PH regulation and control deamination separation device for ammonium tungstate and molybdate mixed solution

Abstract

The utility model discloses a pH regulation and control deamination separation device for an ammonium tungstate and molybdate mixed solution, and belongs to the technical field of green extraction of rare metals. Aiming at the problems of high acid consumption, waste of ammonia resources, low tungsten-molybdenum separation efficiency and the like in the traditional process, the device realizes green production and efficient resource circulation through collaborative design of a preheating system, a pH regulation and control system and an efficient separation system. The preheating system adopts a plate heat exchanger to recover waste heat of a mixed solution, the pH regulation and control system removes free ammonia and condenses and recovers high-quality ammonia water through a steam direct injection heat convection technology, the high-quality ammonia water is directly reused for production, and acid consumption and equipment corrosion risks are remarkably reduced. The efficient separation system is combined with five-stage counter-current extraction, six-stage clarification and an N1923-sulfonated kerosene-octanol system, so that the tungsten-molybdenum separation efficiency is improved to 98% or above. The device has the advantages of energy conservation and emission reduction, ammonia-containing wastewater discharge and energy consumption are reduced, the whole process is high in automation degree, and an efficient and environment-friendly integrated solution is provided for tungsten-molybdenum smelting.

Description

TECHNICAL FIELD

[0001] The utility model belongs to the field of green extraction and high -efficient separation and purification of rare metal, and relates to a pH regulation and ammonia separation device of ammonium tungstate-molybdate mixed solution. BACKGROUND

[0002] Tungsten-molybdenum smelting mainly prepares ammonium paratungstate (APT) or ammonium molybdate as precursor, and then prepares powder or alloy according to subsequent requirements, and in the preparation of ammonium paratungstate or ammonium molybdate, ammonia water or ammonium salt is often introduced, especially in the extraction and separation of tungsten and molybdenum in the acid decomposition mother liquor by the white tungsten ore acid decomposition-macroporous resin adsorption-ammonia desorption process, the prepared ammonia water (the concentration of free ammonia in the prepared ammonia water is 80g / L-100g / L) is used to cyclically desorb the saturated macroporous resin, and ammonium molybdate-ammonium tungstate-ammonia water mixed solution is obtained, the solution often contains molybdenum with a concentration of 50g / L-100g / L, WO3 with a concentration of 10g / L-50g / L, and free ammonia with a concentration of 20g / L-40g / L, which has high utilization value, but tungsten and molybdenum are difficult to separate efficiently.

[0003] At present, for the extraction and separation of tungsten and molybdenum in the ammonium molybdate-ammonium tungstate-ammonia water mixed solution, mainly adopts acid precipitation or extraction process and device to realize.

[0004] The acid precipitation process is to add sulfuric acid, nitric acid or hydrochloric acid to make the pH value of the ammonium molybdate-ammonium tungstate-ammonia water mixed solution decrease from alkaline to acidic, and under the condition of heating, tungsten is precipitated in the form of tungstic acid, and molybdenum can enter the acid precipitation mother liquor due to the high acidity environment, but this process and equipment have significant defects, the acid consumption is large, the equipment corrosion is serious, the separation effect of tungsten and molybdenum is poor, and a large amount of ammonia-containing acidic wastewater is generated, which is difficult to treat and has high cost.

[0005] The extraction separation process mainly adopts acid to adjust the pH value first, and then carries out extraction separation, and the typical representative is primary amine N1923 extraction, which meets the technical requirements of tungsten and molybdenum separation, but a large amount of acid is consumed, free ammonia is converted into ammonium salt, the added value is low, and high efficient utilization is not realized. INVENTION CONTENTS

[0006] This invention addresses the problems of excessive acid consumption, untapped ammonia utilization, and limited tungsten-molybdenum separation efficiency in adjusting the pH of ammonium molybdate-ammonium tungstate-ammonium water mixed solutions during tungsten smelting. It develops a pH-controlled ammonia removal and separation device for ammonium molybdate mixed solutions. First, the mixed solution is heated through a preheating system. The heated solution is then pumped into a pH control system, where direct injection thermal convection efficiently removes and recovers free ammonia, achieving green pH control. The pH-adjusted solution then enters a high-efficiency separation system using an N1923-sulfonated kerosene-octanol system. This system utilizes a two-stage clarification-five-stage extraction-two-stage clarification-two-stage back-extraction-one-stage clarification-one-stage back-extraction-two-stage clarification tank, operating in a counter-current manner to achieve efficient separation of tungsten and molybdenum from the pH-adjusted solution. This results in significant energy savings, emission reduction, and other benefits.

[0007] This utility model provides a pH-controlled deammoniation separation device for an ammonium tungstate / molybdate mixed solution, comprising a preheating system, a pH control system, and a high-efficiency separation system, wherein:

[0008] The preheating system is used to achieve green heating of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution. It includes a first solution storage tank storing the ammonium molybdate-ammonium tungstate-ammonium water mixed solution. The first solution storage tank is connected to a first centrifugal pump through a pipe equipped with a ball valve. The first centrifugal pump is used to pump the ammonium molybdate-ammonium tungstate-ammonium water mixed solution to a plate heat exchanger, thereby completing the preheating of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution. The first centrifugal pump and the plate heat exchanger are connected through a pipe equipped with a ball valve and a thermometer. The ammonium molybdate-ammonium tungstate-ammonium water mixed solution is first stored in the first solution storage tank, and then pumped into the plate heat exchanger by the first centrifugal pump. After the preheating is completed, the ammonium molybdate-ammonium tungstate-ammonium water mixed solution enters the pH control system through a pipe equipped with a thermometer and a ball valve.

