Ion exchange system and method for extracting tungsten from a high concentration tungsten ore leach

Abstract

The present application relates to the field of hydrometallurgy, and particularly relates to an ion exchange system and method for extracting tungsten from high-concentration tungsten ore leaching solution, wherein the ion exchange system for extracting tungsten from high-concentration tungsten ore leaching solution comprises a double-layer multi-way valve system layered in an up-down manner, the double-layer multi-way valve system comprises an upper multi-way valve and a lower multi-way valve, and cation exchange resin and anion exchange resin are filled in resin columns of the upper multi-way valve and the lower multi-way valve respectively. The present application can realize effective adsorption of tungstate in 250g / L high-concentration sodium tungstate mother liquor by using ion exchange resin, and the tungsten adsorption amount reaches more than 200g / kg, which is higher than the conventional level of 150-180g / kg in the current industry. Moreover, the mother liquor can directly enter the multi-way valve system after pressure filtration without the need of dilution to reduce the mother liquor concentration, so that the wastewater discharge in the tungsten hydrometallurgy process is reduced by more than 70%, and the amount of eluant is reduced by more than 20%.

Description

Technical Field

[0001] This invention relates to the field of hydrometallurgy, and specifically to an ion exchange system and method for extracting tungsten from high-concentration tungsten ore leachate. Background Technology

[0002] Tungsten metal, in its elemental form, is a silvery-white, lustrous metal with high hardness, a high melting point, and stable chemical properties. It is primarily used to manufacture lamp filaments and high-speed cutting alloy steel, as well as superhard molds. It is also used in optical and chemical instruments. Currently, the most important tungsten source in my country is APT (ammonium paratungstate), accounting for more than half of the national production. However, the domestic tungsten industry currently mostly uses high-temperature alkaline leaching combined with resin extraction for APT extraction.

[0003] Currently, most hydrometallurgical tungsten smelting processes in the industry utilize ion exchange technology. Specifically, the tungsten ore alkali leaching solution is first subjected to tungsten-alkali separation to obtain sodium tungstate, which is then dissolved for ion exchange extraction of tungsten. The sodium tungstate formed in this method contains a large amount of alkali. High concentrations of alkali inhibit the binding of resin and tungstate ions. If the alkali level is too high, the resin adsorption capacity is too low to achieve industrial-scale operational value. Therefore, the concentrated dissolved solution needs to be diluted from approximately 250-300 g / L to 20 g / L for ion exchange adsorption of tungsten. This process requires a large amount of dilution water.

[0004] Meanwhile, the adsorption tailings are high-salt wastewater, and the large daily generation of these tailings places a significant environmental burden on tungsten extraction companies, requiring substantial investment in wastewater treatment. Furthermore, the large volume of wastewater can have a significant negative impact on the local ecosystem. Currently, wastewater treatment has become a pressing problem for the tungsten hydrometallurgical industry. Summary of the Invention

[0005] In the existing technology, when using ion exchange resin to adsorb tungsten, the performance characteristics of the anion exchange resin used in the tungsten industry are limited, requiring a large amount of water to be used for dilution before adsorption, which brings about significant environmental pressure and relatively high production costs.

[0006] Therefore, the technical problem to be solved by the present invention is that the existing technology of using ion exchange resin to adsorb tungsten has the disadvantages of high environmental pressure and high production cost. The present invention provides an ion exchange system and method for extracting tungsten from high-concentration tungsten ore leachate to solve the above problems.

[0007] This invention uses another resin to treat the mother liquor, reducing the alkalinity of the mother liquor before the anion exchange resin adsorbs tungstate ions. At the same time, it combines multi-way valve technology to improve the utilization rate of the two resins, reduce water consumption and eluent consumption. Since multi-way valves are used for adsorption, the adsorption section in the system must be connected in series with multiple columns. However, simply using two multi-way valves in series cannot achieve this function. Therefore, this technology has developed a multi-way valve structure with upper and lower layers to achieve high-efficiency tungstate ion adsorption.

[0008] Specifically, the technical solution provided by this invention is as follows:

[0009] An ion exchange system for extracting tungsten from a high-concentration tungsten ore leaching solution includes a two-layer multi-way valve system, comprising an upper multi-way valve and a lower multi-way valve; the resin columns of the upper and lower multi-way valves are respectively filled with cation exchange resin and anion exchange resin.

