Treatment method of slurry for removing vanadium from aluminum powder

Abstract

The invention provides a treatment method of aluminum powder vanadium removal slurry, which comprises the following steps: distilling the aluminum powder vanadium removal slurry under a first temperature condition, and removing a first substance to obtain a first distillation residue; under a second temperature condition, distilling the first distillation residue, and removing a second substance to obtain a second distillation residue; distilling the second distillation residue under a third temperature condition, and removing a third substance to obtain a third distillation residue; and reacting the third distillation residue with molten magnesium metal, and after the reaction is completed, carrying out post-treatment on the obtained product to obtain the titanium-vanadium alloy. According to the method, separation of multiple substances in the aluminum powder vanadium removal slurry is achieved through multi-stage distillation at different temperatures, and the final distillation residues are subjected to magnesiothermic reduction reaction to obtain the titanium-vanadium alloy. Therefore, the utilization of various resources in the aluminum powder vanadium removal slurry is realized, and the comprehensive utilization value of the aluminum powder vanadium removal slurry is improved.

Description

Technical Field

[0001] The invention belongs to the field of chemical separation, specifically relates to the field of titanium chemical technology, and in particular to a method for treating aluminum powder vanadium removal slurry. Background Art

[0002] Titanium tetrachloride is an important raw material for the production of titanium dioxide and titanium sponge. Boiling chlorination method and molten salt chlorination method are the main methods for producing titanium tetrachloride in industry at present. However, there are a lot of impurities in the obtained products and they cannot meet the production needs of titanium dioxide and titanium sponge. It is necessary to obtain qualified refined titanium tetrachloride products through refining and impurity removal. According to the different boiling points of impurity elements and titanium tetrachloride, they can be divided into three types of impurities: low boiling point, high boiling point and similar boiling point. Among them, high boiling point impurities such as FeCl3 can be removed by sedimentation, distillation, rectification and other methods, low boiling point impurities such as SiCl4 can be removed by plate distillation, and impurities with similar boiling points such as VOCl3 and VCl4 need to be removed by chemical means, among which VOCl3 has the highest content and is the most representative. In industrial production, vanadium can be separated and removed by copper wire removal, H2S removal, organic matter removal and aluminum powder removal. Among them, copper wire removal of vanadium has been eliminated due to low production capacity load and poor processing environment, and the highly toxic H2S removal of vanadium has only been applied in Toho Titanium Industry, Japan. The technology of organic vanadium removal is mainly concentrated in most TiCl4 production enterprises in Europe, America, Japan and my country. Aluminum powder vanadium removal can not only effectively prevent organic vanadium removal reagents from entering titanium tetrachloride, but also effectively remove oxygen impurities in titanium tetrachloride. It is widely used in titanium sponge production enterprises such as Vismp Avisma in Russia.

[0003] In the prior art, the aluminum powder vanadium removal slurry mainly realizes the recycling of TiCl4 by hydrolysis sedimentation and slurry evaporation. For example: Patent application No. 201910543643.3 proposes a method for removing aluminum from crude titanium aluminum tetrachloride powder vanadium removal slurry, and finally obtains low-aluminum TiCl4 and bottom concentrated slurry. Patent application No. 201310589820.4 discloses a method for preparing iron vanadate from crude titanium aluminum tetrachloride powder vanadium removal slag. Patent application No. 201310589810.0 proposes a method for preparing alkali metal vanadate from crude titanium aluminum tetrachloride powder vanadium removal slag. However, the above patent applications mainly focus on the recycling of titanium and vanadium resources, and still fail to maximize the characteristics and advantages of aluminum powder vanadium removal slurry. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention aims to provide a method for treating aluminum powder vanadium removal slurry.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention provides a method for treating aluminum powder vanadium removal slurry, comprising the following steps: (1) distilling the aluminum powder vanadium removal slurry under a first temperature condition to remove the first substance and obtain a first distillation residue; (2) distilling the first distillation residue under a second temperature condition to remove the second substance and obtain a second distillation residue; (3) distilling the second distillation residue under a third temperature condition to remove the third substance, thereby obtaining a third distillation residue; (4) reacting the third distillation residue with molten metal magnesium, and after the reaction is complete, post-treating the obtained product to obtain a titanium-vanadium alloy.

[0006] In one embodiment of the method for treating aluminum powder vanadium removal slurry according to the present invention, in step (1), the aluminum powder vanadium removal slurry is distilled at 137° C. to 170° C. to remove TiCl 4 .