[0009] The pH control system utilizes direct steam injection and thermal convection to efficiently remove and recover free ammonia from a mixed solution of ammonium molybdate, ammonium tungstate, and ammonia, achieving green pH control. It includes a vertical pH adjustment tower, divided into three sections: bottom, middle, and top. Each section is equipped with a thermometer to monitor the temperature inside the tower, and all thermometers are electrically connected to a data processor. The heated ammonium molybdate-ammonium tungstate-ammonium solution enters the top of the pH adjustment tower through a pipe equipped with a thermometer and a ball valve. The bottom of the tower has a support bracket for fixing the tower, and a level gauge is connected to the bottom to monitor the liquid level and prevent direct steam injection from escaping. An automatic regulating valve is also installed at the bottom of the pH adjustment tower. Electrically connected to the data processor, the automatic regulating valve is connected to the bottom of the pH adjusting tower via a steam valve. The pH adjusting tower also has a bottom liquid outlet. After the pH value is adjusted by the pH adjusting tower, the ammonium molybdate-ammonium tungstate mixed solution flows out from the bottom liquid outlet and enters the plate heat exchanger through a pipe equipped with a ball valve and a thermometer. In the plate heat exchanger, it exchanges heat with the ammonium molybdate-ammonium tungstate-ammonium water mixed solution. Then, it enters the second solution storage tank through a pipe equipped with a ball valve and a thermometer. The ammonia-containing gas at the top of the pH adjusting tower is introduced into the tubular heat exchanger through a pipe equipped with a ball valve. It exchanges heat with cold tap water to achieve the purpose of cooling and condensation. The high-quality ammonia water prepared by heat exchange and condensation of ammonia gas enters the condensed ammonia water storage tank through a pipe equipped with a ball valve.

[0010] The high-efficiency separation system is used for the efficient separation of tungsten and molybdenum in an ammonium molybdate-ammonium tungstate mixed solution after pH adjustment and heat exchange. It includes a solution cooling tank, a second centrifugal pump, a first high-level tank, and an extraction separation tank. The extraction separation tank has fifteen stages: five extraction stages, six clarification stages, two back-extraction stages, and one regeneration stage, distributed as follows: second-stage clarification - fifth-stage extraction - second-stage clarification - second-stage back-extraction - first-stage clarification - first-stage back-extraction - second-stage clarification. After heat exchange in the second solution storage tank, the ammonium molybdate-ammonium tungstate mixed solution flows to the solution cooling tank under gravity. The solution cooling tank is connected to the second centrifugal pump via a pipe equipped with a ball valve. Driven by the second centrifugal pump, the ammonium molybdate-ammonium tungstate mixed solution after heat exchange in the solution cooling tank is pumped into the first high-level tank. The first high-level tank is equipped with an overflow pipe with a ball valve to prevent solution overflow. The extraction tank is connected to the extraction stage 1 of the extraction separation tank via a pipe equipped with a flow meter and a ball valve. The flow rate is controlled by the flow meter to maintain stable flow. After heat exchange, the ammonium molybdate-ammonium tungstate mixed solution enters the extraction separation tank from the extraction stage 1. It then undergoes five-stage cascade countercurrent extraction and two-stage cascade clarification to obtain the raffinate. The organic phase enters from the extraction stage 5 and undergoes five-stage cascade countercurrent extraction to obtain the loaded organic phase. After two stages of clarification, the clarified loaded organic phase is obtained. The back-extraction agent enters from the back-extraction stage 1 and undergoes two stages of cascade countercurrent back-extraction. After contacting the clarified loaded organic phase, the back-extraction solution is obtained. The back-extraction solution is the blank organic phase. The blank organic phase then undergoes one stage of clarification, one stage of regeneration, and two stages of clarification to obtain the clarified blank organic phase. The regenerator enters from the regeneration stage 1 to regenerate the blank organic phase, obtaining the regenerated solution.

[0011] In some embodiments of this utility model, the cold tap water comes from a circulating cooling water storage tank. A cooling spray pipe is provided above the circulating cooling water storage tank. The cold tap water in the circulating cooling water storage tank is connected to a circulating pump through a pipe with a ball valve. Driven by the circulating pump, the water enters a tubular heat exchanger through a pipe with a ball valve to exchange heat and complete the condensation function of ammonia-containing gas. After heat exchange, the tap water flows into the cooling spray pipe through a pipe with a ball valve. After being sprayed and cooled by the cooling spray pipe, it enters the circulating cooling water storage tank, thus forming a cycle.

[0012] As some embodiments of this utility model, the high-efficiency separation system further includes a second high-level tank, a third high-level tank, and a fourth high-level tank. The second high-level tank is filled with an organic phase, the third high-level tank is filled with a back-extraction agent, and the fourth high-level tank is filled with a regenerator.

[0013] As some embodiments of this utility model, the second high-level tank is connected to the extraction stage 5 of the extraction separation tank through a pipe with a flow meter, the third high-level tank is connected to the back-extraction stage 1 of the extraction separation tank through a pipe with a flow meter, and the fourth high-level tank is connected to the regeneration stage 1 of the extraction separation tank through a pipe with a flow meter.

[0014] As a preferred embodiment of some embodiments of the present invention, the clarified blank organic phase is pumped back into the second high-level tank.

[0015] As a preferred embodiment of this utility model, the first solution storage tank is made of PPH wound material, is cylindrical (φ3560mm×h5000mm), and has a volume of 50m³. 3 .

