Separation method and separation system for titanium-containing ore

Abstract

The invention discloses a titanium-containing ore separation method and a titanium-containing ore separation system. The separation method comprises the following steps: carrying out fluorination reaction on a fluorinating agent and titanium-containing ore to obtain a fluorinated product; carrying out first-stage sublimation-desublimation treatment on the fluorinated product to obtain a mixture of silicon-containing fluoride and an unreacted fluorinating agent and first-stage sublimation residues; performing second-stage sublimation-desublimation treatment on the first-stage sublimation residues to obtain titanium-containing fluoride and second-stage sublimation residues; and carrying out third-stage sublimation-desublimation treatment on the second-stage sublimation residues to obtain vanadium-containing fluoride and third-stage sublimation residues. According to the separation method provided by the invention, silicon oxide, titanium oxide, vanadium oxide, iron oxide and the like in the ore react with the fluorinating agent to generate a mixture containing various fluorides; and sublimating fluorides corresponding to the elements from a mixture generated by the fluorination reaction at different temperature sections, so as to separate and purify a target product.

Description

Technical Field

[0001] The present invention belongs to the technical field of separation and utilization of titanium-containing ore resources, and particularly relates to a separation method and a separation system for titanium-containing ore. Background Art

[0002] Titanium dioxide (TiO 2 ) is commonly known as titanium white powder and is the third largest inorganic chemical product after synthetic ammonia and phosphatic chemicals. It has high chemical stability, heat resistance, weather resistance, good whiteness, tinting strength and covering power, and is considered to be the best white pigment and an important chemical product in the world at present. It is currently widely used in fields such as coatings, plastics, rubber, papermaking, chemical fibers, inks, cosmetics, etc.

[0003] At present, there are mainly two methods for realizing the industrial production of titanium white powder, namely the sulfuric acid method and the chlorination method. The sulfuric acid method process is more mature than the chlorination method, has a long process flow, is intermittently operated in the production process, has high energy consumption, and has a large amount of "three wastes" emissions. It is clearly proposed that the construction of new sulfuric acid method titanium white powder production plants will be restricted, and the development of new titanium white powder production technologies with high efficiency, low consumption and low pollution will be encouraged. The chlorination method belongs to the encouraged process technology, but the chlorination method has high requirements for raw material quality and can only produce rutile-type titanium white powder products. Therefore, the chlorination method process is restricted by the shortage of high-quality titanium ore resources and the limited source of chlorination method raw materials; second, the patent cost for the construction of production devices is high and the cost is relatively high. Therefore, the development of a new titanium white powder production process with independent intellectual property rights, low requirements for raw material quality, clean environmental protection, low energy consumption and high product purity is crucial for accelerating the development of the titanium white powder industry in China.

[0004] The process method of producing titanium white powder by the fluorination method solves the problems such as high pollution and high energy consumption faced by the existing sulfuric acid method process; however, the fluorination products generated in the process of producing titanium white powder by the fluorination method have a complex composition and a relatively high impurity content. How to effectively separate and purify the target product is crucial for the integrity, economy and large-scale industrial application of the entire process system. Summary of the Invention

[0005] The main object of the present invention is to provide a separation method and a separation system for titanium-containing ore to overcome the deficiencies of the prior art.

[0006] To achieve the foregoing invention object, the technical solutions adopted by the present invention include: An embodiment of the present invention provides a separation method for titanium-containing ore, which includes: Making a fluorinating agent react with the titanium-containing ore to obtain a fluorination product; wherein, the titanium-containing ore includes at least titanium element; Performing primary sublimation-condensation treatment on the fluorination product to obtain a mixture of silicon fluoride and unreacted fluorinating agent, and primary sublimation residues; Perform a secondary sublimation-condensation treatment on the primary sublimation residue to obtain titanium fluoride and a secondary sublimation residue; Perform a tertiary sublimation-condensation treatment on the secondary sublimation residue to obtain vanadium fluoride and a tertiary sublimation residue.

[0007] An embodiment of the present invention also provides a separation system for titanium-containing ore, which is applied to the foregoing separation method and is characterized by including: A fluorination reaction unit that can at least cause a fluorinating agent to react with titanium-containing ore to form a fluorination product; A primary sublimation-condensation unit that can at least perform a primary sublimation-condensation treatment on the fluorination product; A secondary sublimation-condensation unit that can at least perform a primary sublimation-condensation treatment on the fluorination product; And a tertiary sublimation-condensation unit that can at least perform a primary sublimation-condensation treatment on the fluorination product.

