrated chlorides, alkaline earth metal chlorides and their hydrated chlorides, aluminum trichloride and its hydrated chlorides, and ferric trichloride and its hydrated chlorides.

[0011] 3) Turn on the stirrer in the mixing tank to stir and make the reagent and purified titanium tetrachloride fully mix and react;

[0012] 4) The reacted liquid is introduced into a distillation apparatus, and purified titanium tetrachloride with an organic impurity content of <0.0001% is obtained by distillation.

[0013] In one embodiment of the present invention, the method further includes the step of:

[0014] 5) Drain and collect the distillate, and then return the collected distillate to the vanadium removal process.

[0015] In one embodiment of the present invention, in step 2), the reagent is introduced into the mixing tank at 0.01%-0.02% of the mass of titanium tetrachloride.

[0016] In one embodiment of the present invention, in step 3), the stirring time is 30-60 min.

[0017] In one embodiment of the present invention, in step 5), the solid content of the distillation base liquid is maintained at 100-150 g / L.

[0018] In one embodiment of the present invention, in step 5), the distillation bottom liquid is returned to the vanadium removal process by a pump.

[0019] In one embodiment of the present invention, in step 2), the hydrated chloride of the alkali metal includes lithium chloride monohydrate.

[0020] In one embodiment of the present invention, in step 2), the hydrated chloride of alkaline earth metals includes calcium chloride dihydrate.

[0021] In one embodiment of the present invention, in step 2), the hydrated chloride of aluminum trichloride includes aluminum trichloride hexahydrate, and the hydrated chloride of ferric chloride includes ferric chloride hexahydrate.

[0022] In one embodiment of the present invention, the organic impurity removal rate in purified titanium tetrachloride reaches 99.99%.

[0023] By adopting the above technical solution, the present invention has the following advantages compared with the prior art:

[0024] The method of the present invention achieves a high removal rate of organic impurities in purified titanium tetrachloride, reaching 99.99%. Furthermore, the process of the present invention is simple, requires little equipment investment, and has low energy consumption. Attached Figure Description

[0025] Figure 1 shows a schematic flowchart of a method for removing organic impurities from refined titanium tetrachloride provided by the present invention. Detailed Implementation

[0026] It should be understood that the embodiments of the invention shown in the exemplary embodiments are merely illustrative. Although only a few embodiments have been described in detail in this invention, those skilled in the art will readily recognize that various modifications are possible without substantially departing from the teachings of the invention. Accordingly, all such modifications should be included within the scope of the invention. Other substitutions, modifications, variations, and deletions can be made to the design, operating conditions, and parameters of the following exemplary embodiments without departing from the spirit of the invention.

[0027] As shown in Figure 1, the present invention provides a method for removing organic impurities from purified titanium tetrachloride, comprising the following steps:

[0028] S101: Open the titanium tetrachloride valve and introduce the vanadium-removed refined titanium tetrachloride into the mixing tank;

[0029] S102: Open the reagent valve and introduce the reagent into the mixing tank, wherein the reagent includes, but is not limited to: alkali metal chloride and its hydrated chloride, alkaline earth metal chloride and its hydrated chloride, aluminum trichloride and its hydrated chloride, and ferric trichloride and its hydrated chloride.

[0030] S103: Turn on the stirrer in the mixing tank to stir and make the reagent and purified titanium tetrachloride fully mix and react;

[0031] S104: The reacted liquid is introduced into a distillation apparatus, and purified titanium tetrachloride with an organic impurity content of <0.0001% is obtained by distillation.

[0032] Through the above-mentioned technical solution of the present invention, the present invention achieves a high organic matter removal rate of 99.99% in purified titanium tetrachloride, and the process of the present invention is simple, requires little equipment investment, and has low energy consumption.

[0033] The above method further includes the steps of: draining and collecting the distillate, and then returning the collected distillate to the vanadium removal process.

[0034] In the above method, in step S102, the reagent is introduced into the mixing tank at 0.01%-0.02% of the mass of titanium tetrachloride. The reagent can be, for example, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, aluminum trichloride, ferric chloride, lithium chloride, ferric chloride hexahydrate, aluminum trichloride hexahydrate, calcium chloride dihydrate, lithium chloride monohydrate, etc.