[0016] As a preferred embodiment of this utility model, the first centrifugal pump is a plastic-lined corrosion-resistant type with a power of 2.2 kW·h.

[0017] As a preferred embodiment of this utility model, the plate heat exchanger is detachable, with the main body made of 316L stainless steel, the heat exchange fins made of titanium, the fin texture being a shallow corrugated thin rectangular channel, the number of heat exchange fins being 180, the fin thickness being 0.5mm, and the plate area being 0.72m². 2 Operating pressure: 0MPa~0.8MPa; Flow rate: 0.5m³ / h 3 / h~5m 3 / h, inlet and outlet temperature difference 10℃~30℃.

[0018] As a preferred embodiment of this utility model, the pH adjustment tower is made of carbon steel and has a size of φ40cm×1000cm.

[0019] As a preferred embodiment of this utility model, the second solution storage tank is made of PPH wound material, cylindrical in shape with a diameter of φ3560mm × h5000mm, and a volume of 50m³. 3 .

[0020] As a preferred embodiment of this utility model, the tubular heat exchanger is made of titanium, with an outer diameter of 700mm, a length of 3000mm, and a heat exchange area of ​​100m². 2 .

[0021] As a preferred embodiment of this utility model, the condensed ammonia water storage tank is made of stainless steel and has a tank volume of 2m³. 3 .

[0022] As a preferred embodiment of this utility model, the volume of the circulating cooling water storage tank is 600m³. 3 (20m×10m×3m), cast-in-place cement.

[0023] As a preferred embodiment of the present invention, the cooling spray pipe is provided in 3 sets.

[0024] As a preferred embodiment of this utility model, the circulating pump is a vertical pump with a power of 11 kW·h.

[0025] As a preferred embodiment of this utility model, the pipes in the pH control system are galvanized pipes with a diameter of DN100mm.

[0026] As a preferred embodiment of this utility model, the solution cooling tank is made of PPH wound material, cylindrical in shape with a diameter of φ3560mm × h5000mm, and a volume of 50m³. 3 .

[0027] As a preferred embodiment of this utility model, the second centrifugal pump is a plastic corrosion-resistant type with a power of 2.2 kW·h.

[0028] As a preferred embodiment of this utility model, the first, second, third, and fourth high-level grooves are made of PPH wound material, cylindrical in shape with a diameter of φ1000mm × h1273mm, and a volume of 1m³. 3 .

[0029] As a preferred embodiment of this utility model, the extraction separation tank is made of PPH material, and the size of each stage is 5000mm×800mm×1000mm.

[0030] Compared with the prior art, the beneficial effects of this utility model are as follows:

[0031] 1. Significantly reduces acid consumption and equipment corrosion risk: The efficient removal and recovery of free ammonia is achieved through direct steam injection thermal convection technology, avoiding the consumption of large amounts of acid in traditional acid precipitation processes. This fundamentally reduces the amount of acid reagents used, while also reducing the corrosive damage of acid to equipment and extending the service life of the equipment.

[0032] 2. Significantly Improved Tungsten-Molybdenum Separation Efficiency: A multi-stage countercurrent extraction and clarification process (five-stage extraction, six-stage clarification, and two-stage back-extraction), combined with an N1923-sulfonated kerosene-octanol extraction system, achieves highly efficient separation of tungsten and molybdenum in an ammonium molybdate-ammonium tungstate mixed solution. As shown in the examples, the WO3 concentration in the raffinate can be reduced to below 0.05 g / L, and the Mo concentration in the back-extraction solution is below 5.12 g / L, with a separation purity significantly superior to traditional processes.

[0033] 3. High-value recovery and utilization of ammonia resources: The pH control system condenses ammonia-containing gas through a tubular heat exchanger to recover and prepare high-quality ammonia water with a concentration of 160g / L to 220g / L, which can be directly used for subsequent process recycling. This solves the drawback of converting ammonia into low-value-added ammonium salts in traditional processes, improves resource utilization, and reduces raw material costs.

[0034] 4. Outstanding energy saving and emission reduction effects: The coordinated design of the preheating system and plate heat exchanger realizes the recycling of waste heat and reduces energy consumption; at the same time, the efficient recovery of ammonia greatly reduces the discharge of ammonia-containing wastewater, reduces the difficulty and cost of wastewater treatment, and the overall process meets the requirements of green production.

[0035] 5. Enhanced process automation and stability: Through the linkage control of data processor and automatic regulating valve, the temperature, liquid level and steam flow of the pH adjustment tower are monitored and adjusted in real time to ensure the stability of the pH adjustment process, reduce manual intervention and improve process controllability and production efficiency. Attached Figure Description

[0036] To more clearly illustrate the specific embodiments of this utility model 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 only one embodiment of this utility model. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0037] Figure 1 This is a schematic diagram of the pH-controlled deammoniation separation device for ammonium tungstate molybdate mixed solution according to an embodiment of this utility model.