[0008] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The separation method of titanium-containing ore provided by the present invention reacts a fluorinating agent with titanium, vanadium, and titanium elements in the titanium-containing ore to form corresponding fluorides, achieving the purpose of selectively obtaining target elements. At the same time, the separation method of the present invention has low requirements for vanadium-titanium raw materials and does not limit the types and contents of their impurity elements. Compared with other methods, it has the advantage of wide adaptability to raw materials; (2) The separation method of titanium-containing ore provided by the present invention reacts metal oxides such as silicon oxide, titanium oxide, vanadium oxide, and iron oxide contained in the ore with a fluorinating agent to form a mixture containing various fluorides, and then uses the difference in sublimation temperatures of various fluorides to make the fluorides corresponding to each element sublimate from the generated mixture at different temperature ranges and recover them by cooling and condensation to separate and purify the target product; at the same time, impurities such as calcium, magnesium, and iron in the ore are left in the slag. The present invention effectively solves the technical problem of difficult separation and purification of various target products in the titanium ore resource utilization process; (3) Compared with the prior art, the present invention has a simple process flow, is easy to operate, is clean and environmentally friendly, and can effectively reduce costs. Description of the Drawings

[0009] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0010] Figure 1It is a schematic diagram of a separation system for titanium-containing ore in a typical embodiment of the present invention. Detailed implementation manners

[0011] In view of the defects of the prior art, the inventors of this case have, through long-term research and a large number of practices, been able to propose the technical solution of the present invention. The present invention aims at the problems of many types of impurity elements, large contents, complex impurity components in titanium-containing ore, and difficulty in extracting and separating various elements. By reacting metal oxides such as silicon oxide, titanium oxide, vanadium oxide, and iron oxide in the ore with a fluorinating agent to generate a mixture containing fluorides corresponding to various elements, and then utilizing the differences in the sublimation temperatures of various fluorides, the silicon-containing fluoride ((NH 4 ) 2 SiF 6 ), titanium-containing fluoride ((NH 4 ) 2 TiF 6 ), and vanadium-containing fluoride ((NH 4 ) 3 VF 6 ) are successively sublimated from the mixture at different temperature ranges, and then the various sublimates are cooled and condensed and collected respectively, so as to separate and purify the target products; at the same time, impurity elements such as calcium, magnesium, and iron in the ore are left in the slag. The present invention effectively solves the technical problem of difficult separation and purification of various target compounds in the titanium dioxide production process by the fluorination method.

[0012] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts belong to the scope of protection of the present invention.

[0013] Specifically, as an aspect of the technical solution of the present invention, a separation method for titanium-containing ore involved therein includes: Making a fluorinating agent react with titanium-containing ore to obtain a fluorinated product; wherein, the titanium-containing ore includes at least titanium element; Performing a first-stage sublimation-condensation treatment on the fluorinated product to obtain a mixture of silicon-containing fluoride and unreacted fluorinating agent, and a first-stage sublimation residue; Performing a second-stage sublimation-condensation treatment on the first-stage sublimation residue to obtain titanium-containing fluoride and a second-stage sublimation residue; Performing a third-stage sublimation-condensation treatment on the second-stage sublimation residue to obtain vanadium-containing fluoride and a third-stage sublimation residue.

[0014] Specifically, in the present invention, titanium ore powder (i.e., the aforementioned titanium-containing ore) and a fluorinating agent are uniformly mixed in a certain ratio, and then a fluorination reaction occurs at a specified time (30 - 180 min) and temperature (180°C - 250°C) to obtain a fluorination product. The fluorination product first undergoes a primary sublimation process at a specified sublimation temperature (300°C - 450°C) and time (30 - 180 min), and a primary sublimate (NH 4 ) 2 SiF 6 and a mixture of unreacted fluorinating agent are obtained. After cooling it to below 80°C - 160°C, the corresponding sublimation product is obtained. Then, the primary sublimation residue undergoes a secondary sublimation process at a specified sublimation temperature (650°C - 800°C) and time (30 - 180 min), and a secondary sublimate (NH 4 ) 2 TiF 6 is obtained. After cooling it to 80°C - 180°C, the corresponding sublimation product is obtained. Subsequently, the secondary sublimation residue undergoes a tertiary sublimation process at a specified sublimation temperature (1100°C - 1200°C) and time (30 - 180 min), and a tertiary sublimate (NH 4 ) 3 VF 6 is obtained. After cooling it to 80°C - 180°C, the corresponding sublimation product is obtained. After the fluoride undergoes three-stage sublimation, the final residue is slag containing impurities such as calcium, magnesium, and iron.

[0015] In some preferred embodiments, the separation method includes: uniformly mixing the fluorinating agent pair with the titanium-containing ore and carrying out a fluorination reaction at 180 - 250°C.

[0016] In some preferred embodiments, the time of the fluorination reaction is 30 - 180 min.

[0017] In some preferred embodiments, the fluorinating agent includes ammonium fluoride and / or ammonium bifluoride.

[0018] In some preferred embodiments, the mass ratio of the titanium-containing ore to the fluorinating agent is 1:3.2 - 1:6.

[0019] In some preferred embodiments, the titanium-containing ore includes silicon oxide, titanium oxide, vanadium oxide, iron oxide, etc.

[0020] In some preferred embodiments, the separation method includes: heating the fluorination product to a first sublimation temperature for primary sublimation treatment to obtain a primary sublimation product and a primary sublimation residue; and, cooling the primary sublimation product to a first sublimation temperature for primary sublimation treatment to obtain a mixture containing silicon fluoride and unreacted fluorinating agent.