[0007] In one embodiment of the method for treating aluminum powder vanadium removal slurry according to the present invention, in step (2), the first distillation residue is distilled at 316° C. to 440° C. to remove FeCl 3 and AlCl 3 .

[0008] In one embodiment of the method for treating aluminum powder vanadium removal slurry according to the present invention, in step (3), the second distillation residue is distilled at 440°C to 600°C to remove VOCl2, VCl3 and TiCl3.

[0009] In one embodiment of the method for treating aluminum powder vanadium removal slurry according to the present invention, in step (4), the amount of metal magnesium added is 1.1 to 2 times the theoretical amount, and the reaction temperature is 650°C to 900°C.

[0010] In one embodiment of the method for treating aluminum powder vanadium removal slurry according to the present invention, the distillation operation in steps (1) to (3) and the reaction in step (4) are carried out under a protective atmosphere.

[0011] In one embodiment of the method for treating aluminum powder vanadium removal slurry described in the present invention, the protective atmosphere is one or more of argon, helium, and neon.

[0012] In one embodiment of the method for treating aluminum powder vanadium removal slurry according to the present invention, in step (4), the post-treatment includes a step of cooling the product.

[0013] In one embodiment of the method for treating aluminum powder vanadium removal slurry according to the present invention, the post-treatment further includes the step of removing excess metallic magnesium, MgCl2 by-product and residual chloride ions in the product.

[0014] In one embodiment of the method for treating aluminum powder vanadium removal slurry according to the present invention, the post-treatment further includes the step of drying the product.

[0015] Compared with the prior art, the beneficial technical effects of the present invention are: The processing method of the aluminum powder vanadium removal slurry of the present invention first separates TiCl4 by distillation at a relatively low temperature, and then further increases the temperature to separate FeCl3 and AlCl3, and then continues to increase the temperature to separate substances such as chlorovanadium oxychloride, and the final distillation residue reacts with molten metal magnesium to prepare a titanium-vanadium alloy. Due to the distillation at different temperatures in multiple stages, the separation of various substances such as TiCl4, FeCl3, AlCl3, VOCl2, VCl3, TiCl3 in the aluminum powder vanadium removal slurry is achieved, and the final distillation residue is subjected to a magnesium thermal reduction reaction to obtain a titanium-vanadium alloy. Thus, the utilization of various resources in the aluminum powder vanadium removal slurry is achieved, the comprehensive utilization value of the aluminum powder vanadium removal slurry is improved, the potential economic benefits are achieved, and the distillation residue can be extended to other aluminum powder vanadium removal enterprises, and the titanium-vanadium alloy has a good prospect for promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0017] Figure 1 The present invention is a schematic flow chart of the method for treating aluminum powder vanadium removal slurry. DETAILED DESCRIPTION

[0018] The following is a further detailed description of the embodiments of the present disclosure in conjunction with the accompanying drawings and examples. The detailed description of the following embodiments and the accompanying drawings are used to exemplarily illustrate the principles of the present disclosure, but cannot be used to limit the scope of the present disclosure. The present disclosure can be implemented in many different forms and is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims.

[0019] The present disclosure provides these embodiments to make the present disclosure thorough and complete, and to fully express the scope of the present disclosure to those skilled in the art. It should be noted that unless otherwise specifically stated, the relative arrangement of the parts and steps, the composition of the materials, the numerical expressions and the numerical values ​​set forth in these embodiments should be interpreted as being merely exemplary, and not as limiting.

[0020] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0021] The terms "including" and "having" and any variations thereof in the specification and claims of the present invention and the above-mentioned drawings are intended to cover non-exclusive inclusions; the terms "first", "second", etc. in the specification and claims of the present disclosure or the above-mentioned drawings are used to distinguish different objects, rather than to describe a specific order. "Multiple" means two or more, unless otherwise clearly and specifically limited.

[0022] The overall concept of the treatment method of aluminum powder vanadium removal slurry of the present invention is: first, TiCl4 is separated by distillation at a relatively low temperature; second, FeCl3 and AlCl3 are separated at a relatively high temperature; then, the temperature is continued to be raised to separate substances such as vanadium oxychloride; finally, the final distillation residue is reacted with molten metal magnesium to prepare a titanium-vanadium alloy.

[0023] like Figure 1 As shown, the present invention provides a method for treating aluminum powder vanadium removal slurry, the method comprising the following steps: (1) Under a first temperature condition, distilling the aluminum powder vanadium removal slurry to remove the first substance and obtain a first distillation residue.