[0010] Preferably, the upper multi-way valve and the lower multi-way valve are each composed of a plurality of resin columns, and the dual-layer multi-way valve system also includes an intermediate layer, in which a connecting plate is provided; the resin columns in the upper multi-way valve and the lower multi-way valve are each divided into three parts; the resin columns of the first part in the upper multi-way valve and the resin columns of the first part in the lower multi-way valve are sequentially interconnected through the connecting plate to form an adsorption zone; the resin columns of the second part in the upper multi-way valve are connected in series and / or in parallel to form a washing zone, and the resin columns of the second part in the lower multi-way valve are connected in series and / or in parallel to form a washing zone; the resin columns of the third part in the upper multi-way valve are connected in series and / or in parallel to form an analytical zone, and the resin columns of the third part in the lower multi-way valve are connected in series and / or in parallel to form an analytical zone.

[0011] The high-concentration mother liquor after tungsten-alkali separation from the alkali leaching solution of wolframite is subjected to adsorption treatment in the adsorption zone. The resin columns in the water washing zone of the upper and lower multi-way valves are washed by water. The resin columns in the desorption zone of the upper and lower multi-way valves are desorbed by desorption solution.

[0012] The water washing zones in both the upper and lower multi-way valves are set in two groups, one after the adsorption zone and the other after the desorption zone.

[0013] Preferably, the connection method of the resin columns in the adsorption zone includes, but is not limited to, six columns in series, five columns in series, two parallel four series, and two parallel three series. In addition, different numbers of resin columns can be connected in series and then in parallel in the adsorption zone, such as two series and three series in parallel, or three series and four series in parallel.

[0014] And / or, the connection method of the resin columns in the washing zone includes, but is not limited to, three columns connected in series;

[0015] And / or, the connection methods of the resin columns in the analytical region include, but are not limited to, six columns in series, five columns in series, two parallel four series, and two parallel three series.

[0016] Preferably, the upper multi-way valve and the lower multi-way valve are each composed of 10-30 resin columns; preferably, a total of 2-10 resin columns in the upper and lower multi-way valves are directly connected through the connecting plate of the intermediate layer to form an adsorption zone; the cation exchange resin of the upper multi-way valve performs the function of alkalinity reduction, and the anion exchange resin of the lower multi-way valve performs the function of tungstate adsorption; more preferably, a total of 6 resin columns are connected to form an adsorption zone.

[0017] Preferably, the ratio of the number of resin columns in the upper multi-way valve to the lower multi-way valve is (1:3)-(3:1), wherein preferably the number of resin columns in the upper multi-way valve and the lower multi-way valve is the same.

[0018] Preferably, in the upper multi-way valve, the number of resin columns in the water washing zone after adsorption is 1-10, preferably 3; the number of resin columns in the desorption zone is 2-10, preferably 6; and the number of resin columns in the water washing zone after desorption is 1-10, preferably 3.

[0019] And / or, in the lower multi-way valve, the number of resin columns in the water washing zone after adsorption is 1-10, preferably 3; the number of resin columns in the desorption zone is 2-10, preferably 6; and the number of resin columns in the water washing zone after desorption is 1-10, preferably 3.

[0020] And / or, the resin column can switch between the adsorption zone, the washing zone, the desorption zone and the washing zone by the rotation of the upper and lower multi-way valves driven by the motor.

[0021] This invention also provides an ion exchange method for extracting tungsten from high-concentration tungsten ore leachate. The method utilizes the aforementioned ion exchange system for extracting tungsten from high-concentration tungsten ore leachate. The exchange process includes: the high-concentration mother liquor of wolframite alkaline leachate after tungsten-alkali separation is first passed through the cation exchange resin column in the upper multi-way valve adsorption zone to reduce alkalinity; the treated mother liquor then enters the anion exchange resin column in the lower multi-way valve adsorption zone to adsorb tungstate ions.

[0022] Preferably, the specific application process includes the following steps:

[0023] 1) The high-concentration mother liquor, which has undergone tungsten-alkali separation pretreatment, is pumped into the cation exchange resin in the upper multi-way valve adsorption zone to reduce the alkalinity of the mother liquor.

[0024] 2) The mother liquor with reduced alkalinity from the upper multi-way valve system enters the anion exchange resin in the adsorption zone of the lower multi-way valve through the connecting plate between the upper and lower multi-way valves to adsorb tungstate.