[0038] The labels in the attached diagram are as follows: 1. First solution storage tank; 2. First centrifugal pump; 3. Plate heat exchanger; 4. pH adjustment tower; 5. Second solution storage tank; 6. Solution cooling tank; 7. Second centrifugal pump; 8. First high-level tank; 9. Extraction separation tank; 10. Tubular heat exchanger; 11. Ammonia condensate storage tank; 12. Circulating cooling water storage tank; 13. Circulating pump; 14. Second high-level tank; 15. Third high-level tank; 16. Fourth high-level tank; 17. Thermometer; 18. Ball valve; 19. Flip-plate level gauge; 20. Cooling spray pipe; 21. Flow meter; 22. Thermometer; 23. Data processor; 24. Automatic regulating valve; 25. Steam valve. Detailed Implementation

[0039] To make the technical means, creative features, objectives and effects of this utility model easy to understand, the technical solutions in the specific embodiments of this utility model are clearly and completely described below to further illustrate this utility model. Obviously, the specific embodiments described are only a part of the embodiments of this utility model, and not all of them.

[0040] Example 1: This example describes a pH-controlled deammoniation separation device for a mixed solution of ammonium tungstate and molybdate. Figure 1As shown, the system includes a preheating system, a pH control system, and a high-efficiency separation system. To better illustrate the effects of this invention, this embodiment uses the actual operation of the device for explanation. The tungsten smelting solution containing ammonium molybdate-ammonium tungstate-ammonium water is a loaded resin after D318 resin adsorbs low-concentration molybdenum and tungsten solutions. The solution is obtained by circulating and desorbing ammonia water with a free ammonia concentration of 100 g / L. This solution contains WO3 28.6 g / L, Mo 64.13 g / L, and free ammonia 31.22 g / L.

[0041] First, a preheating system is used to raise the temperature of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution. The preheating system includes a first solution storage tank 1 containing the ammonium molybdate-ammonium tungstate-ammonium water mixed solution. The first solution storage tank 1 is connected to a first centrifugal pump 2 through a pipe equipped with a ball valve 18. The first centrifugal pump 2 is used to pump the ammonium molybdate-ammonium tungstate-ammonium water mixed solution to a plate heat exchanger 3, thereby completing the preheating of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution. The first centrifugal pump 2 and the plate heat exchanger 3 are connected through a pipe equipped with a ball valve 18, and a thermometer 17 is installed in the pipe. The ammonium molybdate-ammonium tungstate-ammonium water mixed solution is first stored in the first solution storage tank 1, and then pumped into the plate heat exchanger 3 by the first centrifugal pump 2. After the preheating is completed, the ammonium molybdate-ammonium tungstate-ammonium water mixed solution enters the pH control system through the pipe equipped with the thermometer 17 and the ball valve 18. In this embodiment, the first solution storage tank 1 is made of PPH wound material, is cylindrical (φ3560mm×h5000mm), and has a volume of 50m³. 3 The first centrifugal pump 2 is a plastic-lined corrosion-resistant type with a power of 2.2 kW·h. The plate heat exchanger 3 is a detachable type, with the main body made of 316L stainless steel and the heat exchange fins made of titanium. The heat exchange fins have a shallow corrugated thin rectangular channel pattern, with 180 heat exchange fins, a thickness of 0.5 mm, and a plate area of ​​0.72 m². 2 Operating pressure: 0MPa~0.8MPa; Flow rate: 0.5m³ / h 3 / h~5m 3 / h, inlet and outlet temperature difference 10℃~30℃.

[0042] Then, a pH control system (steam direct injection thermal convection) is used to efficiently remove and recover free ammonia from the ammonium molybdate-ammonium tungstate-ammonium water mixed solution, while simultaneously achieving green pH control. This includes a vertical pH adjustment tower 4, which is divided into three parts: the bottom, the middle, and the top. Each part is equipped with a thermometer 22 to monitor the temperature inside the pH adjustment tower 4. The thermometers 22 are electrically connected to a data processor 23. The ammonium molybdate-ammonium tungstate-ammonium water mixed solution, after being heated by a plate heat exchanger 3, enters the pH adjustment tower through a pipe equipped with a thermometer 17 and a ball valve 18. The pH adjusting tower 4 has a support bracket at its top and bottom, and a level gauge 19 at its bottom to monitor the bottom liquid level and prevent direct injection of hot steam from escaping. An automatic regulating valve 24 is also installed at the bottom of the pH adjusting tower 4, electrically connected to a data processor 23. The automatic regulating valve 24 communicates with the bottom of the pH adjusting tower 4 via a steam valve 25. The pH adjusting tower 4 also has a bottom liquid outlet, from which the ammonium molybdate-ammonium tungstate mixed solution, after pH adjustment, exits. After flowing out, the ammonia gas enters the plate heat exchanger 3 through a pipe equipped with a ball valve 18 and a thermometer 17, where it exchanges heat with the ammonium molybdate-ammonium tungstate-ammonium water mixed solution. Then, it enters the second solution storage tank 5 through another pipe equipped with a ball valve 18 and a thermometer 17. The ammonia-containing gas at the top of the pH adjustment tower 4 is introduced into the tubular heat exchanger 10 through a pipe equipped with a ball valve 18, where it exchanges heat with cold tap water to achieve cooling and condensation. The high-quality ammonia water prepared from the condensed ammonia gas then enters the condensed ammonia water storage tank 11 through a pipe equipped with a ball valve 18. In this embodiment, cold tap water originates from a circulating cooling water storage tank 12. A cooling spray pipe 20 is installed above the circulating cooling water storage tank 12. The cold tap water in the circulating cooling water storage tank 12 is connected to a circulating pump 13 through a pipe equipped with a ball valve 18. Driven by the circulating pump 13, the water enters the tubular heat exchanger 10 through the pipe equipped with the ball valve 18 for heat exchange, completing the condensation function of the ammonia-containing gas. After heat exchange, the tap water flows through the pipe equipped with the ball valve 18 into the cooling spray pipe 20. After being sprayed and cooled by the cooling spray pipe 20, it enters the circulating cooling water storage tank 12, thus forming a cycle. In this embodiment, the pH adjustment tower 4 is made of carbon steel with dimensions of φ40cm×1000cm; the second solution storage tank 5 is made of PPH wound material, cylindrical with dimensions of φ3560mm×h5000mm and a volume of 50m³. 3 The tubular heat exchanger 10 is made of titanium, with an outer diameter of 700mm, a length of 3000mm, and a heat exchange area of ​​100m². 2 The condensed ammonia storage tank 11 is made of stainless steel and has a volume of 2m³. 3 The volume of the circulating cooling water storage tank 12 is 600 m³. 3(20m×10m×3m), cast-in-place cement; 3 sets of cooling spray pipes 20; Circulation pump 13 is a vertical pump with a power of 11KW·h; The pipes in the pH control system are galvanized pipes with a diameter of DN100mm.

