Equipment and method for preparing hydrated manganese oxalate from high-calcium-magnesium vanadium precipitation waste acid solution

Abstract

The invention discloses equipment and a method for preparing hydrated manganese oxalate from high-calcium-magnesium vanadium precipitation waste acid liquor, and belongs to the technical field of resource recovery. Equipment for preparing hydrated manganese oxalate from high-calcium-magnesium vanadium precipitation waste acid liquor comprises a first mixing box and further comprises a discharging pipe fixedly arranged at the bottom of the first mixing box, the first mixing box is communicated with a second mixing box through an acid liquor pipe, and ultrasonic probes are detachably arranged in the first mixing box and the second mixing box; the alkali solution pipe is communicated with the interior of the first mixing box; one end of the waste liquid feeding pipe and one end of the oxalic acid solution feeding pipe are communicated with the interior of the second mixing box; by adopting the device, all reaction solutions are rapidly and uniformly mixed in a high-speed impinging stream and ultrasonic strengthening mode, the problem that the impurity content of a manganese oxalate product is high due to component difference of micro-regions in a solution system is solved, accurate regulation and control of the reaction are realized, and the yield of the manganese oxalate product is improved. And finally, a high-purity hydrated manganese oxalate product which can be continuously produced is obtained.

Description

Technical Field

[0001] The invention relates to the technical field of resource recovery, and in particular to a device and a method for preparing hydrated manganese oxalate from high-calcium and magnesium vanadium precipitation waste acid solution. Background Art

[0002] Vanadium is an important strategic resource, widely used in metallurgy, chemical industry, and new materials. It is an important material indispensable for the development of modern industry, modern national defense, and modern science and technology. Vanadium is mainly found in vanadium-titanium magnetite. The vanadium slag, a byproduct of the vanadium-titanium magnetite concentrate treated by the blast furnace-converter process, is the main raw material for vanadium extraction. At present, the industrialized vanadium slag vanadium extraction processes mainly include sodium roasting-water leaching vanadium extraction and calcium roasting-acid leaching vanadium extraction. The calcium roasting vanadium extraction process is to add calcium salt to the vanadium slag for high-temperature oxidation roasting, so that the vanadium in the vanadium slag is converted into acid-soluble or alkali-soluble calcium vanadate. Since vanadium-titanium magnetite usually contains manganese, magnesium, and calcium, a large amount of manganese is leached into the acid leaching solution after calcium roasting-acid leaching of the vanadium slag. Ammonium salt is added to the acid leaching solution to obtain direct acid precipitation to obtain polyammonium vanadate precipitation, so as to achieve the separation and extraction of vanadium. The byproduct waste acid liquid after vanadium extraction is the calcium roasting-acid leaching-ammonium salt vanadium precipitation waste liquid. Since the waste liquid is recycled many times in the vanadium extraction process, elements such as manganese, calcium, and magnesium in the waste liquid continue to accumulate in the waste liquid, among which the content of Mn in the waste liquid is as high as 5-20g / L, which has a high recycling value. As the idea of ​​green circular economic development continues to gain popularity, the more environmentally friendly vanadium slag calcination roasting vanadium extraction process has gradually replaced the sodium roasting vanadium extraction process as the mainstream process, and the extraction of valuable elements from a large amount of calcination roasting-acid leaching-ammonium salt vanadium precipitation waste liquid has gradually been put on the agenda. Among them, the manganese oxalate precipitate is formed by the reaction of oxalic acid and oxalate with manganese ions in the solution, which has been applied to the removal of manganese in vanadium extraction mother liquor. This method can not only remove manganese impurities, but also reduce the amount of calcium and magnesium ions in the solution, thereby purifying the solution.