[0025] 3) The feed solution that has completed the first-stage tungstate adsorption enters the upper multi-way valve again to further reduce the alkalinity before entering the lower multi-way valve for the second-stage tungstate adsorption; this process is repeated alternately to perform multi-stage alkalinity reduction and tungstate adsorption.

[0026] Preferably, the concentration of sodium hydroxide in the high-concentration mother liquor is 70-100 g / L, and the pH of the mother liquor after exchange treatment is 12-14, preferably 13-14.

[0027] Preferably, the single-column resin filling volume ratio of the upper multi-way valve and the lower multi-way valve is 1:(3-15), more preferably 1:7, to ensure that the pH of the mother liquor treated by the upper multi-way valve is qualified, the tungsten adsorption capacity of the exchange resin of the lower multi-way valve is higher than 200g / kg, the tungsten concentration of the adsorbed tail liquid is less than 0.1g / L, and the switching frequency of the two resin columns is consistent, so as to achieve smooth and stable operation of the entire system.

[0028] Preferably, the inlet flow rate of the mother liquor in the adsorption zone is 0.3-5 BV / h relative to the anion exchange resin loading of the lower multi-way valve, preferably 1 BV / h.

[0029] Preferably, the switching angle between the upper multi-way valve and the lower multi-way valve is 5-60°, preferably 20°, and this switching angle is based on the 18 resin column system.

[0030] Preferably, the switching angular velocity between the upper multi-way valve and the lower multi-way valve discs is 1-100° / s, and more preferably 40° / s.

[0031] Preferably, the switching interval between the upper multi-way valve and the lower multi-way valve discs is 0.1-5h, more preferably 0.1-2h, and even more preferably 50min.

[0032] Preferably, the resin columns in the upper and lower multi-way valves are driven by a single motor to rotate at the same frequency, while the intermediate connecting plate and the inlet and outlet pipes remain stationary, thereby enabling the upper and lower multi-way valves to be used together.

[0033] Alternatively, two motors can be used to drive the upper and lower multi-way valves respectively to rotate the cutting column at different frequencies. The top motor drives the upper multi-way valve, and the bottom motor drives the lower multi-way valve, so as to facilitate the adjustment of the operation mode of the two exchange resins and the switching of the operation status at any time.

[0034] Preferably, two motors are used to control the upper and lower multi-way valve discs respectively, and the rotation frequency can be changed as needed to ensure the system's sealing and flexibility, as well as the accuracy of column switching.

[0035] Preferably, the desorption agent used for the cation exchange resin in the upper multi-way valve is a strong acid solution with a mass percentage concentration of 2-30%, and more preferably an aqueous sulfuric acid solution with a mass percentage concentration of 8%.

[0036] Preferably, the desorption agent used for the anion exchange resin in the lower multi-way valve is a mixed solution of 100-450 g / L ammonium chloride aqueous solution and 20-200 g / L ammonia solution, and more preferably a mixed aqueous solution of 250 g / L ammonium chloride aqueous solution and 100 g / L ammonia solution.

[0037] Preferably, the cation exchange resin desorption flow rate in the upper multi-way valve is 0.2-10 BV / h, and more preferably 2 BV / h.

[0038] Preferably, the desorption flow rate of the anion exchange resin in the lower multi-way valve is 0.2-10 BV / h, and more preferably 1 BV / h.

[0039] Preferably, the water flow rate in the water washing zone of the upper multi-way valve and the lower multi-way valve is 0.2-10 BV / h, preferably 4 BV / h.

[0040] Preferably, the cation exchange resin in the upper multi-way valve is a macroporous or gel-based strong or weak acid cation exchange resin, and the resin matrix is ​​at least one of styrene-based, acrylic-based, and acrylonitrile-based, preferably D113 type macroporous weak acid cation exchange resin.

[0041] Preferably, the anion exchange resin in the lower multi-way valve is a macroporous or gel-type strong or weak base anion exchange resin, and the resin matrix is ​​at least one of styrene-based, acrylic-based, and acrylonitrile-based resins, preferably a uniform particle size of 201×8 type gel strong base anion exchange resin.

[0042] Preferably, the mother liquor is introduced into the container from top to bottom or the order of the upper and lower resin columns is adjusted to be introduced from bottom to top, with the top-inlet and bottom-outlet method being preferred.

