System and method for collaborative mineral phase conversion of ammonium sulfate residue and rhodochrosite in electrolytic manganese residue

Abstract

The present application relates to a kind of ammonium sulfate residue in electrolytic manganese residue and rhodochrosite collaborative mineral phase conversion system and method, belong to metallurgical beneficiation field.The ammonium sulfate residue in electrolytic manganese residue and rhodochrosite collaborative mineral phase conversion system of the present application includes feed bin, venturi dryer, first cyclone separator, second cyclone separator, suspension mixing bin, third cyclone separator, first flow seal valve, suspension mineral phase collaborative conversion furnace, fourth cyclone separator, second flow seal valve, first cooling cyclone, second cooling cyclone, third cooling cyclone, ball mill, spiral classifier, water immersion tank, first filter press, acid leaching tank, second filter press, noble liquid collector, filter residue collector;The present application adopts suspension roasting ammonium sulfate residue and rhodochrosite powder sulfur-fixing ammonium removal process roasting, sulfur-fixing, ammonium removal efficiency is high, production continuity is good, with low leaching acid consumption, environmental protection effect is good, meet the national green environmental protection requirement, be suitable for large-scale industrial production and the like advantages.

Description

Technical Field

[0001] This invention belongs to the field of metallurgical mineral processing technology, and specifically relates to a system and method for the synergistic mineral phase transformation of ammonium sulfate slag and rhodochrosite in electrolytic manganese slag. Background Technology

[0002] Manganese and manganese alloys are essential raw materials for the steel, aluminum alloy, magnetic materials, and chemical industries. Currently, the industrial production of high-purity manganese typically employs electrolytic manganese processing. The method involves adding concentrated sulfuric acid and anolyte to manganese ore powder, allowing the manganese in the ore powder to leach into the solution. The leachate is then neutralized (pH adjustment), oxidized (iron removal), sulfided (heavy metal removal), and filtered to obtain a qualified electrolyte. During the neutralization process, adjusting the pH by adding ammonia to a weak acid solution produces a certain amount of ammonium sulfate crystals. Therefore, controlling the harmful ammonium sulfate residue in electrolytic manganese slag to achieve its harmless treatment and meet relevant standards for waste gas pollutant management is crucial. Thus, a method for harmlessly treating ammonium sulfate residue and alleviating its storage and disposal problems is urgently needed. This not only aligns with the concept of sustainable development and environmental protection but also effectively improves resource utilization.

[0003] Patent CN201910870330.9 relates to a method for treating electrolytic manganese slag, proposing to wash the slag with clean water, followed by cyclic washing with an alkaline solution, ultimately achieving the goal of collecting water-soluble manganese and ammonium sulfate. This method achieves the harmless treatment of electrolytic manganese slag, but it requires a large amount of alkaline solution and has a low recovery rate of water-soluble manganese. It suffers from problems such as low efficiency, low resource utilization, and a narrow range of process applicability.

[0004] Therefore, the development of new technologies and industrial equipment for the harmless utilization of ammonium sulfate slag to obtain high-quality manganese ore products, and the realization of efficient and clean production of ammonium sulfate slag and rhodochrosite ore, has significant economic and social value. Summary of the Invention

[0005] This invention addresses the technical problems of existing traditional manganese ore leaching processes, such as low processing capacity, high cost, large dosage of leaching agents, and environmental pollution, by providing an industrial apparatus and method for improving manganese leaching rate and simultaneously harmlessly treating electrolytic manganese slag.

[0006] A system for co-conversion of ammonium sulfate residue and rhodochrosite in electrolytic manganese slag includes a feed hopper (3), a venturi dryer (6), a first cyclone separator (7), a second cyclone separator (8), a suspension mixing hopper (9), a third cyclone separator (10), a first flow sealing valve (11), a suspension phase co-conversion furnace (12), a fourth cyclone separator (13), a second flow sealing valve (14), a first cooling cyclone (15), a second cooling cyclone (16), a third cooling cyclone (17), a ball mill (20), a spiral classifier (21), a water immersion tank (22), a first filter press (23), an acid leaching tank (24), a second filter press (25), a precious liquor collector (26), and a filter residue collector (27).