[0003] The difficulty in preparing high-purity hydrated manganese oxalate by recycling oxalic acid and oxalate from the waste liquid of calcination roasting-acid leaching-ammonium salt vanadium precipitation is mainly that the waste liquid has accumulated a large amount of manganese, calcium, magnesium and other ions due to repeated recycling in the vanadium extraction process, and the oxalate formed is insoluble. The solubility product of manganese oxalate is 1.9×10-13, the solubility product of calcium oxalate is 2.32×10-9, and the solubility product of magnesium oxalate is 4.83×10-6. Under acidic conditions, oxalic acid mainly exists in the form of H2C2O4 and HC2O4-, and a small amount exists in the form of C2O42-, so OH- needs to be added to the solution. The conventional stirring method will cause huge differences in the acidity and alkalinity of the solution and the C2O42- concentration in the instantaneous micro-region, resulting in a certain amount of calcium oxalate, magnesium oxalate, calcium hydroxide, and magnesium hydroxide impurities in the precipitated product. It is impossible to achieve a controllable directional precipitation reaction of calcium oxalate, and it can only achieve the purpose of removing impurities and purifying the solution. The purity of the obtained manganese oxalate product is not high. Summary of the invention

[0004] The purpose of the present invention is to solve the problem in the prior art that the manganese, calcium and magnesium contents in the waste liquid of vanadium-titanium magnetite calcination-acid leaching-ammonium salt vanadium precipitation in China are relatively high, and the purity of manganese oxalate recovered by the traditional oxalate precipitation method is not high, which seriously affects its economic efficiency. A device and method for preparing hydrated manganese oxalate from high-calcium and magnesium vanadium precipitation waste acid liquid are proposed.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A device for preparing hydrated manganese oxalate from high-calcium and magnesium vanadium precipitation waste acid liquid, comprising a first mixing box, and also comprising: a discharge pipe fixedly arranged at the bottom of the first mixing box, a first valve fixedly arranged on the discharge pipe, the first mixing box is connected to a second mixing box through an acid liquid pipe, ultrasonic probes are disassembled and arranged in the first mixing box and a second valve is fixedly arranged on the acid liquid pipe; an alkali solution pipe is connected to the first mixing box; a waste liquid feed pipe and an oxalic acid solution feed pipe, one end of each of the waste liquid feed pipe and the oxalic acid solution feed pipe is connected to the second mixing box.

[0007] In order to facilitate cleaning and maintenance of the first mixing box and the second mixing box, preferably, the first mixing box and the second mixing box are respectively provided with a first box cover and a second box cover that are removable on the top, and a plurality of mounting holes are provided on the first box cover and the second box cover, and the ultrasonic probe is arranged in the mounting hole, and the two ends of the acid liquid pipe are respectively fixedly connected to the first box cover and the second mixing box, the alkaline solution pipe is fixedly arranged on the first box cover, and the waste liquid feed pipe and the oxalic acid solution feed pipe are both fixedly arranged on the second box cover.

[0008] In order to facilitate the assembly and disassembly of the ultrasonic probe and to facilitate its maintenance or replacement, a limit slot is further provided in the first box cover, a connecting plate is slidably provided in the limit slot, a clamping block is fixedly provided at one end of the connecting plate, a clamping slot is provided on the ultrasonic probe housing, the clamping block is engaged with the clamping slot, and a spring is provided in the limit slot, the two ends of the spring are respectively abutted against the limit slot and the connecting plate, a rack plate is fixedly provided at the other end of the connecting plate, a rotating shaft is rotatably provided in the first box cover, a gear meshing with the rack plate is fixedly provided at one end of the rotating shaft, and a knob is fixedly provided at the other end of the rotating shaft.

[0009] A method for preparing hydrated manganese oxalate from high-calcium and magnesium vanadium precipitation waste acid solution comprises the above-mentioned equipment for preparing hydrated manganese oxalate from high-calcium and magnesium vanadium precipitation waste acid solution, and also comprises the following steps: firstly, calcification roasting-acid leaching-ammonium salt vanadium precipitation waste liquid is fully mixed with oxalic acid solution for a primary reaction; then, an alkaline solution is easily mixed after mixing at a certain rate, and a secondary reaction is carried out to obtain a manganese oxalate suspension at a product discharge port; and finally, high-purity hydrated manganese oxalate solid powder is obtained by filtering and drying.

[0010] Preferably, the concentration of the oxalic acid solution is 5%-9%, and the ratio of the amount of the oxalic acid substance introduced to the amount of the Mn substance introduced into the acid solution is 1:2-1:1.

[0011] Preferably, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, or a mixture of the two.

[0012] Furthermore, the pH value of the alkaline solution is 12-13.5.