[0021] Further, the first sublimation temperature is 300°C to 450°C.

[0022] Further, the time for the first-stage sublimation treatment is 30 to 180 minutes.

[0023] Further, the first condensation temperature is 80°C to 160°C.

[0024] Further, the time for the first-stage condensation treatment is 10 to 180 minutes.

[0025] Further, the silicon-containing fluoride includes (NH 4 ) 2 SiF 6 .

[0026] In some preferred embodiments, the separation method includes: heating the first-stage sublimation residue to a second sublimation temperature for a second-stage sublimation treatment to obtain a second-stage sublimation product and a second-stage sublimation residue; and cooling the second-stage sublimation product to a second condensation temperature for a second-stage condensation treatment to obtain a titanium-containing fluoride.

[0027] Further, the second sublimation temperature is 650°C to 800°C.

[0028] Further, the time for the second-stage sublimation treatment is 30 to 180 minutes.

[0029] Further, the second condensation temperature is 80°C to 180°C.

[0030] Further, the time for the second-stage condensation treatment is 10 to 180 minutes.

[0031] Further, the titanium-containing fluoride includes (NH 4 ) 2 TiF 6 .

[0032] Further, the titanium-containing fluoride is at least used for preparing titanium dioxide.

[0033] In some preferred embodiments, the separation method includes: heating the second-stage sublimation residue to a third sublimation temperature for a third-stage sublimation treatment to obtain a third-stage sublimation product and a third-stage sublimation residue; and cooling the third-stage sublimation product to a third condensation temperature for a third-stage condensation treatment to obtain a vanadium-containing fluoride.

[0034] Further, the third sublimation temperature is 1100°C to 1200°C.

[0035] Further, the time for the three - stage sublimation treatment is 30 to 180 minutes.

[0036] Further, the third sublimation temperature is 80°C to 180°C.

[0037] Further, the time for the three - stage condensation treatment is 10 to 180 minutes.

[0038] Further, the vanadium - containing fluoride includes (NH 4 ) 3 VF 6 .

[0039] Further, the vanadium - containing fluoride is at least used for preparing vanadium oxide.

[0040] In some preferred embodiments, the fluorination product includes silicon - containing fluoride, titanium - containing fluoride and vanadium - containing fluoride.

[0041] In some preferred embodiments, the titanium - containing ore includes at least titanium and any one or a combination of two or more of silicon, vanadium, and iron elements.

[0042] Further, the titanium - containing ore further includes any one or a combination of calcium, magnesium, aluminum, manganese, and chromium elements, and is not limited thereto.

[0043] In some preferred embodiments, the separation method further includes: re - using the mixture of the silicon - containing fluoride obtained from the first - stage sublimation - condensation treatment and the unreacted fluorinating agent for the fluorination reaction.

[0044] In some preferred embodiments, the separation method further includes: separating the mixture of the silicon - containing fluoride obtained from the first - stage sublimation - condensation treatment and the unreacted fluorinating agent to obtain the silicon - containing fluoride and the fluorinating agent respectively; the silicon - containing fluoride is at least used for preparing silicon dioxide.

[0045] In some preferred embodiments, the separation method further includes: removing impurities and purifying the three - stage sublimation residue to obtain FeF 3 .

[0046] Further, the FeF 3 is at least used for preparing lithium iron phosphate.

[0047] In some more specific embodiments, the separation method of the titanium - containing ore includes: (1) Fluorination reaction: The titanium-containing ore powder and the fluorinating agent are uniformly mixed in proportion, and after they fully react with each other, a mixture containing fluorides corresponding to various elements is obtained. The fluorinating agent is one or a mixture of two of ammonium fluoride and ammonium bifluoride, and the proportion of ammonium fluoride is 0-100%. The mass ratio of the titanium ore powder to the fluorinating agent is 1:3.2-1:6 (the mass of the fluorinating agent is calculated as ammonium fluoride), the fluorination reaction temperature is 180°C-250°C, and the time is 30-180 min.

[0048] Specifically, when the fluorinating agent is NH 4 HF 2 , the titanium-containing ore powder and the fluorinating agent react in the fluorination furnace as follows: 4FeTiO 3 +26NH 4 HF 2 +O 2 =4(NH 4 ) 3 TiF 7 +4(NH 4 ) 3 +FeF 6 +4NH 3 +14H 2 O 4FeO+12NH 4 HF 2 +O 2 =4(NH 4 ) 3 FeF 6 +6H 2 O TiO 2 +4NH 4 HF 2 =(NH 4 ) 3 TiF 7 +NH 3 +HF+2H 2 CaO+NH 4 HF 2 =CaF 2 + NH 3 +H 2 O SiO 2 +4NH 4 HF 2 =(NH 4 ) 3 SiF 7 +NH 3 +HF +2H 2 O (2)Primary sublimation - condensation: After heating the mixture obtained in step (1) to a certain temperature, silicon fluoride ((NH 4 ) 2 SiF 6 ) and the unreacted fluorinating agent will first sublime, and then the condensed silicon fluoride and the unreacted fluorinating agent are collected by cooling to obtain the primary sublimation residue. The primary sublimation temperature is 300°C to 450°C, and the time is 30 to 180 min; the primary condensation temperature is 80°C to 160°C, and the time is 10 to 180 min.