[0024] (2) distilling the first distillation residue under a second temperature condition to remove the second substance and obtain a second distillation residue.

[0025] (3) distilling the second distillation residue under a third temperature condition to remove the third substance, thereby obtaining a third distillation residue.

[0026] (4) reacting the third distillation residue with molten magnesium metal, wherein the amount of magnesium metal added is 1.1 to 2 times of the theoretical amount, and an excess amount of magnesium metal is added to ensure a complete and sufficient reaction. After the reaction is complete, the obtained product is post-treated to obtain a titanium-vanadium alloy.

[0027] In one embodiment of the method for treating aluminum powder vanadium removal slurry of the present invention, in step (1), the temperature of distilling and separating TiCl4 in the aluminum powder vanadium removal slurry is controlled to be above the boiling point of TiCl4 (137°C) and below the boiling point of the impurity AlCl3 (178°C). Therefore, the aluminum powder vanadium removal slurry is distilled at 137°C to 170°C to remove TiCl4.

[0028] In one embodiment of the method for treating aluminum powder vanadium removal slurry of the present invention, in step (2), the temperature for distilling and separating impurities such as FeCl3 and AlCl3 in the aluminum powder vanadium removal slurry needs to be higher than the boiling point of FeCl3 (316°C) and lower than the disproportionation temperature of TiCl3 (440°C). Therefore, the first distillation residue is distilled at 316°C to 440°C to remove FeCl3 and AlCl3.

[0029] In one embodiment of the method for treating aluminum powder vanadium removal slurry of the present invention, in step (3), the second distillation residue is distilled at 440°C to 600°C to remove VOCl2, VCl3 and TiCl3.

[0030] In one embodiment of the method for treating aluminum powder vanadium removal slurry of the present invention, in step (4), the reaction temperature is 650°C to 900°C.

[0031] In one embodiment of the method for treating aluminum powder vanadium removal slurry of the present invention, the distillation operation in steps (1) to (3) and the reaction in step (4) are carried out under a protective atmosphere. In one embodiment of the method for treating aluminum powder vanadium removal slurry of the present invention, the protective atmosphere is one or more of argon, helium, and neon.

[0032] When substances such as vanadium oxychloride (VOCl2, VCl3) are separated, reactions of formula (1) to (3) occur to generate low-boiling-point VCl4, VOCl, VOCl3, and TiCl4, thereby achieving separation, while high-boiling-point substances VCl2 and TiCl2 enter the final distillation residue (third distillation residue).

[0033]

[0034] The VCl2 and TiCl2 in the final distillation residue react with molten metal magnesium to produce a titanium-vanadium alloy.

[0035]

[0036] Those skilled in the art should understand that the collection devices for the above-mentioned distillation stages are independent of each other to facilitate the separation of different distillation products.

[0037] In one embodiment of the method for treating aluminum powder vanadium removal slurry of the present invention, in step (4), the post-treatment includes a step of cooling the product.

[0038] In one embodiment of the method for treating aluminum powder vanadium removal slurry of the present invention, the post-treatment also includes the step of removing excess metallic magnesium, MgCl2 by-product and residual chloride ions in the product.

[0039] In one embodiment of the method for treating aluminum powder vanadium removal slurry of the present invention, the post-treatment further includes the step of drying the product.

[0040] The processing method of aluminum powder vanadium removal slurry of the present invention realizes the separation of various substances such as TiCl4, FeCl3, AlCl3, VOCl2, VCl3, TiCl3 and the like in the aluminum powder vanadium removal slurry by performing multi-stage distillation at different temperatures on the aluminum powder vanadium removal slurry, and performs magnesium thermal reduction reaction on the final distillation residue to obtain titanium-vanadium alloy, thereby improving the comprehensive utilization value of the aluminum powder vanadium removal slurry and having good prospects for promotion and application.

[0041] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0042] Example 1 (1) 1000 g of aluminum powder vanadium removal slurry was placed in a distillation furnace protected by argon gas, and the distillation temperature was controlled to be 150°C. After the distillation was completed, the first distillation residue was obtained. The distillation product collection device was removed to obtain 890 g of distillation product (TiCl4).

[0043] (2) Connect a new distillation collection device, control the distillation temperature to 350°C to distill the first distillation residue, and obtain the second distillation residue after the distillation is completed. Dismantle the distillation product collection device to obtain 12g of distillation product (FeCl3, AlCl3).