[0013] Furthermore, the amount of the alkaline solution introduced is adjusted according to the pH value of the product outlet solution, and the pH value of the product outlet solution is maintained at 3.4-3.6 by controlling the amount of the alkaline solution introduced.

[0014] Furthermore, the flow rate of the oxalic acid solution is 2-4 m / s, the flow rate of the calcification roasting-acid leaching-ammonium salt vanadium precipitation waste liquid is 2-4 m / s, and the flow rate of the alkaline solution is 3-5 m / s.

[0015] Preferably, the drying temperature is 10°C-100°C.

[0016] Compared with the prior art, the present invention provides a device and method for preparing hydrated manganese oxalate from high calcium and magnesium vanadium precipitation waste acid solution, which has the following beneficial effects:

[0017] 1. The device for preparing hydrated manganese oxalate from high-calcium and magnesium vanadium precipitation waste acid solution, by reacting oxalate with manganese ions in the calcification roasting-acid leaching-ammonium salt vanadium precipitation waste solution, and then using an alkaline solution to increase the pH value of the mixed solution, adopts the device, uses high-speed impact flow and ultrasonic enhancement to achieve rapid mixing of each reaction solution, avoids the problem of high impurity content of manganese oxalate products caused by component differences in micro-regions in the solution system, achieves precise control of the reaction, and finally obtains a high-purity hydrated manganese oxalate product that can be produced continuously, and the device is simple to operate and control, has high process adaptability, does not require heating, has no temperature requirements, and has extremely low operating costs;

[0018] 2. The equipment for preparing hydrated manganese oxalate from high-calcium-magnesium vanadium precipitation waste acid solution has a mounting hole on the box cover, which facilitates the installation of the ultrasonic probe in the mixing box, and a card block is slidably arranged in the mounting hole to fix the ultrasonic probe to prevent the ultrasonic probe from shaking during use, thereby affecting normal use, and a sealing ring is arranged in the mounting hole to improve the sealing effect between the ultrasonic probe and the mounting hole, reduce the leakage of the solution, and improve the use effect;

[0019] 3. The method for preparing hydrated manganese oxalate from high-calcium and magnesium vanadium precipitation waste acid solution adopts the oxalate precipitation method, a micro-region flash reaction, and a high-speed impact flow + ultrasonic enhancement method to vigorously mix the solution, thereby achieving precise control of the precipitation reaction process, and finally obtaining a high-purity hydrated manganese oxalate product that can be continuously produced. The reaction speed is fast, continuous operation can be achieved, and a high-purity manganese oxalate product can be obtained in a solution environment with high calcium and magnesium.

[0020] The parts not involved in the equipment are the same as the existing technology or can be implemented by the existing technology. The present invention uses oxalate to react with manganese ions in the calcification roasting-acid leaching-ammonium salt vanadium precipitation waste liquid, and then uses an alkaline solution to increase the pH value of the mixed solution. The device uses high-speed impact flow and ultrasonic enhancement to achieve rapid mixing of each reaction solution, avoids the problem of high impurity content of the manganese oxalate product caused by the component differences in micro-regions in the solution system, achieves precise control of the reaction, and finally obtains a high-purity hydrated manganese oxalate product that can be produced continuously. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a schematic diagram of the structure of a device for preparing hydrated manganese oxalate from high calcium and magnesium vanadium precipitation waste acid solution proposed by the present invention;

[0022] Figure 2 This is a front view of a device for preparing hydrated manganese oxalate from high calcium and magnesium vanadium precipitation waste acid solution proposed by the present invention;

[0023] Figure 3 This is a schematic diagram of the structure of the first box cover of an apparatus for preparing hydrated manganese oxalate from high calcium and magnesium vanadium precipitation waste acid solution proposed by the present invention;

[0024] Figure 4 The present invention provides a schematic structural diagram of a device block for preparing hydrated manganese oxalate from high calcium and magnesium vanadium precipitation waste acid solution.