[0049] (3)Secondary sublimation - condensation: After continuing to heat the primary sublimation residue obtained in step (2) to a certain temperature, titanium fluoride ((NH 4 ) 2 TiF 6 ) will sublime, and then the condensed titanium fluoride is collected by cooling to obtain the secondary sublimation residue. The secondary sublimation temperature is 650°C to 800°C, and the time is 30 to 180 min; the secondary condensation temperature is 80°C to 180°C, and the time is 10 to 180 min.

[0050] (4)Tertiary sublimation - condensation: After continuing to heat the secondary sublimation residue obtained in step (3) to a certain temperature, vanadium fluoride ((NH 4 ) 3 VF 6 ) will sublime, and then the condensed vanadium fluoride is collected by cooling to obtain the tertiary sublimation residue. The tertiary sublimation temperature is 1100°C to 1200°C, and the time is 30 to 180 min; the tertiary condensation temperature is 80°C to 180°C, and the time is 10 to 180 min.

[0051] (5)The tertiary sublimation residue obtained in step (4) is slag containing impurities such as calcium, magnesium, and iron, mainly in the form of FeF 3 . After impurity removal and purification of the tertiary sublimation residue, high - purity FeF 3 can be used as a raw material for the production of lithium iron phosphate.

[0052] Another aspect of the embodiment of the present invention also provides a separation system for titanium - containing ore, which is applied to the foregoing separation method and includes: A fluorination reaction unit, which can at least cause a fluorinating agent to react with titanium - containing ore to form a fluorination product; A primary sublimation - condensation unit, which can at least perform primary sublimation - condensation treatment on the fluorination product; A secondary sublimation - condensation unit, which can at least perform primary sublimation - condensation treatment on the fluorination product; And, a tertiary sublimation - condensation unit, which is capable of performing at least primary sublimation - condensation treatment on the fluorinated product.

[0053] In some preferred embodiments, the fluorination reaction unit includes a mixing device and a fluorination furnace.

[0054] In some preferred embodiments, the primary sublimation - condensation unit includes a primary sublimation device and a primary condensation device.

[0055] In some preferred embodiments, the secondary sublimation - condensation unit includes a secondary sublimation device and a secondary condensation device.

[0056] In some preferred embodiments, the tertiary sublimation - condensation unit includes a tertiary sublimation device and a tertiary condensation device.

[0057] In some preferred embodiments, the separation system further includes: an impurity removal and purification unit.

[0058] Further, the impurity removal and purification unit is capable of performing at least impurity removal and purification treatment on the residues of the tertiary sublimation.

[0059] In some more specific embodiments, the schematic diagram of the separation system for titanium - containing ore is as Figure 1 shown, specifically including: titanium ore powder metering tank 1; fluorinating agent metering tank 2; mixer 3; fluorination furnace 4; primary sublimator 5; primary condenser 6; secondary sublimator 7; secondary condenser 8; tertiary sublimator 9; tertiary condenser 10; titanium ore powder metering tank feed pipeline 11; fluorinating agent metering tank feed pipeline 12; mixer titanium ore powder feed pipeline 13; mixer fluorinating agent feed pipeline 14; fluorination furnace feed line 15; fluorinated product discharge pipeline 16; fluorination furnace tail gas discharge pipeline 17; primary sublimation residue discharge pipeline 18; (NH 4 ) 2 SiF 6 and the remaining fluorinating agent sublimation discharge pipeline 19; (NH 4 ) 2 TiF 6 and the remaining fluorinating agent condensate discharge pipeline 20; secondary sublimation residue discharge pipeline 21; (NH 4 ) 2 TiF 6 sublimation discharge pipeline 22; (NH 4 ) 2 TiF 6 condensate discharge pipeline 23; tertiary sublimation residue discharge pipeline 24; (NH 4 ) 3 VF 6 sublimation discharge pipeline 25; for (NH 4 ) 3 VF6 Sublimation product discharge pipeline 26.

[0060] The technical solution of the present invention will be further described in detail below in conjunction with several preferred embodiments and the accompanying drawings. The following embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation manners and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0061] In the following embodiments, the experimental materials used can be obtained from conventional biochemical reagent companies without special instructions.

[0062] In the following embodiments, 1 kg of titanium-containing ore powder is taken for the reaction.

[0063] Example 1 (1) Fluorination reaction: The titanium-containing ore powder and ammonium fluoride are uniformly mixed according to a mass ratio of 1:4, and the two react fully at 200 °C for 100 min to obtain a mixture containing fluorides corresponding to various elements.

[0064] (2) First-stage sublimation-sublimation: The mixture obtained in step (1) is heated to 350 °C and kept warm for 100 min. Silicon fluoride ((NH 4 ) 2 SiF 6 ) and the unreacted fluorinating agent will first sublime, and then the first-stage sublimation product after sublimation is collected by cooling to 100 °C, and the first-stage sublimation residue is obtained. By characterizing, the first-stage sublimation product is a mixture of silicon fluoride and unreacted ammonium fluoride.