[0043] The high-efficiency separation system is used for the efficient separation of tungsten and molybdenum in an ammonium molybdate-ammonium tungstate mixed solution after pH adjustment and heat exchange. It includes a solution cooling tank 6, a second centrifugal pump 7, a first high-level tank 8, an extraction separation tank 9, a second high-level tank 14, a third high-level tank 15, and a fourth high-level tank 16. The extraction separation tank 9 has fifteen stages: five extraction stages, six clarification stages, two back-extraction stages, and one regeneration stage, distributed as follows: second-stage clarification - fifth-stage extraction - second-stage clarification - second-stage back-extraction - first-stage clarification - first-stage back-extraction - second-stage clarification. The second solution storage tank 5, after heat exchange, separates the molybdenum... The ammonium-ammonium tungstate mixed solution flows to the solution cooling tank 6 under gravity. The solution cooling tank 6 is connected to the second centrifugal pump 7 via a pipe equipped with a ball valve 18. Driven by the second centrifugal pump 7, the ammonium molybdate-ammonium tungstate mixed solution, after heat exchange in the solution cooling tank 6, is pumped into the first high-level tank 8. The second high-level tank 14 contains the organic phase, the third high-level tank 15 contains the back-extraction agent, and the fourth high-level tank 16 contains the regenerant. The first high-level tank 8 is equipped with an overflow pipe equipped with a ball valve 18 to prevent solution overflow. The first high-level tank 8 is connected to the extraction tank via a pipe equipped with a flow meter 21 and a ball valve 18. The extraction stage 1 of extraction tank 9 is connected, and the flow rate is controlled by flow meter 21 to maintain stable flow control. The second high-level tank 14 is connected to the extraction stage 5 of extraction tank 9 through a pipe equipped with flow meter 21. The third high-level tank 15 is connected to the back-extraction stage 1 of extraction tank 9 through a pipe equipped with flow meter 21. The fourth high-level tank 16 is connected to the regeneration stage 1 of extraction tank 9 through a pipe equipped with flow meter 21. After heat exchange, the ammonium molybdate-ammonium tungstate-ammonium water mixed solution enters extraction tank 9 from extraction stage 1, and then undergoes five-stage cascade countercurrent extraction and two-stage cascade clarification to obtain... In the raffinate, the organic phase enters from extraction stage 5 and undergoes five stages of cascade countercurrent extraction to obtain a loaded organic phase. This is followed by two stages of clarification to obtain a clarified loaded organic phase. The back-extraction agent enters from back-extraction stage 1 and undergoes two stages of cascade countercurrent back-extraction. After contacting the clarified loaded organic phase, a back-extraction solution is obtained, resulting in a blank organic phase. This blank organic phase undergoes one stage of clarification, one stage of regeneration, and two stages of clarification to obtain a clarified blank organic phase, which is then pumped back to the second high-level tank 14. The regenerator enters from regeneration stage 1 to regenerate the blank organic phase, yielding a regenerated solution. In this embodiment, the solution cooling tank 6 is made of PPH wound material, cylindrical in shape with a diameter of φ3560mm × h5000mm and a volume of 50m³. 3 The second centrifugal pump 7 is a plastic corrosion-resistant type with a power of 2.2 kW·h; the first high-level tank 8, the second high-level tank 14, the third high-level tank 15, and the fourth high-level tank 16 are made of PPH wound material, cylindrical in shape with a diameter of φ1000mm × h1273mm and a volume of 1m³.3 The extraction separation tank 9 is made of PPH material, and the dimensions of each stage are 5000mm×800mm×1000mm.