[0025] In the figure: 1. discharge pipe; 2. first mixing box; 201. first box cover; 202. mounting hole; 203. limit groove; 3. ultrasonic probe; 301. slot; 4. alkaline solution pipe; 5. acid solution pipe; 6. second mixing box; 7. waste liquid feed pipe; 8. oxalic acid solution feed pipe; 9. block; 901. connecting plate; 902. rack plate; 903. gear; 904. knob. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0027] In the description of the present invention, it is necessary to understand that the terms "upper", "lower", "front", "back", "left", "right", "top", "bottom", "inside", "outside", etc., indicating the orientation or position relationship are based on the orientation or position relationship shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0028] Embodiment 1:

[0029] Reference Figure 1-Figure 4 , a device for preparing hydrated manganese oxalate from high-calcium-magnesium vanadium precipitation waste acid solution, comprising a first mixing box 2, and also comprising: a discharge pipe 1 is fixedly arranged at the bottom of the first mixing box 2, a first valve is fixedly arranged on the discharge pipe 1, a second valve is fixedly arranged on the acid liquid pipe 5, the first valve and the second valve are preferably solenoid valves, a second mixing box 6 is connected to the top of the first mixing box 2 through the acid liquid pipe 5, and an ultrasonic probe 3 is disassembled and arranged in the first mixing box 2 and the second mixing box 6, the ultrasonic probe 3 is connected to an ultrasonic generator, and after receiving the electrical signal generated by the ultrasonic generator, the ultrasonic probe 3 converts it into mechanical vibration through the internal piezoelectric ceramic element, thereby generating a strong cavitation effect in the liquid. The mixing of different components in the liquid is promoted by local strong vibration, so that efficient and uniform liquid mixing can be achieved, and the frequency of the ultrasonic generator is 20KHZ-80KHZ, preferably 20KHZ; the alkaline solution pipe 4 is connected to the first mixing box 2; the waste liquid feed pipe 7 and the oxalic acid solution feed pipe 8, one end of the waste liquid feed pipe 7 and the oxalic acid solution feed pipe 8 are both connected to the second mixing box 6, wherein the angle range between the alkaline solution pipe 4 and the acid liquid pipe 5 is: 20°-80°, and the angle range between the waste liquid feed pipe 7 and the oxalic acid solution feed pipe 8 is: 20°-80°, here, we preferably set the two angles to 80°, and the pipe diameter range is: 5mm-25mm, preferably 5mm.

[0030] When in use, oxalate is reacted with manganese ions in the waste liquid of calcification roasting-acid leaching-ammonium salt vanadium precipitation, and then the pH value of the mixed solution is increased by using an alkaline solution. The device is used to achieve rapid mixing of the reaction solutions by means of high-speed impact flow and ultrasonic enhancement, thereby avoiding the problem of high impurity content of the manganese oxalate product caused by the component differences in micro-regions in the solution system, achieving precise control of the reaction, and finally obtaining a high-purity hydrated manganese oxalate product that can be produced continuously. In addition, the device is simple to operate and control, has high process adaptability, does not require heating, has no temperature requirements, and has extremely low operating costs.

[0031] Reference Figure 1-Figure 3 The tops of the first mixing box 2 and the second mixing box 6 are respectively detachably provided with a first box cover 201 and a second box cover, wherein the first box cover 201 and the second box cover can be fixed by means of screws, buckles or hasps. Here, we prefer hasps, which are easy to assemble and disassemble, simple in structure, convenient for cleaning and maintenance of the mixing box, and improve the use effect. In addition, a sealing gasket is provided between the box cover and the mixing box to reduce the leakage of the solution. Multiple groups of mounting holes 202 are provided on the first box cover 201 and the second box cover, and the mounting holes 202 are respectively provided with two to six groups. Here, we prefer three groups. Ultrasonic probes 3 are provided in the three groups of mounting holes 202, and sealing rings are provided at the inner bottom of the mounting holes 202. The outer shell of the ultrasonic probe 3 is abutted against the sealing ring to improve the ultrasonic probe 3 and the mounting hole 202 to reduce leakage, and the two ends of the acid liquid pipe 5 are fixedly connected to the first box cover 201 and the second mixing box 6 respectively, that is, one end of the acid liquid pipe 5 is fixedly connected to the top of the first box cover 201, and the other end of the acid liquid pipe 5 is fixedly connected to the bottom of the second mixing box 6, and the alkali solution pipe 4 is also fixedly arranged on the first box cover 201, and then the waste liquid feeding pipe 7 and the oxalic acid solution feeding pipe 8 are fixedly arranged on the top of the second box cover. When in use, the first box cover 201 and the second box cover are respectively disassembled and arranged on the first mixing box 2 and the second mixing box 6, and are fixed to the first mixing box 2 and the second mixing box 6 in a buckle manner, which is convenient for assembly and disassembly, and is convenient for cleaning and maintenance of the first mixing box 2 and the second mixing box 6, thereby improving the use effect.