[0035] In the above method, the stirring time in S103 is 30-60 min.

[0036] In the above method, in S105, the solid content of the distillation bottom liquid is maintained at 100-150 g / L, and the distillation bottom liquid is returned to the vanadium removal process by a pump.

[0037] In the above method, in S102, the hydrated chloride of alkali metals includes lithium chloride monohydrate; the hydrated chloride of alkaline earth metals includes calcium chloride dihydrate; the hydrated chloride of aluminum trichloride includes aluminum trichloride hexahydrate; and the hydrated chloride of ferric chloride includes ferric trichloride hexahydrate.

[0038] In the above method, the removal rate of organic impurities in purified titanium tetrachloride reaches 99.99%.

[0039] The technical solutions of the present invention will be described in detail below through specific embodiments.

[0040] The technical solution adopted in this embodiment of the invention is as follows: the provided reagent is added to a mixing tank and fully mixed and reacted with the vanadium-removed refined titanium tetrachloride. Then, the reaction solution is introduced into a distillation device, and refined titanium tetrachloride with low organic impurity content is obtained by distillation. The distillation bottom liquid is discharged periodically to achieve the stability of the distillation bottom liquid, and the discharged distillation bottom liquid is returned to the vanadium removal process.

[0041] The present invention provides a method for removing organic impurities from purified titanium tetrachloride, the specific steps of which are as follows:

[0042] (1) Open the titanium tetrachloride valve and introduce the vanadium-removed refined titanium tetrachloride into the mixing tank;

[0043] (2) Open the reagent valve and add the reagent to the mixing tank at 0.01%-0.02% of the mass of titanium tetrachloride. The reagent includes, but is not limited to: alkali metal chlorides and their hydrated chlorides, alkaline earth metal chlorides and their hydrated chlorides, aluminum trichloride and its hydrated chlorides, and ferric trichloride and its hydrated chlorides.

[0044] (3) Turn on the stirrer in the mixing tank and stir for 30-60 minutes to ensure that the reagent and titanium tetrachloride are fully mixed and reacted.

[0045] (4) The reacted liquid is introduced into a distillation apparatus and purified titanium tetrachloride with an organic impurity content of <0.0001% is obtained by distillation;

[0046] (5) Discharge and collect the distillation bottom liquid at regular intervals to keep the solid content of the distillation bottom liquid at 100-150g / L, and return the distillation bottom liquid to the vanadium removal process through a pump.

[0047] Example 1

[0048] A method for removing organic impurities from purified titanium tetrachloride, comprising the following steps:

[0049] (1) Open the titanium tetrachloride valve and introduce 86.6 kg of vanadium-removed refined titanium tetrachloride into the mixing tank;

[0050] (2) Open the reagent valve and add 17.32g of sodium chloride reagent to the mixing tank;

[0051] (3) Turn on the stirrer in the mixing tank and stir for 35 minutes to ensure that the reagent and purified titanium tetrachloride are fully mixed and reacted.

[0052] (4) The reaction liquid is introduced into a distillation apparatus and purified titanium tetrachloride with an organic impurity content of <0.0001% is obtained by distillation, that is, 85.437 kg of purified titanium tetrachloride is distilled out.

[0053] (5) The distillation bottom liquid is discharged periodically and introduced into the titanium tetrachloride collection tank. The solid content of the distillation bottom liquid is maintained at 100g / L, and it is returned to the vanadium removal process by pump.

[0054] Example 2

[0055] A method for removing organic impurities from purified titanium tetrachloride, comprising the following steps:

[0056] (1) Open the titanium tetrachloride valve and introduce 5000 kg of vanadium-removed refined titanium tetrachloride into the mixing tank;

[0057] (2) Open the reagent valve and add 1 kg of calcium chloride reagent into the mixing tank;

[0058] (3) Turn on the stirrer in the mixing tank and stir for 40 minutes to ensure that the reagent and purified titanium tetrachloride are fully mixed and reacted.

[0059] (4) The reaction liquid is introduced into a distillation device and purified titanium tetrachloride with an organic impurity content of <0.0001% is obtained by distillation, that is, 4950 kg of purified titanium tetrachloride is distilled out.