[0044] (3) Continue to connect a new distillation collection device, control the distillation temperature to 500°C to distill the second distillation residue, and obtain the third distillation residue after the distillation is completed. Dismantle the distillation product collection device to obtain 40g of distillation product (VOCl2, VCl3, TiCl3).

[0045] (4) The third distillation residue was added to molten magnesium metal under argon protection at 700°C (the amount of magnesium metal added was 1.1 times the theoretical amount), and the product was fully reacted. After the product was cooled, 1-2% hydrochloric acid was used to wash away excess magnesium metal and MgCl2 by-products, and then deionized water was used to wash away residual chloride ions. After drying at 120°C for 12 hours, 17g of titanium-vanadium alloy was obtained.

[0046] Example 2 (1) 1000g of aluminum powder vanadium removal slurry was placed in a distillation furnace protected by argon gas, and the distillation temperature was controlled to be 160°C. After the distillation was completed, the first distillation residue was obtained. The distillation product collection device was removed to obtain 900g of distillation product (TiCl4).

[0047] (2) Connect a new distillation collection device, control the distillation temperature to 400°C to distill the first distillation residue, and obtain the second distillation residue after the distillation is completed. Dismantle the distillation product collection device to obtain 14g of distillation product (FeCl3, AlCl3).

[0048] (3) Continue to connect a new distillation collection device, control the distillation temperature to 500°C to distill the second distillation residue, and obtain the third distillation residue after the distillation is completed. Dismantle the distillation product collection device to obtain 43g of distillation product (VOCl2, VCl3, TiCl3).

[0049] (4) The third distillation residue was added into molten magnesium metal at 750°C under argon protection (the amount of magnesium metal added was 1.3 times the theoretical amount), and the product was fully reacted. After the product was cooled, 1-2% hydrochloric acid was used to wash away excess magnesium metal and MgCl2 by-products, and then deionized water was used to wash away residual chloride ions. After drying at 120°C for 12 h, 12 g of titanium-vanadium alloy was obtained.

[0050] Example 3 (1) 1000 g of aluminum powder vanadium removal slurry was placed in a distillation furnace protected by helium, and the distillation temperature was controlled to be 170°C. After the distillation was completed, the first distillation residue was obtained. The distillation product collection device was removed to obtain 905 g of distillation product (TiCl4).

[0051] (2) Connect a new distillation collection device, control the distillation temperature to 440°C to distill the first distillation residue, and obtain the second distillation residue after the distillation is completed. Dismantle the distillation product collection device to obtain 13.5g of distillation product (FeCl3, AlCl3).

[0052] (3) Continue to connect a new distillation collection device, control the distillation temperature to 600°C to distill the second distillation residue, and obtain the third distillation residue after the distillation is completed. Dismantle the distillation product collection device to obtain 44.5g of distillation product (VOCl2, VCl3, TiCl3).

[0053] (4) The third distillation residue was added to molten magnesium metal under helium protection at 800°C (the amount of magnesium metal added was 1.5 times the theoretical amount), and the product was fully reacted. After the product was cooled, 1-2% hydrochloric acid was used to wash away excess magnesium metal and MgCl2 by-products, and then deionized water was used to wash away residual chloride ions. After drying at 120°C for 12 hours, 37g of titanium-vanadium alloy was obtained.

[0054] Example 4 (1) 1000g of aluminum powder vanadium removal slurry was placed in a distillation furnace protected by neon gas, and the distillation temperature was controlled to be 137°C. After the distillation was completed, the first distillation residue was obtained. The distillation product collection device was removed to obtain 903g of distillation product (TiCl4).

[0055] (2) Connect a new distillation collection device, control the distillation temperature to 316°C to distill the first distillation residue, and obtain the second distillation residue after the distillation is completed. Dismantle the distillation product collection device to obtain 11.5g of distillation product (FeCl3, AlCl3).

[0056] (3) Continue to connect a new distillation collection device, control the distillation temperature to 440°C to distill the second distillation residue, and obtain the third distillation residue after the distillation is completed. Dismantle the distillation product collection device to obtain 45.5g of distillation product (VOCl2, VCl3, TiCl3).

[0057] (4) The third distillation residue was added to molten magnesium metal at 650°C under neon protection (the amount of magnesium metal added was 1.8 times the theoretical amount), and the product was fully reacted. After the product was cooled, 1-2% hydrochloric acid was used to wash away excess magnesium metal and MgCl2 by-products, and then deionized water was used to wash away residual chloride ions. After drying at 120°C for 12 hours, 40 g of titanium-vanadium alloy was obtained.