[0032] Reference Figure 1-Figure 4A limiting groove 203 is provided in the first box cover 201, a connecting plate 901 is slidably provided in the limiting groove 203, a clamping block 9 is fixedly provided at one end of the connecting plate 901, a clamping groove 301 is provided on the shell of the ultrasonic probe 3, the clamping block 9 is engaged and connected with the clamping groove 301, and a spring is provided in the limiting groove 203, the two ends of the spring are respectively against the limiting groove 203 and the connecting plate 901, and a rack plate 902 is fixedly provided at the other end of the connecting plate 901, a rotating shaft is rotatably provided in the first box cover 201, a gear 903 meshing with the rack plate 902 is fixedly provided at one end of the rotating shaft, and a knob 904 is fixedly provided at the other end of the rotating shaft, here, we provide two groups of connecting plates 901 and clamping blocks 9, which are respectively located on both sides of the mounting hole 202, that is, there are two groups of rack plates 902, two The sliding directions of the rack plates 902 are parallel to each other, and are respectively located on both sides of the gear 903, and are meshed with the gear 903. When the gear 903 rotates, the two rack plates 902 can be driven to move closer to or farther from each other at the same time, so as to fix or loosen the ultrasonic probe 3 and improve the use effect. When in use, the ultrasonic probe 3 is placed in the mounting hole 202. After the ultrasonic probe 3 is installed in place, the clamping block 9 is just engaged with the clamping groove 301. When the ultrasonic probe 3 needs to be removed, the knob 904 is used to rotate the shaft and the gear 903 to drive the two rack plates 902 to move away from each other. At this time, the two clamping blocks 9 all slide out of the clamping groove 301, and the ultrasonic probe 3 can be removed, which is convenient for maintenance and replacement of the ultrasonic probe 3, thereby improving the use effect. In addition, the ultrasonic probe 3 is easy to assemble and disassemble, and the structure is simple and reliable.

[0033] Embodiment 2:

[0034] Based on Example 1, a method for preparing hydrated manganese oxalate from high calcium and magnesium vanadium precipitation waste acid solution is proposed.

[0035] A method for preparing hydrated manganese oxalate from high-calcium and magnesium vanadium precipitation waste acid solution comprises the above-mentioned equipment for preparing hydrated manganese oxalate from high-calcium and magnesium vanadium precipitation waste acid solution, and also comprises the following steps: firstly, calcification roasting-acid leaching-ammonium salt vanadium precipitation waste liquid is fully mixed with oxalic acid solution for a primary reaction; then, an alkaline solution is easily mixed after mixing at a certain rate, and a secondary reaction is carried out to obtain a manganese oxalate suspension at a product discharge port; and finally, high-purity hydrated manganese oxalate solid powder is obtained by filtering and drying.

[0036] When in use, the oxalate precipitation method is used, through micro-area flash reaction, the solution is strongly mixed by high-speed impact flow + ultrasonic enhancement, so as to achieve precise control of the precipitation reaction process, and finally obtain a high-purity hydrated manganese oxalate product that can be produced continuously. The reaction speed is fast, continuous operation can be achieved, and a high-purity manganese oxalate product (manganese oxalate purity ≥99.5%) can be obtained in a high calcium and magnesium solution environment.

[0037] The concentration of the oxalic acid solution is 5%-9%, and the ratio of the amount of the oxalic acid substance introduced to the amount of the Mn substance introduced into the acid solution is 1:2-1:1. Here, we preferably set the ratio to 1:2.

[0038] The alkaline solution is one or a mixture of sodium hydroxide solution or potassium hydroxide solution, and here, we prefer sodium hydroxide solution. And the pH value of the alkaline solution is 12-13.5, preferably 12.