[0065] (3) Second-stage sublimation-sublimation: The first-stage sublimation residue obtained in step (2) is continuously heated to 700 °C and kept warm for 100 min. Titanium fluoride ((NH 4 ) 2 TiF 6 ) will sublime, and then the second-stage sublimation product after sublimation is collected by cooling to 100 °C, and the second-stage sublimation residue is obtained; among them, by characterizing, the second-stage sublimation product is titanium fluoride with a purity of 93.97%.

[0066] (4) Third-stage sublimation-sublimation: The second-stage sublimation residue obtained in step (3) is continuously heated to 1100 °C and kept warm for 100 min. Vanadium fluoride ((NH 4 ) 3 VF 6 ) will sublime, and then the third-stage sublimation product after sublimation is collected by cooling to 100 °C, and the third-stage sublimation residue is obtained; among them, by characterizing, the third-stage sublimation product is vanadium fluoride with a purity of 95.17%.

[0067] (5)The tertiary sublimation residue obtained in step (4) is titanium ore slag containing impurities such as calcium, magnesium, and iron, mainly in the form of FeF 3 . After impurity removal and purification of the tertiary sublimation residue, higher-purity FeF 3 can be used as a raw material for the production of lithium iron phosphate.

[0068] Example 2 (1) Fluorination reaction: The titanium ore powder and ammonium bifluoride are uniformly mixed at a mass ratio of 1:3.2, and the two react fully at 180°C for 180 minutes to obtain a mixture of fluorides corresponding to various elements.

[0069] (2) Primary sublimation - condensation: The mixture obtained in step (1) is heated to 300°C and kept warm for 180 minutes. Silicon fluoride ((NH 4 ) 2 SiF 6 ) and the unreacted fluorinating agent will first sublime, and then the primary condensation product after condensation is collected by cooling to 80°C, and a primary sublimation residue is obtained. By characterization, the primary condensation product is a mixture of silicon fluoride and unreacted ammonium fluoride.

[0070] (3) Secondary sublimation - condensation: The primary sublimation residue obtained in step (2) is continuously heated to 650°C and kept warm for 180 minutes. Titanium fluoride ((NH 4 ) 2 TiF 6 ) will sublime, and then the secondary condensation product after condensation is collected by cooling to 80°C, and a secondary sublimation residue is obtained; among them, by characterization, the secondary condensation product is titanium fluoride with a purity of 94.78%.

[0071] (4) Tertiary sublimation - condensation: The secondary sublimation residue obtained in step (3) is continuously heated to 1150°C and kept warm for 180 minutes. Vanadium fluoride ((NH 4 ) 3 VF 6 ) will sublime, and then the tertiary condensation product after condensation is collected by cooling to 80°C, and a tertiary sublimation residue is obtained; among them, by characterization, the tertiary condensation product is vanadium fluoride with a purity of 96.65%.

[0072] (5) The tertiary sublimation residue obtained in step (4) is titanium ore slag containing impurities such as calcium, magnesium, and iron, mainly in the form of FeF 3 . After impurity removal and purification of the tertiary sublimation residue, higher-purity FeF 3 can be used as a raw material for the production of lithium iron phosphate.

[0073] Example 3 (1)Fluorination reaction: The titanium-containing ore powder and ammonium fluoride are uniformly mixed at a mass ratio of 1:6, and the two react fully at 250 °C for 30 min to obtain a mixture of fluorides corresponding to various elements.

[0074] (2)Primary sublimation-condensation: The mixture obtained in step (1) is heated to 450 °C and kept warm for 30 min. Silicon fluoride ((NH 4 ) 2 SiF 6 ) and the unreacted fluorinating agent will first sublime, and then the primary condensation product after condensation is collected by cooling to 160 °C, and a primary sublimation residue is obtained. By characterization, the primary condensation product is a mixture of silicon fluoride and unreacted ammonium fluoride.

[0075] (3)Secondary sublimation-condensation: The primary sublimation residue obtained in step (2) is continuously heated to 800 °C and kept warm for 30 min. Titanium fluoride ((NH 4 ) 2 TiF 6 ) will sublime, and then the secondary condensation product after condensation is collected by cooling to 180 °C, and a secondary sublimation residue is obtained; among them, by characterization, the secondary condensation product is titanium fluoride with a purity of 92.72%.

[0076] (4)Tertiary sublimation-condensation: The secondary sublimation residue obtained in step (3) is continuously heated to 1200 °C and kept warm for 30 min. Vanadium fluoride ((NH 4 ) 3 VF 6 ) will sublime, and then the tertiary condensation product after condensation is collected by cooling to 180 °C, and a tertiary sublimation residue is obtained; among them, by characterization, the tertiary condensation product is vanadium fluoride with a purity of 98.67%.