[0058] Example 5 (1) 1000g of aluminum powder vanadium removal slurry was placed in a distillation furnace protected by neon gas, and the distillation temperature was controlled to be 155°C. After the distillation was completed, the first distillation residue was obtained. The distillation product collection device was removed to obtain 925g of distillation product (TiCl4).

[0059] (2) Connect a new distillation collection device, control the distillation temperature to 330°C to distill the first distillation residue, and obtain the second distillation residue after the distillation is completed. Dismantle the distillation product collection device to obtain 13.5g of distillation product (FeCl3, AlCl3).

[0060] (3) Continue to connect a new distillation collection device, control the distillation temperature to 450°C to distill the second distillation residue, and obtain the third distillation residue after the distillation is completed. Dismantle the distillation product collection device to obtain 38g of distillation product (VOCl2, VCl3, TiCl3).

[0061] (4) The third distillation residue was added into molten magnesium metal under neon protection at 900°C (the amount of magnesium metal added was twice the theoretical amount), and the product was fully reacted. After the product was cooled, 1-2% hydrochloric acid was used to wash away excess magnesium metal and MgCl2 by-products, and then deionized water was used to wash away residual chloride ions. After drying at 120°C for 12 hours, 23.5 g of titanium-vanadium alloy was obtained.

[0062] It should be particularly pointed out that the various components or steps in the above-mentioned embodiments can be cross-linked, replaced, added, or deleted with each other. Therefore, the combinations formed by these reasonable arrangements and combinations should also fall within the scope of protection of the present invention, and the scope of protection of the present invention should not be limited to the embodiments.

[0063] A person skilled in the art should understand that the discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope of the disclosure of the embodiments of the present invention (including the claims) is limited to these examples; under the concept of the embodiments of the present invention, the technical features in the above embodiments or different embodiments can also be combined, and there are many other changes in different aspects of the embodiments of the present invention as described above, which are not provided in detail for the sake of simplicity. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the embodiments of the present invention should be included in the protection scope of the embodiments of the present invention.

Claims

1. A method for treating aluminum powder vanadium removal slurry, characterized in that: The following steps are involved: (1) distilling the aluminum powder vanadium removal slurry under a first temperature condition to remove the first substance and obtain a first distillation residue; (2) distilling the first distillation residue under a second temperature condition to remove the second substance and obtain a second distillation residue; (3) distilling the second distillation residue under a third temperature condition to remove the third substance, thereby obtaining a third distillation residue; (4) reacting the third distillation residue with molten metal magnesium, and after the reaction is complete, post-treating the obtained product to obtain a titanium-vanadium alloy.

2. The method for treating aluminum powder vanadium removal slurry according to claim 1, characterized in that: In step (1), the aluminum powder vanadium removal slurry is distilled at 137°C to 170°C to remove TiCl4.

3. The method for treating aluminum powder vanadium removal slurry according to claim 1, characterized in that: In step (2), the first distillation residue is distilled at 316°C to 440°C to remove FeCl3 and AlCl3.

4. The method for treating aluminum powder vanadium removal slurry according to claim 1, characterized in that: In step (3), the second distillation residue is distilled at 440°C to 600°C to remove VOCl2, VCl3, and TiCl3.

5. The method for treating aluminum powder vanadium removal slurry according to claim 1, characterized in that: In step (4), the amount of magnesium metal added is 1.1 to 2 times the theoretical amount, and the reaction temperature is 650°C to 900°C.

6. The method for treating aluminum powder vanadium removal slurry according to claim 1, characterized in that: The distillation operation in steps (1) to (3) and the reaction in step (4) are carried out under a protective atmosphere.

7. The method for treating aluminum powder vanadium removal slurry according to claim 6, characterized in that: The protective atmosphere is one or more of argon, helium and neon.

8. The method for treating aluminum powder vanadium removal slurry according to claim 1, characterized in that: In step (4), the post-treatment includes a step of cooling the product.

9. The method for treating aluminum powder vanadium removal slurry according to claim 8, characterized in that: The post-treatment also includes the step of removing excess metallic magnesium, MgCl2 byproduct and residual chloride ions in the product.

10. The method for treating aluminum powder vanadium removal slurry according to claim 9, characterized in that: The post-treatment also includes a step of drying the product.

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