[0039] When in use, the amount of the alkaline solution introduced is adjusted according to the pH value of the product outlet solution, and the pH value of the product outlet solution is maintained at 3.4-3.6, preferably 3.4, by controlling the amount of the alkaline solution introduced.

[0040] During use, the flow rate of the oxalic acid solution is 2-4 m / s, the flow rate of the calcification roasting-acid leaching-ammonium salt vanadium precipitation waste liquid is 2-4 m / s, and the flow rate of the alkaline solution is 3-5 m / s.

[0041] When the manganese oxalate suspension is dried, the drying temperature is 10°C-100°C, and the drying temperature is preferably 10°C.

[0042] In the present invention, the waste liquid of calcination roasting-acid leaching-ammonium salt vanadium precipitation from a vanadium smelter in Panxi area is taken as an example, wherein the waste liquid contains V: 1.25g / L, Mn: 17.5g / L, Ca: 20g / L, Mg: 10g / L, and the pH value of the waste liquid is 2. The equipment for recovering and preparing high-purity hydrated manganese oxalate from the waste liquid of calcination roasting-acid leaching-ammonium salt vanadium precipitation is a multi-tube structure, which includes a discharge pipe 1, a first mixing box 2, an ultrasonic probe 3, an alkaline solution pipe 4, an acid solution pipe 5, a second mixing box 6, a waste liquid feed pipe 7 and an oxalic acid solution feed pipe 8; and the inner diameter of the pipe is 5mm. The frequency of the ultrasonic generator is 20KHZ, and the number of ultrasonic probes 3 is 3; oxalic acid solution is fed into the oxalic acid solution feed pipe 8, and the calcification roasting-acid leaching-ammonium salt vanadium precipitation waste liquid is passed into the waste liquid feed pipe 7, and then the alkali solution is fed through the alkali solution pipe 4, the oxalic acid solution and the calcification roasting-acid leaching-ammonium salt vanadium precipitation waste liquid enter the second mixing box 6 and mix well, and then flow out from the acid liquid pipe 5, the acid liquid pipe 5 and the alkali solution pipe 4 merge into the first mixing box 2, and finally flow out from the discharge pipe 1, the angle between the waste liquid feed pipe 7 and the oxalic acid solution feed pipe 8 is 80°, and the angle between the acid liquid pipe 5 and the alkali solution pipe 4 is 80°. The oxalic acid solution, the waste liquid of calcination roasting-acid leaching-ammonium salt vanadium precipitation, and the alkaline solution are reacted at a certain rate through a device for recovering manganese from the waste liquid of calcination roasting-acid leaching-ammonium salt vanadium precipitation, and a manganese oxalate suspension is obtained at the product outlet, and a high-purity hydrated manganese oxalate solid powder is obtained by filtering and drying. The concentration of the oxalic acid solution is 5%, and the ratio of the amount of oxalic acid introduced to the amount of Mn introduced into the acid solution is 1:2. The alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, or a mixture of the two, and the pH value is 12. The amount of alkaline solution introduced is adjusted according to the pH value of the product outlet solution, and the pH value of the product outlet solution is maintained at 3.4 by controlling the amount of alkaline solution introduced. The flow rate of the oxalic acid solution is 2m / s, the flow rate of the waste liquid of calcination roasting-acid leaching-ammonium salt vanadium precipitation is 2m / s, the flow rate of the alkaline solution is 3m / s, and the drying temperature is 10°C. The device and process for recovering and preparing high-purity hydrated manganese oxalate from calcination roasting-acid leaching-ammonium salt vanadium precipitation waste liquid are adopted to finally obtain high-purity hydrated manganese oxalate with a purity of 99.65% and a recovery rate of 91.23%.

[0043] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A device for preparing hydrated manganese oxalate from waste acid solution of high calcium and magnesium vanadium precipitation, comprising a first mixing box (2), characterized in that: Also includes: A discharge pipe (1) is fixedly arranged at the bottom of the first mixing box (2), a first valve is fixedly arranged on the discharge pipe (1), the first mixing box (2) is connected to the second mixing box (6) through an acid liquid pipe (5), an ultrasonic probe (3) is detachably arranged in both the first mixing box (2) and the second mixing box (6), and a second valve is fixedly arranged on the acid liquid pipe (5); an alkaline solution pipe (4) connected to the first mixing box (2); A waste liquid feed pipe (7) and an oxalic acid solution feed pipe (8), one end of each of the waste liquid feed pipe (7) and the oxalic acid solution feed pipe (8) are connected to the second mixing box (6).