[0043] The technical solution of this invention has the following advantages:

[0044] An ion exchange system for extracting tungsten from high-concentration tungsten ore leachate comprises a two-layer multi-port valve system, consisting of an upper multi-port valve and a lower multi-port valve. The resin columns of the upper and lower multi-port valves are respectively filled with cation exchange resin and anion exchange resin. This ion exchange system can directly feed a high-concentration sodium tungstate solution after tungsten-alkali separation into the multi-port valve ion exchange system for tungsten adsorption. By using two resins in combination and employing the two-layer multi-port valve device, the performance of the resins can be maximized. Compared to traditional fixed-bed anion resin adsorption, it can reduce wastewater discharge by more than 75%, significantly reducing annual wastewater treatment costs, greatly alleviating the environmental pressure on tungsten extraction enterprises, lowering operating costs, and improving economic efficiency. It provides a new solution for resin-based tungsten extraction. Compared to extraction and chemical methods, resin-based tungsten extraction offers greater competitiveness, and its high degree of automation reduces labor costs for enterprises. Attached Figure Description

[0045] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0046] Figure 1 This is a three-dimensional structural diagram of the dual-layer multi-way valve system used in the embodiments of the present invention;

[0047] Figure 2 yes Figure 1 A schematic diagram of the main structure of a dual-layer multi-way valve system;

[0048] Figure 3 yes Figure 1 A top view of the structure of a dual-layer multi-way valve system;

[0049] Figure 4 This is the method used in Example 1. Figure 1 The operating process flow diagram of the dual-layer multi-way valve system;

[0050] 1-Top motor, 2-Bottom motor, 3-Upper multi-way valve filled with cation exchange resin, 4-Lower multi-way valve filled with anion exchange resin, 5-Inlet pipe for the adsorption zone of the upper multi-way valve, 6-Inlet pipe for the desorption zone of the upper multi-way valve, 7-Inlet pipe for the washing zone of the upper multi-way valve, 8-Outlet pipe for the adsorption zone of the lower multi-way valve, 9-Inlet pipe for the washing zone of the lower multi-way valve, 10-Inlet pipe for the desorption zone of the lower multi-way valve, 11-Outlet pipe for the first peak liquid of the desorption zone of the lower multi-way valve, 12-Outlet pipe for the peak liquid of the desorption zone of the lower multi-way valve, 13-Outlet pipe for the last section of the desorption zone of the lower multi-way valve, 14-Outlet pipe for the desorption zone of the upper multi-way valve, 15-Outlet pipe for the washing zone of the upper multi-way valve, 16-Lower multi-way valve The discharge pipeline of the washing zone consists of the following components: 5 - the solution in the feed pipeline of the upper multi-way valve adsorption zone is a mother liquor with a tungsten concentration ≥250g / L, with a flow rate of 1BV / h; 6 - the solution in the feed pipeline of the upper multi-way valve desorption zone is a sulfuric acid solution with a mass fraction of 8%, with a flow rate of 2BV / h; 7 - the water in the feed pipeline of the upper multi-way valve washing zone has a flow rate of 4BV / h; 8 - the solution in the discharge pipeline of the lower multi-way valve adsorption zone is an adsorption tail liquid with a tungsten concentration <0.01g / L; 9 - the water in the feed pipeline of the lower multi-way valve washing zone has a flow rate of 4BV / h; and 10 - the solution in the feed pipeline of the lower multi-way valve desorption zone is a desorption solution of 250g / L ammonium chloride and 100g / L ammonia water, with a flow rate of 1BV / h. Detailed Implementation

[0051] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0052] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0053] Example 1