[0077] (5)The tertiary sublimation residue obtained in step (4) is a titanium ore slag containing impurities such as calcium, magnesium, and iron, mainly in the form of FeF 3 . After impurity removal and purification of the tertiary sublimation residue, higher-purity FeF 3 can be used as a raw material for the production of lithium iron phosphate.

[0078] Example 4 (1)Fluorination reaction: The titanium-containing ore powder and the fluorinating agent (where the mass ratio of ammonium fluoride to ammonium bifluoride is 1:1) are uniformly mixed at a mass ratio of 1:4, and the two react fully at 200 °C for 100 min to obtain a mixture of fluorides corresponding to various elements.

[0079] (2)Primary sublimation - condensation: Heat the mixture obtained in step (1) to 400 °C and hold for 100 min. The silicon fluoride ((NH 4 ) 2 SiF 6 ) and the unreacted fluorinating agent will first sublime, and then the primary condensation product after condensation is collected by cooling to 100 °C, and the primary sublimation residue is obtained. By characterization, the primary condensation product is a mixture of silicon fluoride and unreacted ammonium fluoride.

[0080] (3)Secondary sublimation - condensation: Continue to heat the primary sublimation residue obtained in step (2) to 700 °C and hold for 100 min. The titanium fluoride ((NH 4 ) 2 TiF 6 ) will sublime, and then the secondary condensation product after condensation is collected by cooling to 100 °C, and the secondary sublimation residue is obtained; among them, by characterization, the secondary condensation product is titanium fluoride with a purity of 96.16%.

[0081] (4)Tertiary sublimation - condensation: Continue to heat the secondary sublimation residue obtained in step (3) to 1150 °C and hold for 100 min. The vanadium fluoride ((NH 4 ) 3 VF 6 ) will sublime, and then the tertiary condensation product after condensation is collected by cooling to 120 °C, and the tertiary sublimation residue is obtained; among them, by characterization, the tertiary condensation product is vanadium fluoride with a purity of 97.19%.

[0082] (5)The tertiary sublimation residue obtained in step (4) is a titanium ore slag containing impurities such as calcium, magnesium, and iron, mainly in the form of FeF 3 . After impurity removal and purification of the tertiary sublimation residue, higher - purity FeF 3 can be used as a raw material for the production of lithium iron phosphate.

[0083] Comparative Example 1 The method is the same as that of Example 1, except that the first sublimation temperature is 230 °C (lower than 300 - 450 °C); (1)Fluorination reaction: Uniformly mix titanium - containing ore powder and ammonium fluoride in a mass ratio of 1:4, and allow them to react fully at 200 °C for 100 min to obtain a mixture containing fluorides corresponding to various elements.

[0084] (2)Primary sublimation - condensation: Heat the mixture obtained in step (1) to 230 °C and hold for 100 min, and then the primary condensation product is collected by cooling to 100 °C, and the primary sublimation residue is obtained. By characterization, the primary condensation product is only ammonium fluoride (or ammonium bifluoride).

[0085] (3) Secondary sublimation - condensation: The primary sublimation residue obtained in step (2) is continuously heated to 700 °C and held for 100 min, and then the secondary condensation product is collected by cooling to 100 °C, and the secondary sublimation residue is obtained; among them, the secondary condensation product is characterized as a mixture of silicon fluoride and titanium fluoride.

[0086] (4) Tertiary sublimation - condensation: The secondary sublimation residue obtained in step (3) is continuously heated to 1100 °C and held for 100 min, and vanadium fluoride ((NH 4 ) 3 VF 6 ) will sublime out, and then the condensed tertiary condensation product is collected by cooling to 100 °C, and the tertiary sublimation residue is obtained; among them, the purity of the vanadium fluoride after condensation is characterized as 96.85%.

[0087] (5) The tertiary sublimation residue obtained in step (4) is titanium ore slag containing impurities such as calcium, magnesium, and iron, mainly in the form of FeF 3 . After impurity removal and purification of the tertiary sublimation residue, higher - purity FeF 3 can be used as a raw material for the production of lithium iron phosphate.

[0088] Comparative Example 2 The method is the same as that in Example 1, except that the second sublimation temperature is 510 °C (lower than 650 - 800 °C); (1) Fluorination reaction: The titanium - containing ore powder and ammonium fluoride are uniformly mixed according to a mass ratio of 1:4, and the two react fully at 200 °C for 100 min to obtain a mixture of fluorides corresponding to various elements.

[0089] (2) Primary sublimation - condensation: The mixture obtained in step (1) is heated to 350 °C and held for 100 min, and silicon fluoride ((NH 4 ) 2 SiF 6 ) and the unreacted fluorinating agent will first sublime out, and then the condensed primary condensation product is collected by cooling to 100 °C, and the primary sublimation residue is obtained. The primary condensation product is characterized as a mixture of silicon fluoride and unreacted ammonium fluoride.

[0090] (3) Secondary sublimation - condensation: The primary sublimation residue obtained in step (2) is continuously heated to 510 °C and held for 100 min, and there is no sublimation product.