2. The device for preparing hydrated manganese oxalate from waste acid solution of high calcium and magnesium vanadium precipitation according to claim 1, characterized in that: The first mixing box (2) and the second mixing box (6) are respectively provided with a first box cover (201) and a second box cover which are detachable on the top. The first box cover (201) and the second box cover are both provided with a plurality of mounting holes (202). The ultrasonic probe (3) is arranged in the mounting hole (202), and the two ends of the acid liquid pipe (5) are respectively fixedly connected to the first box cover (201) and the second mixing box (6). The alkaline solution pipe (4) is fixedly arranged on the first box cover (201), and the waste liquid feed pipe (7) and the oxalic acid solution feed pipe (8) are both fixedly arranged on the second box cover.

3. The device for preparing hydrated manganese oxalate from waste acid solution of high calcium and magnesium vanadium precipitation according to claim 2, characterized in that: A limiting groove (203) is provided in the first box cover (201), a connecting plate (901) is slidably arranged in the limiting groove (203), a clamping block (9) is fixedly arranged at one end of the connecting plate (901), a clamping groove (301) is provided on the shell of the ultrasonic probe (3), the clamping block (9) is engaged with the clamping groove (301), a spring is provided in the limiting groove (203), two ends of the spring are respectively against the limiting groove (203) and the connecting plate (901), a rack plate (902) is fixedly arranged at the other end of the connecting plate (901), a rotating shaft is rotatably arranged in the first box cover (201), a gear (903) meshing with the rack plate (902) is fixedly arranged at one end of the rotating shaft, and a knob (904) is fixedly arranged at the other end of the rotating shaft.

4. A method for preparing hydrated manganese oxalate from waste acid solution of high calcium and magnesium vanadium precipitation, using the device for preparing hydrated manganese oxalate from waste acid solution of high calcium and magnesium vanadium precipitation as claimed in any one of claims 1 to 3, characterized in that: The following steps are also included: Firstly, the waste liquid of calcination roasting-acid leaching-ammonium salt vanadium precipitation is fully mixed with the oxalic acid solution for a primary reaction; then the alkaline solution is easily mixed at a certain rate after mixing to carry out a secondary reaction, and a manganese oxalate suspension is obtained at the product discharge port; finally, a high-purity hydrated manganese oxalate solid powder is obtained by filtering and drying.

5. A method for preparing hydrated manganese oxalate from high calcium and magnesium vanadium precipitation waste acid solution according to claim 4, characterized in that: The concentration of the oxalic acid solution is 5%-9%, and the ratio of the amount of the oxalic acid substance introduced to the amount of the Mn substance introduced into the acid solution is 1:2-1:

1.

6. The method for preparing hydrated manganese oxalate from waste acid solution of high calcium and magnesium vanadium precipitation according to claim 4, characterized in that: The alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, or a mixture of the two.

7. The method for preparing hydrated manganese oxalate from waste acid solution of high calcium and magnesium vanadium precipitation according to claim 6, characterized in that: The pH value of the alkaline solution is 12-13.

5.

8. The method for preparing hydrated manganese oxalate from waste acid solution containing high calcium and magnesium vanadium precipitation according to claim 7, characterized in that: The amount of the alkaline solution introduced is adjusted according to the pH value of the product outlet solution, and the pH value of the product outlet solution is maintained at 3.4-3.6 by controlling the amount of the alkaline solution introduced.

9. The method for preparing hydrated manganese oxalate from waste acid solution of high calcium and magnesium vanadium precipitation according to claim 8, characterized in that: The flow rate of the oxalic acid solution is 2-4 m / s, the flow rate of the calcification roasting-acid leaching-ammonium salt vanadium precipitation waste liquid is 2-4 m / s, and the flow rate of the alkaline solution is 3-5 m / s.

10. The method for preparing hydrated manganese oxalate from waste acid solution containing high calcium and magnesium vanadium precipitation according to claim 4, characterized in that: The drying temperature is 10°C-100°C.

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