[0060] (5) The distillation bottom liquid is discharged periodically and introduced into the titanium tetrachloride collection tank. The solid content of the distillation bottom liquid is maintained at 120 g / L, and it is returned to the vanadium removal process by pump.

[0061] Example 3

[0062] A method for removing organic impurities from purified titanium tetrachloride, comprising the following steps:

[0063] (1) Open the titanium tetrachloride valve and introduce 1000 kg of vanadium-removed refined titanium tetrachloride into the mixing tank;

[0064] (2) Open the reagent valve and add 100g of ferric chloride reagent to the mixing tank;

[0065] (3) Turn on the stirrer in the mixing tank and stir for 30 minutes to ensure that the reagent and titanium tetrachloride are fully mixed and reacted.

[0066] (4) The reaction liquid is introduced into a distillation device and purified titanium tetrachloride with an organic impurity content of <0.0001% is obtained by distillation, that is, 990 kg of purified titanium tetrachloride is distilled out.

[0067] (5) The distillation bottom liquid is discharged periodically and introduced into the titanium tetrachloride collection tank. The solid content of the distillation bottom liquid is maintained at 150 g / L, and it is returned to the vanadium removal process by pump.

[0068] Example 4

[0069] A method for removing organic impurities from purified titanium tetrachloride, comprising the following steps:

[0070] (1) Open the titanium tetrachloride valve and introduce 5000 kg of vanadium-removed refined titanium tetrachloride into the mixing tank;

[0071] (2) Open the reagent valve and add 1 kg of aluminum trichloride reagent into the mixing tank;

[0072] (3) Turn on the stirrer in the mixing tank and stir for 45 minutes to ensure that the reagent and titanium tetrachloride are fully mixed and reacted.

[0073] (4) The reaction liquid is introduced into a distillation device and purified titanium tetrachloride with an organic impurity content of <0.0001% is obtained by distillation, that is, 4930 kg of purified titanium tetrachloride is distilled out.

[0074] (5) The distillation bottom liquid is discharged periodically and introduced into the titanium tetrachloride collection tank. The solid content of the distillation bottom liquid is maintained at 130 g / L, and it is returned to the vanadium removal process by pump.

[0075] Example 5

[0076] A method for removing organic impurities from purified titanium tetrachloride, comprising the following steps:

[0077] (1) Open the titanium tetrachloride valve and introduce 500 kg of vanadium-removed refined titanium tetrachloride into the mixing tank.

[0078] (2) Open the reagent valve and add 100g of lithium chloride monohydrate reagent to the mixing tank;

[0079] (3) Turn on the stirrer in the mixing tank and stir for 60 minutes to ensure that the reagent and titanium tetrachloride are fully mixed and reacted.

[0080] (4) The reacted liquid is introduced into a distillation apparatus and purified titanium tetrachloride with an organic content of <0.0001% is obtained by distillation, i.e., 455 kg of purified titanium tetrachloride is distilled out.

[0081] (5) The distillation bottom liquid is discharged periodically and introduced into the titanium tetrachloride collection tank. The solid content of the distillation bottom liquid is maintained at 120 g / L, and it is returned to the vanadium removal process by pump.

[0082] Example 6

[0083] A method for removing organic impurities from purified titanium tetrachloride, comprising the following steps:

[0084] (1) Open the titanium tetrachloride valve and introduce 800 kg of vanadium-removed refined titanium tetrachloride into the mixing tank;

[0085] (2) Open the reagent valve and add 120g of calcium chloride dihydrate reagent to the mixing tank;

[0086] (3) Turn on the stirrer in the mixing tank and stir for 60 minutes to ensure that the reagent and titanium tetrachloride are fully mixed and reacted.

[0087] (4) The reacted liquid is introduced into a distillation apparatus and purified titanium tetrachloride with an organic content of <0.0001% is obtained by distillation, i.e., 795 kg of purified titanium tetrachloride is distilled out.

[0088] (5) The distillation bottom liquid is discharged periodically and introduced into the titanium tetrachloride collection tank. The solid content of the distillation bottom liquid is maintained at 120 g / L, and it is returned to the vanadium removal process by pump.