[0054] This embodiment provides an ion exchange system for tungsten extraction from high-concentration tungsten ore leaching solutions. The system includes a two-layer multi-port valve system, with the upper multi-port valve system comprising an upper multi-port valve, a lower multi-port valve, and several resin columns. The combination of the two-layer multi-port valve system and the resin columns enables the adsorption of high-concentration sodium tungstate solution. The two-layer multi-port valve system used in this embodiment is an 18-column system, and its three-dimensional structure is as follows: Figure 1 As shown, the main view structure is as follows: Figure 2 As shown, the top view of the structure is as follows Figure 3As shown, the distribution of the 36 resin columns in the upper and lower multi-way valves, the connection method in each area, and the liquid flow are as follows: Figure 4 As shown. This embodiment uses... Figures 1-3 The ion exchange system shown extracts tungsten from a high-concentration tungsten ore leaching solution (mother liquor). The specific process is as follows: the mother liquor enters the upper multi-way valve adsorption zone feed pipe 5 for tungsten adsorption; the adsorption tail liquid flows out from the lower multi-way valve adsorption zone discharge pipe 8. In the upper multi-way valve, the eluent enters the upper multi-way valve 3 filled with cation exchange resin from the upper multi-way valve eluent zone feed pipe 6 for eluent analysis, and then flows out from the upper multi-way valve eluent zone discharge pipe 14. Water enters the upper multi-way valve 3 filled with cation exchange resin from the upper multi-way valve washing zone feed pipe 7 for washing, and then flows out from the upper multi-way valve washing zone discharge pipe 15. In the lower multi-way valve, water flows out from the lower multi-way valve washing zone feed pipe 9. The resin enters the lower multi-way valve 4 filled with anion exchange resin for washing, and then flows out from the discharge pipe of the washing zone of the lower multi-way valve. The eluent enters the lower multi-way valve 4 filled with anion exchange resin from the feed pipe 10 of the lower multi-way valve for eluent analysis. Among them, the first peak liquid flows out from the first peak liquid discharge pipe 11 of the eluent analysis zone of the lower multi-way valve, the peak liquid flows out from the peak liquid discharge pipe 12 of the eluent analysis zone of the lower multi-way valve, and the last liquid flows out from the last liquid discharge pipe 13 of the eluent analysis zone of the lower multi-way valve. The upper multi-way valve 3 filled with cation exchange resin and the lower multi-way valve 4 filled with anion exchange resin are rotated by the top motor 1 and the bottom motor 2, respectively, realizing the switching of the resin column in the adsorption zone, the washing zone and the eluent analysis zone.

[0055] In this embodiment, the eluent in the upper multi-way valve eluent zone is an 8% sulfuric acid solution, and the eluent in the lower multi-way valve eluent zone is a mixed solution of ammonium chloride and ammonia, wherein the concentration of ammonium chloride is 250 g / L and the concentration of ammonia is 100 g / L. The solution in the feed pipeline of the upper multi-way valve adsorption zone is a mother liquor with a tungsten concentration of 250 g / L and a sodium hydroxide concentration of 100 g / L. The resin packed in the upper multi-way valve is D113 type macroporous weak acid cation exchange resin, with a single resin column packing volume of 200 mL. The resin packed in the lower multi-way valve is uniform particle size 201×8 type gel strong base anion exchange resin, with a single resin column packing volume of 1400 mL. The upper multi-way valve switches at an angle of 20° each time, with a switching interval of 50 min. The lower multi-way valve switches at an angle of 20° each time, with a switching interval of 50 min. Some parameters in this embodiment are shown in Table 1, and the test data are shown in Table 3.

[0056] Example 2

[0057] The difference between this embodiment and Embodiment 1 is that the upper multi-way valve is filled with 001×7 type strong acid cation exchange resin. Other conditions are the same as in Embodiment 1. Some parameters in this embodiment are shown in Table 1, and the test data are shown in Table 3.

[0058] Example 3

[0059] The difference between this embodiment and Embodiment 1 is that the lower multi-way valve is filled with LSD-363S macroporous polyamine resin. Other conditions are the same as in Embodiment 1. Some parameters in this embodiment are shown in Table 1, and the test data are shown in Table 3.

[0060] Example 4

[0061] The difference between this embodiment and Embodiment 1 is that the filling volume of a single resin column in the upper multi-way valve is 400 mL. Other conditions are the same as in Embodiment 1. Some parameters in this embodiment are shown in Table 1, and the test data are shown in Table 3.

[0062] Example 5

[0063] The difference between this embodiment and Embodiment 1 is that the filling volume of a single resin column in the lower multi-way valve is 2000 mL. Other conditions are the same as in Embodiment 1. Some parameters in this embodiment are shown in Table 1, and the test data are shown in Table 3.

[0064] Example 6

[0065] The difference between this embodiment and embodiment 1 is that the upper multi-way valve switches at an angle of 40° each time, and the switching interval is 50 minutes. Other conditions are the same as in embodiment 1. Some parameters in this embodiment are shown in Table 2, and the test data are shown in Table 3.