[0044] The overall operation of the pH-controlled deammonium separation device for an ammonium tungstate-ammonium tungstate mixed solution in this embodiment is as follows: The ammonium molybdate-ammonium tungstate-ammonium water mixed solution is first stored in the first solution storage tank 1, and then pumped into the plate heat exchanger 3 by the first centrifugal pump 2. The flow rate of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution being pumped is controlled at 0.5 m³ / s. 3 The temperature of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution was measured at 28.5℃. After heat exchange in plate heat exchanger 3, the temperature of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution reached 76.5℃. Simultaneously, the temperature of the bottom liquid outlet of pH adjusting tower 4 was 98℃. After heat exchange in plate heat exchanger 3, the temperature of the bottom liquid outlet of plate heat exchanger 3 was 80.5℃. The preheated ammonium molybdate-ammonium tungstate-ammonium water mixed solution was pumped into pH adjusting tower 4. Steam was directly injected from the top of the bottom liquid level. The steam injection rate was consistent with the flow rate of pH adjusting tower 4. The temperatures at the bottom, middle, and top of the tower are linked. The bottom temperature is controlled at 98℃~101℃, the middle temperature at 94℃~97℃, and the top temperature at 90℃~93℃. The ammonium molybdate-ammonium tungstate-ammonium water mixed solution, after passing through pH adjustment tower 4, is discharged from the bottom of the tower at a temperature of 98℃, indicating complete removal of free ammonia and a pH value of 7.5~8.5. The ammonia-containing gas at the top of the tower is cooled by water in tubular heat exchanger 10, with a tap water flow rate of 40 m³ / h entering the tubular heat exchanger 10. 3 The inlet water temperature is 28℃, and the outlet water temperature is 34℃. After being treated by three sets of cooling spray pipes 20, the effluent enters the circulating cooling water storage tank 12 for recycling. The ammonia-containing gas is condensed to form concentrated ammonia water with a concentration of 160g / L to 200g / L. This process adjusts the pH value of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution while preparing high-value concentrated ammonia water from excess ammonia. After pH adjustment, the ammonium molybdate-ammonium tungstate mixed solution is pumped into the first high-level tank 8 by the second centrifugal pump 7 to form the extraction stock solution. The flow rate is then adjusted by the flow meter 21 to enter the extraction separation tank 9, where the first-stage extraction tank is located, with the flow rate controlled at 1.5m³ / h. 3 The organic phase is prepared at a volume fraction of 14% N1923 + 16% octanol + 70% sulfonated kerosene, with the organic phase flow rate controlled at 1.2 m³ / h. 3 The extraction was performed in a five-stage countercurrent cascade. The WO3 content in the extracted loaded organic phase was 35.62 g / L, the WO3 concentration in the raffinate was 0.05 g / L, and the Mo concentration was 62.07 g / L. The stripping agent was ammonia water with a concentration of 80 g / L, and the stripping agent flow rate was controlled at 0.5 m³ / h. 3 The concentration of WO3 in the resulting back-extraction solution was 87.22 g / L and the concentration of Mo was 4.94 g / L.

[0045] The above practical operation shows that this embodiment achieves green pH adjustment and efficient separation of ammonium molybdate-ammonium tungstate-ammonium water mixed solution, and obtains high-purity ammonium molybdate solution and high-tungstate and low-molybdate solution. It also prepares high-value high-concentration ammonia water, reduces the reagent consumption for pH adjustment in traditional processes and equipment, and significantly improves energy saving, emission reduction and efficiency.

[0046] Example 2: The apparatus in this example is the same as that in Example 1, except that the tungsten smelting solution containing ammonium molybdate-ammonium tungstate-ammonium water is a loaded resin after D318 resin adsorbs low concentration molybdenum and tungsten solutions. The solution is obtained by circulating and desorbing ammonia water with a free ammonia concentration of 100 g / L, containing WO3 19.25 g / L, Mo 81.74 g / L, and free ammonia 38.81 g / L.

[0047] The overall operation of the pH-controlled deammoniation separation device for ammonium tungstate molybdate mixed solution in this embodiment is as follows:

[0048] The ammonium molybdate-ammonium tungstate-ammonium water mixed solution is first stored in the first solution storage tank 1, and then pumped into the plate heat exchanger 3 by the first centrifugal pump 2. The flow rate of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution pumped in is controlled at 1 m³ / s. 3 The temperature of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution was measured at 34℃. After heat exchange in plate heat exchanger 3, the temperature of the solution reached 80.5℃. Simultaneously, the temperature of the bottom liquid outlet of pH adjusting tower 4 was 100℃. After heat exchange in plate heat exchanger 3, the temperature of the bottom liquid outlet of plate heat exchanger 3 was 83℃. The preheated ammonium molybdate-ammonium tungstate-ammonium water mixed solution was pumped into pH adjusting tower 4. Steam was directly injected from the top of the bottom liquid level. The steam injection rate was consistent with the bottom liquid level of pH adjusting tower 4. The temperatures at the top and bottom of the tower are linked. The bottom temperature is controlled at 98℃~102℃, the middle temperature at 94℃~96℃, and the top temperature at 91℃~93℃. The ammonium molybdate-ammonium tungstate-ammonium water mixed solution, after passing through pH adjustment tower 4, is discharged from the bottom of the tower at 100℃, indicating complete removal of free ammonia and a pH value of 7.5~8.5. The ammonia-containing gas at the top of the tower is cooled by water in tubular heat exchanger 10, with a tap water flow rate of 60 m³ / h entering the tubular heat exchanger 10. 3 The inlet water temperature is 28℃, and the outlet water temperature is 36℃. After being treated by three sets of cooling spray pipes 20, the effluent enters the circulating cooling water storage tank 12 for recycling. The ammonia-containing gas is condensed to form concentrated ammonia water with a concentration of 180g / L~220g / L. This process adjusts the pH value of the ammonium molybdate-ammonium tungstate-ammonium water mixed solution while preparing high-value concentrated ammonia water from excess ammonia. After pH adjustment, the ammonium molybdate-ammonium tungstate mixed solution is pumped into the first high-level tank 8 by the second centrifugal pump 7 to form the extraction stock solution. The flow rate is then adjusted by the flow meter 21 to enter the extraction separation tank 9, where the first-stage extraction tank is located, with the flow rate controlled at 2.0m³ / h. 3 / h, the organic phase is prepared with a volume fraction of 14% N1923 + 16% octanol + 70% sulfonated kerosene, and the organic phase flow rate is controlled at 1.1m³ / h. 3 The extraction was performed in a five-stage countercurrent cascade. The WO3 content in the extracted supported organic phase was 34.85 g / L, the WO3 concentration in the raffinate was 0.02 g / L, and the Mo concentration was 78.96 g / L. The stripping agent was ammonia water with a concentration of 80 g / L, and the stripping agent flow rate was controlled at 0.5 m³ / h. 3 The resulting back-extraction solution had a WO3 concentration of 76.54 g / L and a Mo concentration of 5.12 g / L.