[0089] Example 7

[0090] A method for removing organic impurities from purified titanium tetrachloride, comprising the following steps:

[0091] (1) Open the titanium tetrachloride valve and introduce 1000 kg of vanadium-removed refined titanium tetrachloride into the mixing tank;

[0092] (2) Open the reagent valve and add 120g of ferric chloride hexahydrate reagent to the mixing tank;

[0093] (3) Turn on the stirrer in the mixing tank and stir for 60 minutes to ensure that the reagent and titanium tetrachloride are fully mixed and reacted.

[0094] (4) The reacted liquid is introduced into a distillation apparatus and purified titanium tetrachloride with an organic content of <0.0001% is obtained by distillation, i.e., 985 kg of purified titanium tetrachloride is distilled out.

[0095] (5) The distillation bottom liquid is discharged periodically and introduced into the titanium tetrachloride collection tank. The solid content of the distillation bottom liquid is maintained at 120 g / L, and it is returned to the vanadium removal process by pump.

[0096] Example 8

[0097] A method for removing organic impurities from purified titanium tetrachloride, comprising the following steps:

[0098] (1) Open the titanium tetrachloride valve and introduce 2000 kg of vanadium-removed refined titanium tetrachloride into the mixing tank;

[0099] (2) Open the reagent valve and add 400g of aluminum trichloride hexahydrate reagent into the mixing tank;

[0100] (3) Turn on the stirrer in the mixing tank and stir for 60 minutes to ensure that the reagent and titanium tetrachloride are fully mixed and reacted.

[0101] (4) The reacted liquid is introduced into a distillation apparatus and purified titanium tetrachloride with an organic content of <0.0001% is obtained by distillation, i.e., 1995 kg of purified titanium tetrachloride is distilled out.

[0102] (5) The distillation bottom liquid is discharged periodically and introduced into the titanium tetrachloride collection tank. The solid content of the distillation bottom liquid is maintained at 140 g / L, and it is returned to the vanadium removal process by pump.

[0103] Through the above embodiments of the present invention, the method of the present invention achieves a high removal rate of organic impurities in refined titanium tetrachloride, reaching 99.99%. Furthermore, the process of the present invention is simple, requires low equipment investment, and has low energy consumption. The removal of residual organic impurities from refined titanium tetrachloride in the present invention can significantly improve the quality of sponge titanium. This technology can be promoted to all sponge titanium enterprises that use organic matter removal to refine titanium tetrachloride.

[0104] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention. Any modifications or equivalent substitutions made to the present invention without departing from the spirit and scope thereof should be covered within the protection scope of the claims of the present invention.

Claims

1. A method for removing organic impurities from purified titanium tetrachloride, characterized in that, Includes the following steps: 1) Open the titanium tetrachloride valve and introduce the vanadium-removed purified titanium tetrachloride into the mixing tank; 2) Open the reagent valve and introduce the reagent into the mixing tank, wherein the reagent is selected from one of the following: sodium chloride, potassium chloride, calcium chloride, magnesium chloride, lithium chloride, and the reagent is introduced into the mixing tank at 0.01%-0.02% of the mass of titanium tetrachloride; 3) Turn on the stirrer in the mixing tank and stir for 30-60 minutes to fully mix the reagent with the purified titanium tetrachloride, so that the residual organic matter in the purified titanium tetrachloride undergoes a complexation reaction with the reagent to form a precipitate, which is then precipitated from the purified titanium tetrachloride; 4) Introduce the reaction solution into a distillation apparatus and obtain purified titanium tetrachloride with an organic impurity content of <0.0001% by distillation; the organic impurity removal rate in the purified titanium tetrachloride reaches 99.99%.

2. The method for removing organic impurities from purified titanium tetrachloride according to claim 1, characterized in that, The method further includes the step: 5) draining and collecting the distillate, and then returning the collected distillate to the vanadium removal process.

3. The method for removing organic impurities from purified titanium tetrachloride according to claim 2, characterized in that, In step 5), the solid content of the distillate is maintained at 100-150 g / L.

4. The method for removing organic impurities from purified titanium tetrachloride according to claim 3, characterized in that, In step 5), the distillate is returned to the vanadium removal process by a pump.

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