[0066] Example 7

[0067] The difference between this embodiment and Embodiment 1 is that the resin column distribution in both the upper and lower multi-way valves is an adsorption zone: water washing zone: desorption zone: water washing zone = 5:4:5:4. In both the upper and lower multi-way valves, the resin columns in the adsorption zone are connected in series with 5 columns, and the resin columns in the water washing zone are connected in series with 4 columns. The resin columns in the desorption zone of the upper multi-way valve are connected in series with 5 columns, and the resin columns in the desorption zone of the lower multi-way valve are connected in series with 5 columns. Other conditions are the same as in Embodiment 1. Some parameters in this embodiment are shown in Table 2, and the test data are shown in Table 3.

[0068] Example 8

[0069] The difference between this embodiment and Embodiment 1 is that the resin column distribution in both the upper and lower multi-way valves is adsorption zone: water washing zone: desorption zone: water washing zone = 8:2:5:3. In both the upper and lower multi-way valves, the resin columns in the adsorption zone are connected in a two-parallel, four-series configuration. The water washing zone after adsorption is connected in a two-column series configuration, and the water washing zone after desorption is connected in a three-column series configuration. The resin columns in the desorption zone of the upper multi-way valve are connected in a five-column series configuration, and the desorption zone of the lower multi-way valve is connected in a five-column series configuration. Other conditions are the same as in Embodiment 1. Some parameters in this embodiment are shown in Table 2, and the test data are shown in Table 3.

[0070] Example 9

[0071] The difference between this embodiment and Embodiment 1 is that the resin columns in the upper multi-way valve adsorption zone are connected in a two-parallel, three-series configuration, while the resin columns in the lower multi-way valve adsorption zone are connected in a six-column series configuration. Other conditions are the same as in Embodiment 1. Some parameters in this embodiment are shown in Table 2, and the test data are shown in Table 3.

[0072] Example 10

[0073] The difference between this embodiment and embodiment 1 is that the resin columns in the upper multi-way valve adsorption zone are connected in series with 6 columns, while the resin columns in the lower multi-way valve adsorption zone are connected in parallel with 3 columns in series. Other conditions are the same as in embodiment 1. Some parameters in this embodiment are shown in Table 2, and the test data are shown in Table 3.

[0074] Table 1

[0075]

[0076] Table 2

[0077]

[0078]

[0079] Table 3

[0080]

[0081] The above results demonstrate that the technical solution of this invention is a new technology for extracting tungsten from high-concentration mother liquor. It allows the high-concentration sodium tungstate solution after tungsten-alkali separation to be directly fed into a multi-valve ion exchange system for tungsten adsorption. By using two resins in combination and employing a double-layer multi-valve device, the resin performance can be maximized. Compared to traditional anion exchange resin fixed-bed adsorption, this method can reduce wastewater discharge by more than 75%, significantly reducing annual wastewater treatment costs, greatly alleviating the environmental pressure on tungsten extraction enterprises, lowering operating costs, and improving economic efficiency. It provides a new solution for resin-based tungsten extraction. Compared to extraction and chemical methods, resin-based tungsten extraction offers greater competitiveness, and its high degree of automation significantly reduces labor costs for enterprises.

[0082] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. An ion exchange system for extracting tungsten from high-concentration tungsten ore leachate, characterized in that, The system includes a two-layer multi-way valve system with upper and lower layers, wherein the upper multi-way valve and the lower multi-way valve are respectively filled with cation exchange resin and anion exchange resin in their resin columns. The upper and lower multi-way valves are each composed of several resin columns. The dual-layer multi-way valve system also includes an intermediate layer with a connecting plate. The resin columns in both the upper and lower multi-way valves are divided into three parts. The resin columns in the first part of the upper multi-way valve and the first part of the lower multi-way valve are sequentially interconnected via the connecting plate to form an adsorption zone. The resin columns in the second part of the upper multi-way valve are connected in series and / or parallel to form a washing zone, and the resin columns in the second part of the lower multi-way valve are connected in series and / or parallel to form a washing zone. The resin columns in the third part of the upper multi-way valve are connected in series and / or parallel to form a desorption zone, and the resin columns in the third part of the lower multi-way valve are connected in series and / or parallel to form a desorption zone. The high-concentration mother liquor after tungsten-alkali separation from the alkali leaching solution of wolframite is subjected to adsorption treatment in the adsorption zone. The resin columns in the water washing zone of the upper and lower multi-way valves are washed by water. The resin columns in the desorption zone of the upper and lower multi-way valves are desorbed by desorption solution. The water washing zones in both the upper and lower multi-way valves are set in two groups, one after the adsorption zone and the other after the desorption zone.