[0049] Through the above practical operation, it has been proven once again that this utility model can achieve green pH adjustment and efficient separation of ammonium molybdate-ammonium tungstate-ammonium water mixed solution, and obtain high-purity ammonium molybdate solution and high-tungstate and low-ammonium molybdate solution, and prepare high-value high-concentration ammonia water, reducing the reagent consumption for pH adjustment in traditional processes and equipment, and significantly improving energy saving, emission reduction and efficiency.

[0050] The main technical features, basic principles, and related advantages of this utility model have been described above. It will be apparent to those skilled in the art that this utility model is not limited to the details of the exemplary embodiments described above, and that it can be implemented in other specific forms without departing from the concept or basic characteristics of this utility model. Therefore, the above-described embodiments should be considered exemplary and non-limiting in all respects. The scope of this utility model is defined by the appended claims rather than the foregoing description, and thus all variations falling within the meaning and scope of equivalents of the claims are intended to be included within this utility model.

[0051] Furthermore, it should be understood that although this specification describes various embodiments, not every embodiment contains only one independent technical solution. This way of describing the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A pH control and deamination separation device for an ammonium tungstate-molybdate mixed solution, comprising a preheating system, a pH value control system and a high-efficiency separation system, characterized in that: the preheating system comprises a first solution storage tank (1), a first centrifugal pump (2) and a plate heat exchanger (3), the first solution storage tank (1) is used for storing an ammonium molybdate-ammonium tungstate-ammonia water mixed solution, the first solution storage tank (1) is connected with the first centrifugal pump (2) through a pipeline provided with a ball valve (18), the first centrifugal pump (2) is used for pumping the ammonium molybdate-ammonium tungstate-ammonia water mixed solution to the plate heat exchanger (3), the first centrifugal pump (2) and the plate heat exchanger (3) are connected through a pipeline provided with a ball valve (18), and a thermometer (17) is arranged in the pipeline, the ammonium molybdate-ammonium tungstate-ammonia water mixed solution is preheated in the plate heat exchanger (3), and then enters the pH value control system through a pipeline provided with a thermometer (17) and a ball valve (18); the pH value control system comprises a vertical pH value control tower (4), a second solution storage tank (5), a tubular heat exchanger (10), a condensed ammonia water storage tank (11), a flip plate liquid level meter (19), a temperature measuring meter (22), a data processor (23) and an automatic adjusting valve (24), the pH value control tower (4) is divided into a tower bottom, a tower middle and a tower top, temperature measuring meters (22) are arranged in the tower bottom, the tower middle and the tower top, the temperature measuring meters (22) are electrically connected with the data processor (23), the preheated ammonium molybdate-ammonium tungstate-ammonia water mixed solution enters the tower top of the pH value control tower (4) through a pipeline provided with a thermometer (17) and a ball valve (18), the tower bottom of the pH value control tower (4) is provided with a bracket for supporting and fixing the pH value control tower (4), the bottom of the pH value control tower (4) is connected with the flip plate liquid level meter (19) and the automatic adjusting valve (24), the automatic adjusting valve (24) is electrically connected with the data processor (23), the automatic adjusting valve (24) is communicated with the tower bottom of the pH value control tower (4) through a pipeline provided with a steam valve (25), the tower bottom of the pH value control tower (4) is further provided with a tower bottom liquid outlet, the ammonium molybdate-ammonium tungstate mixed solution after pH value control flows out from the tower bottom liquid outlet, enters the plate heat exchanger (3) through a pipeline provided with a ball valve (18) and a thermometer (17), exchanges heat with the ammonium molybdate-ammonium tungstate-ammonia water mixed solution in the plate heat exchanger (3), and then enters the second solution storage tank (5) through a pipeline provided with a ball valve (18) and a thermometer (17), and ammonia-containing gas in the tower top of the pH value control tower (4) is introduced into the tubular heat exchanger (10) through a pipeline provided with a ball valve (18), exchanges heat with cold tap water, achieves the purpose of cooling and condensation, high-quality ammonia water prepared by exchanging heat and condensation of ammonia gas enters the condensed ammonia water storage tank (11) through a pipeline provided with a ball valve (18). ​ ​ The high-efficiency separation system comprises a solution cooling tank (6), a second centrifugal pump (7), a first high tank (8) and an extraction separation tank (9), wherein the extraction separation tank (9) has fifteen stages, five stages of extraction, six stages of clarification, two stages of back extraction and one stage of regeneration, and the distribution is two stages of clarification-five stages of extraction-two stages of clarification-two stages of back extraction-one stage of clarification-one stage of back extraction-two stages of clarification; the ammonium molybdate-ammonium tungstate mixed solution after heat exchange in the second solution storage tank (5) flows to the solution cooling tank (6) under the action of gravity, the solution cooling tank (6) is communicated with the second centrifugal pump (7) through a pipeline with a ball valve (18), and the ammonium molybdate-ammonium tungstate mixed solution after heat exchange in the solution cooling tank (6) is pumped into the first high tank (8) under the action of the second centrifugal pump (7); the first high tank (8) is communicated with the extraction 1 stage of the extraction separation tank (9) through a pipeline with a flow meter (21) and a ball valve (18), the ammonium molybdate-ammonium tungstate mixed solution after heat exchange enters the extraction 1 stage of the extraction separation tank (9), and then is subjected to five-stage series countercurrent extraction and two-stage series clarification to obtain a raffinate, the organic phase enters the extraction 5 stage, is subjected to five-stage series countercurrent extraction to obtain a loaded organic phase, and then is subjected to two-stage clarification to obtain the clarified loaded organic phase; the back extraction agent enters the back extraction 1 stage, is subjected to two-stage series countercurrent back extraction, contacts the clarified loaded organic phase, and then obtains a back extraction liquid; the back extraction obtains a blank organic phase, which is subjected to one-stage clarification, one-stage regeneration and two-stage clarification to obtain a clarified blank organic phase; and the regenerant enters the regeneration 1 stage, regenerates the blank organic phase to obtain a regeneration liquid.