[0091] (4) Tertiary sublimation - condensation: The residue after the treatment in step (3) is continuously heated to 1100 °C and held for 100 min, and vanadium fluoride ((NH 4 )3 VF 6 ) will sublime, and then the third-stage sublimation residue is obtained by cooling to 100 °C to collect the sublimated product after sublimation, and the third-stage sublimation residue is obtained; among them, the third-stage sublimated product is characterized as a mixture of vanadium fluoride and titanium fluoride.

[0092] (5) The third-stage sublimation residue obtained in step (4) is titanium ore slag containing impurities such as calcium, magnesium, and iron, mainly in the form of FeF 3 . The third-stage sublimation residue is obtained with higher purity FeF after impurity removal and purification 3 can be used as a raw material for the production of lithium iron phosphate.

[0093] Comparative Example 3 The method is the same as that of Example 1, except that the third sublimation temperature is 910 °C (lower than 1100 °C - 1200 °C); (1) Fluorination reaction: The titanium ore powder and ammonium fluoride are uniformly mixed at a mass ratio of 1:4, and the two react fully at 200 °C for 100 min to obtain a mixture of fluorides corresponding to various elements.

[0094] (2) First-stage sublimation-sublimation: The mixture obtained in step (1) is heated to 350 °C and kept warm for 100 min. The silicon fluoride ((NH 4 ) 2 SiF 6 ) and the unreacted fluorinating agent will first sublime, and then the sublimated product after sublimation is collected by cooling to 100 °C, and the first-stage sublimation residue is obtained. The first-stage sublimated product is characterized as a mixture of silicon fluoride and unreacted ammonium fluoride.

[0095] (3) Second-stage sublimation-sublimation: The first-stage sublimation residue obtained in step (2) is continuously heated to 700 °C and kept warm for 100 min. The titanium fluoride ((NH 4 ) 2 TiF 6 ) will sublime, and then the sublimated product after sublimation is collected by cooling to 100 °C, and the second-stage sublimation residue is obtained; among them, the second-stage sublimated product is characterized as titanium fluoride with a purity of 93.45%.

[0096] (4) Third-stage sublimation-sublimation: The second-stage sublimation residue obtained in step (3) is continuously heated to 910 °C and kept warm for 100 min, and there is no sublimation product.

[0097] (5) The third-stage sublimation residue obtained in step (4) is titanium ore slag containing vanadium fluoride and impurities such as calcium, magnesium, and iron.

[0098] Comparative Example 4 The method is the same as that of Example 1, except that the third sublimation temperature is 2400 °C (higher than 1100 °C to 1200 °C); (1) Fluorination reaction: The titanium-containing ore powder and ammonium fluoride are uniformly mixed at a mass ratio of 1:4, and the two react fully at 200 °C for 100 min to obtain a mixture of fluorides corresponding to various elements.

[0099] (2) First-stage sublimation-condensation: The mixture obtained in step (1) is heated to 350 °C and kept warm for 100 min. Silicon fluoride ((NH 4 ) 2 SiF 6 ) and the unreacted fluorinating agent will first sublime, and then the first-stage condensation product after condensation is collected by cooling to 100 °C, and the first-stage sublimation residue is obtained. By characterizing, the first-stage condensation product is a mixture of silicon fluoride and unreacted ammonium fluoride.

[0100] (3) Second-stage sublimation-condensation: The first-stage sublimation residue obtained in step (2) is continuously heated to 700 °C and kept warm for 100 min. Titanium fluoride ((NH 4 ) 2 TiF 6 ) will sublime, and then the second-stage condensation product after condensation is collected by cooling to 100 °C, and the second-stage sublimation residue is obtained; among them, by characterizing, the second-stage condensation product is titanium fluoride with a purity of 94.89%.

[0101] (4) Third-stage sublimation-condensation: The second-stage sublimation residue obtained in step (3) is continuously heated to 2400 °C and kept warm for 100 min, and then the third-stage condensation product after condensation is collected by cooling to 100 °C, and the third-stage sublimation residue is obtained; among them, by characterizing, the third-stage condensation product is vanadium fluoride and contains impurity elements of iron and magnesium.

[0102] In addition, the inventors of this case also referred to the foregoing embodiments and conducted tests with other raw materials, process operations, and process conditions described in this specification, and all obtained relatively ideal results.

[0103] It should be understood that the technical solutions of the present invention are not limited to the limitations of the above specific implementation cases. Any technical deformation made according to the technical solutions of the present invention without departing from the spirit of the present invention and the scope protected by the claims falls within the protection scope of the present invention.

Claims

1. A method for separating titanium-containing ore, characterized in that: include: A fluoriding agent is allowed to react with a titanium-containing ore to undergo a fluorination reaction to obtain a fluorinated product; wherein the titanium-containing ore at least includes titanium; The fluorinated product is subjected to a primary sublimation-desublimation treatment to obtain a mixture of silicon-containing fluoride and unreacted fluorinating agent, and a primary sublimation residue; Performing secondary sublimation-desublimation treatment on the primary sublimation residue to obtain titanium-containing fluoride and secondary sublimation residue; And, the secondary sublimation residue is subjected to a tertiary sublimation-desublimation treatment to obtain vanadium-containing fluoride and a tertiary sublimation residue.