2. The ion exchange system according to claim 1, characterized in that, The upper multi-way valve and the lower multi-way valve are each composed of 10-30 resin columns; And / or, the ratio of the number of resin columns in the upper multi-way valve and the lower multi-way valve is (1:3) to (3:1); And / or, in the upper multi-way valve, the number of resin columns in the water washing zone after adsorption is 1-10; the number of resin columns in the desorption zone is 2-10; and the number of resin columns in the water washing zone after desorption is 1-10. And / or, in the lower multi-way valve, the number of resin columns in the water washing zone after adsorption is 1-10; the number of resin columns in the desorption zone is 2-10; and the number of resin columns in the water washing zone after desorption is 1-10. And / or, the resin column can switch between the adsorption zone, the washing zone, the desorption zone and the washing zone by the rotation of the upper and lower multi-way valves driven by the motor.

3. The ion exchange system according to claim 2, characterized in that, The upper and lower multi-way valves have a total of 2-10 resin columns directly connected by a connecting plate in the middle layer to form an adsorption zone; the cation exchange resin of the upper multi-way valve completes the alkalinity reduction function, and the anion exchange resin of the lower multi-way valve completes the tungstate adsorption function. And / or, the number of resin columns in the upper multi-way valve and the lower multi-way valve is the same; And / or, in the upper multi-way valve, the number of resin columns in the water washing zone after adsorption is 3; the number of resin columns in the desorption zone is 6; and the number of resin columns in the water washing zone after desorption is 3. And / or, in the lower multi-way valve, the number of resin columns in the water washing zone after adsorption is 3; the number of resin columns in the desorption zone is 6; and the number of resin columns in the water washing zone after desorption is 3.

4. The ion exchange system according to claim 3, characterized in that, The upper and lower multi-way valves are connected by a total of 6 resin columns to form an adsorption zone.

5. An ion exchange method for extracting tungsten from high-concentration tungsten ore leachate, characterized in that, The ion exchange system for extracting tungsten from high-concentration tungsten ore leaching solution according to any one of claims 1-4 is used for exchange treatment. The exchange process includes: the high-concentration mother liquor of wolframite alkaline leaching solution after tungsten-alkali separation is first passed through the cation exchange resin column of the upper multi-way valve adsorption zone to reduce the alkalinity, and the treated mother liquor enters the anion exchange resin column of the lower multi-way valve adsorption zone to adsorb tungstate.

6. The ion exchange method according to claim 5, characterized in that, The specific application process includes the following steps: 1) The high-concentration mother liquor, which has undergone tungsten-alkali separation pretreatment, is pumped into the cation exchange resin in the upper multi-way valve adsorption zone to reduce the alkalinity of the mother liquor. 2) The mother liquor with reduced alkalinity from the upper multi-way valve system enters the anion exchange resin in the adsorption zone of the lower multi-way valve through the connecting plate between the upper and lower multi-way valves to adsorb tungstate. 3) The feed solution that has completed the first-stage tungstate adsorption enters the upper multi-way valve again to further reduce the alkalinity before entering the lower multi-way valve for the second-stage tungstate adsorption; this process is repeated alternately to perform multi-stage alkalinity reduction and tungstate adsorption.

7. The ion exchange method according to claim 5 or 6, characterized in that, The concentration of sodium hydroxide in the high-concentration mother liquor is 70-100 g / L, and the pH of the mother liquor after exchange treatment is 12-14. And / or, the single-column resin filling volume ratio of the upper multi-way valve to the lower multi-way valve is 1:(3-15), which is used to ensure that the pH of the mother liquor treated by the upper multi-way valve is qualified, the tungsten adsorption capacity of the exchange resin of the lower multi-way valve is higher than 200 g / kg, the tungsten concentration of the adsorbed tail liquid is less than 0.1 g / L, and the switching frequency of the two resin columns is consistent, so as to achieve smooth and stable operation of the entire system.

8. The ion exchange method according to claim 7, characterized in that, The pH of the mother liquor after the exchange treatment is 13-14; And / or, the single-column resin filling volume ratio of the upper multi-way valve to the lower multi-way valve is 1:

7.

9. The ion exchange method according to claim 5 or 6, characterized in that, The inlet flow rate of the mother liquor in the adsorption zone is 0.3-5 BV / h compared to the anion exchange resin loading of the lower multi-way valve.