2. The pH controlled deamination separation device for ammonium tungstomolybdate mixed solution according to claim 1, characterized in that, The pH value control system further comprises a circulating cooling water storage tank (12), a circulating pump (13) and a cooling spray pipe (20), the cooling tap water is from the circulating cooling water storage tank (12), the cooling spray pipe (20) is arranged above the circulating cooling water storage tank (12), the cooling tap water in the circulating cooling water storage tank (12) is communicated with the circulating pump (13) through a pipeline with a ball valve (18), the cooling tap water is pumped into the tubular heat exchanger (10) through the pipeline with the ball valve (18) under the action of the circulating pump (13), is subjected to heat exchange to complete the condensation of the ammonia-containing gas, and then flows into the cooling spray pipe (20) through the pipeline with the ball valve (18), is sprayed and cooled through the cooling spray pipe (20), and then enters the circulating cooling water storage tank (12) to form a circulation.

3. The pH controlled deamination separation device of an ammonium tungstomolybdate mixed solution according to claim 1, characterized in that, The high-efficiency separation system further comprises a second high tank (14), a third high tank (15) and a fourth high tank (16), the second high tank (14) is provided with the organic phase, the third high tank (15) is provided with the back extraction agent, and the fourth high tank (16) is provided with the regenerant; the second high tank (14) is communicated with the extraction 5 stage of the extraction separation tank (9) through a pipeline with a flow meter (21), the third high tank (15) is communicated with the back extraction 1 stage of the extraction separation tank (9) through a pipeline with a flow meter (21), and the fourth high tank (16) is communicated with the regeneration 1 stage of the extraction separation tank (9) through a pipeline with a flow meter (21).

4. The pH controlled deamination separation device of claim 3, wherein, The first high tank (8) is provided with an overflow pipe with a ball valve (18), and the clarified blank organic phase is pumped back into the second high tank (14).

5. The pH controlled deamination separation device for ammonium tungstate and ammonium molybdate mixed solution according to claim 1, characterized in that, The first solution storage tank (1) is made of PPH winding and has a cylindrical shape (φ3560mm x h5000mm) with a volume of 50m 3 The first centrifugal pump (2) is made of plastic lining anticorrosion type with a power of 2.2KW·h.

6. The pH controlled deamination separation device of an ammonium tungstomolybdate mixed solution according to claim 1, characterized in that, The plate heat exchanger (3) is detachable, the main material is 316L stainless steel, the heat exchange sheet is titanium material, the heat exchange sheet has shallow wave corrugated thin rectangular channels, the number of heat exchange sheets is 180, the thickness of the heat exchange sheet is 0.5 mm, the plate area is 0.72 m 2 , the working pressure is 0 MPa-0.8 MPa, the flow is 0.5 m 3 / h-5 m 3 / h, and the inlet and outlet temperature difference is 10-30℃.

7. The pH controlled deamination separation device of an ammonium tungstomolybdate mixed solution according to claim 1, characterized in that, The pH adjusting tower (4) is made of carbon steel with a size of φ40 cm x 1000 cm, the second solution storage tank (5) is made of PPH winding with a cylindrical shape of φ3560 mm x h5000 mm and a volume of 50 m 3 ; the tubular heat exchanger (10) is made of titanium material with an outer diameter of 700 mm, a length of 3000 mm, and a heat exchange area of 100 m 2 ; and the condensed ammonia water storage tank (11) is made of stainless steel with a tank volume of 2 m 3 .

8. The pH controlled deamination separation device of claim 2, wherein, The circulating cooling water storage tank (12) has a volume of 600m 3 (20m x 10m x 3m), and is made of cast-in-place cement. The cooling spray pipes (20) are provided with three groups, and the circulating pump (13) is a vertical pump with a power of 11KW·h.

9. The pH controlled deamination separation device of an ammonium tungstomolybdate mixed solution according to claim 1, characterized in that, The material of the solution cooling tank (6) is PPH winding, cylindrical φ3560mm x h5000mm, and the volume is 50m 3 The material of the first high tank (8) is PPH winding, cylindrical φ1000mm x h1273mm, and the volume is 1m 3 The material of the extraction separation tank (9) is PPH, and the size of each stage is 5000mm x 800mm x 1000mm.

10. The pH controlled deamination separation device of claim 3, wherein, The material of the second high tank (14), the third high tank (15) and the fourth high tank (16) is PPH winding, cylindrical φ1000mm x h1273mm, with a volume of 1m 3 .

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