2. The separation method according to claim 1, characterized in that include: The fluorinating agent and the titanium-containing ore are uniformly mixed and a fluorination reaction is carried out at 180-250° C.; and / or, the fluorination reaction time is 30-180 min; and / or, the fluorinating agent comprises ammonium fluoride and / or ammonium bifluoride; And / or, the mass ratio of the titanium-containing ore to the fluorinating agent is 1:3.2 to 1:6; And / or, the titanium-containing ore includes silicon oxide, titanium oxide, vanadium oxide and iron oxide.

3. The separation method according to claim 1, characterized in that include: Heating the fluorinated product to a first sublimation temperature for primary sublimation treatment to obtain a primary sublimation product and a primary sublimation residue; and cooling the primary sublimation product to a first desublimation temperature to perform a primary desublimation treatment to obtain a mixture of silicon-containing fluoride and unreacted fluorinating agent; Preferably, the first sublimation temperature is 300°C~450°C; preferably, the time of the primary sublimation treatment is 30~180min; preferably, the first condensation temperature is 80°C~160°C; preferably, the time of the primary condensation treatment is 10~180min; preferably, the silicon-containing fluoride includes (NH4)2SiF6.

4. The separation method according to claim 1, characterized in that include: Heating the primary sublimation residue to a second sublimation temperature for secondary sublimation to obtain a secondary sublimation product and a secondary sublimation residue; and cooling the secondary sublimation product to a second desublimation temperature to perform secondary desublimation treatment to obtain titanium-containing fluoride; Preferably, the second sublimation temperature is 650°C~800°C; preferably, the time of the secondary sublimation treatment is 30~180min; preferably, the second condensation temperature is 80°C~180°C; preferably, the time of the secondary condensation treatment is 10~180min; preferably, the titanium-containing fluoride includes (NH4)2TiF6; preferably, the titanium-containing fluoride is at least used to prepare titanium dioxide.

5. The separation method according to claim 1, characterized in that include: Heating the secondary sublimation residue to a third sublimation temperature for tertiary sublimation treatment to obtain a tertiary sublimation product and a tertiary sublimation residue; and cooling the three-stage sublimation product to a third desublimation temperature to perform a three-stage desublimation treatment to obtain vanadium-containing fluoride; Preferably, the third sublimation temperature is 1100°C~1200°C; preferably, the time of the three-stage sublimation treatment is 30~180min; preferably, the third condensation temperature is 80°C~180°C; preferably, the time of the three-stage condensation treatment is 10~180min; preferably, the vanadium-containing fluoride includes (NH4)3VF6; preferably, the vanadium-containing fluoride is at least used to prepare vanadium oxide.

6. The separation method according to claim 1, characterized in that: The fluorination products include silicon-containing fluorides, titanium-containing fluorides and vanadium-containing fluorides; And / or, the titanium-containing ore includes at least titanium and any one or a combination of two or more of silicon, vanadium and iron elements; preferably, the titanium-containing ore also includes any one or more combinations of calcium, magnesium, aluminum, manganese and chromium elements.

7. The separation method according to claim 1, characterized in that Also includes: Reusing the mixture of silicon-containing fluoride obtained by the primary sublimation-desublimation treatment and the unreacted fluorinating agent for fluorination reaction; And / or, the separation method further comprises: separating the mixture of the silicon-containing fluoride obtained by the primary sublimation-desublimation treatment and the unreacted fluorinating agent to obtain the silicon-containing fluoride and the fluorinating agent respectively; the silicon-containing fluoride is at least used to prepare silicon dioxide; And / or, the separation method further comprises: removing impurities and purifying the tertiary sublimation residue to obtain FeF3; preferably, the FeF3 is at least used to prepare lithium iron phosphate.

8. A separation system for titanium-containing ore, which is applied to the separation method according to any one of claims 1 to 7, characterized in that include: A fluorination reaction unit, which is at least capable of causing a fluorination reaction between a fluorination agent and a titanium-containing ore to form a fluorination product; A primary sublimation-desublimation unit, which is capable of at least performing a primary sublimation-desublimation treatment on the fluorinated product; A secondary sublimation-desublimation unit, which is capable of performing at least a primary sublimation-desublimation treatment on the fluorinated product; and a three-stage sublimation-desublimation unit, which is capable of performing at least one-stage sublimation-desublimation treatment on the fluorinated product.

9. The separation system according to claim 8, characterized in that: The fluorination reaction unit includes a mixing device and a fluorination furnace; And / or, the primary sublimation-desublimation unit comprises a primary sublimation device and a primary desublimation device; And / or, the secondary sublimation-desublimation unit includes a secondary sublimation device and a secondary desublimation device; And / or, the three-stage sublimation-desublimation unit includes a three-stage sublimation device and a three-stage desublimation device.

10. The separation system according to claim 8, characterized in that Also includes: Impurity removal and purification unit; preferably, the impurity removal and purification unit is capable of at least performing impurity removal and purification treatment on the third-level sublimation residue.

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