10. The ion exchange method according to claim 9, characterized in that, The inlet flow rate of the mother liquor in the adsorption zone is 1 BV / h compared to the anion exchange resin loading of the lower multi-way valve.

11. The ion exchange method according to claim 5 or 6, characterized in that, The switching angle between the upper-level multi-way valve and the lower-level multi-way valve is 5-60° each time. And / or, the switching angular velocity between the two discs of the upper multi-way valve and the lower multi-way valve is 1-100° / s; And / or, the switching interval between the upper multi-way valve and the lower multi-way valve discs is 0.1-5 h.

12. The ion exchange method according to claim 11, characterized in that, The upper multi-way valve and the lower multi-way valve switch at an angle of 20° each time, and this switching angle is based on the 18 resin column system. And / or, the switching angular velocity between the two discs of the upper multi-way valve and the lower multi-way valve is 40° / s; And / or, the switching interval between the upper multi-way valve and the lower multi-way valve discs is 0.1-2 h.

13. The ion exchange method according to claim 12, characterized in that, The switching interval between the upper and lower multi-way valve discs is 50 minutes.

14. The ion exchange method according to claim 5 or 6, characterized in that, The resin columns in the upper and lower multi-way valves are driven by a single motor to rotate at the same frequency, while the intermediate connecting plate and the inlet and outlet pipes remain stationary, thereby enabling the upper and lower multi-way valves to be used together. Alternatively, two motors can be used to drive the upper and lower multi-way valves respectively to rotate the cutting column at different frequencies. The top motor drives the upper multi-way valve, and the bottom motor drives the lower multi-way valve, so as to facilitate the adjustment of the operation mode of the two exchange resins and the switching of the operation status at any time. And / or, the desorption agent used for the cation exchange resin in the upper multi-way valve is a strong acid solution with a mass percentage concentration of 2-30%.

15. The ion exchange method according to claim 14, characterized in that, Two motors are used to control the upper and lower multi-way valve discs respectively. The rotation frequency can be adjusted as needed to ensure the system's sealing and flexibility, as well as the accuracy of column switching. And / or, the desorption agent used for the cation exchange resin in the upper multi-way valve is an 8% (w / w) aqueous sulfuric acid solution.

16. The ion exchange method according to claim 5 or 6, characterized in that, The desorption agent used for the anion exchange resin in the lower multi-way valve is a mixed solution of 100-450 g / L ammonium chloride aqueous solution and 20-200 g / L ammonia solution.

17. The ion exchange method according to claim 16, characterized in that, The desorption agent used for the anion exchange resin in the lower multi-way valve is a mixed aqueous solution of 250 g / L ammonium chloride and 100 g / L ammonia.

18. The ion exchange method according to claim 5 or 6, characterized in that, The cation exchange resin in the upper multi-way valve has a desorption flow rate of 0.2-10 BV / h; And / or, the desorption flow rate of the anion exchange resin in the lower multi-way valve is 0.2-10 BV / h; And / or, the water flow rate in the water washing zone of the upper multi-way valve and the lower multi-way valve is 0.2-10 BV / h.

19. The ion exchange method according to claim 18, characterized in that, The cation exchange resin in the upper multi-way valve has a desorption flow rate of 2 BV / h. And / or, the desorption flow rate of the anion exchange resin in the lower multi-way valve is 1 BV / h; And / or, the water flow rate in the water washing zone of the upper multi-way valve and the lower multi-way valve is 4 BV / h.

20. The ion exchange method according to claim 5 or 6, characterized in that, The cation exchange resin in the upper multi-way valve is a macroporous or gel-type strong or weak acid cation exchange resin, and the resin matrix is ​​at least one of styrene-based, acrylic-based, and acrylonitrile-based. And / or, the anion exchange resin in the lower multi-way valve is a macroporous or gel-type strong or weak base anion exchange resin, and the resin matrix is ​​at least one of styrene-based, acrylic-based, and acrylonitrile-based. And / or, the mother liquor can be fed into the container from top to bottom or the order of the upper and lower resin columns can be adjusted to be from bottom to top.

21. The ion exchange method according to claim 20, characterized in that, The cation exchange resin in the upper multi-way valve is D113 type macroporous weak acid cation exchange resin. And / or, the anion exchange resin in the lower multi-way valve is a uniform particle size 201×8 type gel strong base anion exchange resin. And / or, the mother liquor is introduced in a top-in, bottom-out manner.

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