[0007] The feeding bin (3) is provided with a first feeding belt (1) and a second feeding belt (2) above it for conveying materials to the feeding bin; a loss-in-weight feeder (4) is provided between the feeding bin (3) and the screw feeder (5), the outlet of the loss-in-weight feeder (4) is connected to the inlet of the screw feeder (5) through a pipe, and the outlet of the screw feeder (5) is connected to the inlet of the Venturi dryer (6);

[0008] The top outlet of the Venturi dryer (6) is connected to the inlet of the first cyclone separator (7) via a pipe; the bottom outlet of the first cyclone separator (7) is connected to the top outlet of the third cyclone separator (10) and the inlet of the second cyclone separator (8) via a pipe; the top outlet of the cyclone separator (8) is connected to the bottom air inlet of the Venturi dryer (6) via a pipe; and the bottom outlet of the cyclone separator (8) is connected to the suspended mixing bin (9) via a pipe. The discharge port of the suspended mixing bin (9) is connected to the inlet of the third cyclone separator (10) through a pipe, and the discharge port at the bottom of the third cyclone separator (10) is connected to the inlet of the first flow sealing valve (11) through a pipe; the discharge port of the first flow sealing valve (11) is connected to the first inlet of the suspended mineral phase co-conversion furnace (12) through a pipe, and the discharge port on the side of the fourth cyclone separator (13) is connected to the second inlet of the suspended mineral phase co-conversion furnace (12) through a pipe.

[0009] The upper part of the discharge port of the suspended mineral phase co-conversion furnace (12) is connected to the bottom inlet of the fourth cyclone separator (13) via a pipe; the discharge port of the suspended mineral phase co-conversion furnace (12) is connected to the inlet of the second flow sealing valve (14) via a pipe, and the discharge port of the second flow sealing valve (14) is connected to the inlet of the first cooling cyclone (15) via a pipe; the top discharge port of the first cooling cyclone (15) is connected to the bottom air inlet of the suspended mixing bin (9) via a pipe, and the bottom discharge port of the first cooling cyclone (15) is connected to the top of the third cooling cyclone (17) via a pipe. The discharge port at the end and the inlet of the second cooling cyclone (16) are connected by a pipe; the discharge port at the top of the second cooling cyclone (16) is connected by a pipe to the inlet of the cooling cyclone (15), and the discharge port at the bottom of the second cooling cyclone (16) is connected by a pipe to the inlet of the third cooling cyclone (17); the discharge port at the bottom of the third cooling cyclone (17) is connected by a pipe to the inlet of the collection bin (18), the discharge port of the collection bin (18) is connected by a pipe to the third feeding belt (19), and the third feeding belt (19) is connected by a pipe to the inlet of the ball mill (20);

[0010] Among them, the discharge port of the ball mill (20) is connected to the feed port of the spiral classifier (21) through a pipe, the discharge port of the spiral classifier (21) is connected to the ball mill (20) through a pipe, and the overflow discharge port of the spiral classifier (21) is connected to the feed port of the water immersion tank (22) through a pipe; the discharge port of the water immersion tank (22) is connected to the feed port of the first filter press (23), the liquid discharge port of the first filter press (23) is connected to the feed port of the precious liquid collector (26), and the solid discharge port of the first filter press (23) is connected to the feed port of the acid leaching tank (24) through a pipe; the discharge port of the acid leaching tank (24) is connected to the feed port of the second filter press (25), the liquid discharge port of the second filter press (25) is connected to the feed port of the precious liquid collector (26), and the solid discharge port of the second filter press (25) is connected to the feed port of the filter residue collector (27).

[0011] Furthermore, in the electrolytic manganese slag and rhodochrosite co-conversion system, the top outlet of the fourth cyclone separator (13) is connected to the second tail gas absorber (35) through a pipe, the second tail gas absorber (35) is connected to the induced draft fan (32), the top outlet of the first cyclone separator (7) is connected to the inlet of the dust collector (28) through a pipe, the outlet of the dust collector (28) is connected to the inlet of the induced draft fan (32) through a pipe, the outlet of the dust collector (28) is connected to the inlet of the air chute (29) through a pipe, the outlet of the air chute (29) is connected to the inlet of the pneumatic conveying pump (30) through a pipe; the outlet of the pneumatic conveying pump (30) is connected to the inlet of the third cyclone separator (10) through a pipe; the exhaust gas (34) purified by the induced draft fan (32) is discharged into the atmosphere through the chimney (33).

[0012] Furthermore, the outer wall of the suspended mineral phase co-conversion furnace (12) is equipped with an electric heating device and a heat preservation device, which can ensure that the temperature inside the suspended mineral phase co-conversion furnace (12) is the set temperature; the Venturi dryer (6) and the interior of the suspended mineral phase co-conversion furnace (12) are both equipped with thermocouple temperature measuring devices, which can monitor the temperature of each temperature measuring point in real time through a computer.

[0013] A method for the synergistic mineral phase transformation of ammonium sulfate slag and rhodochrosite in electrolytic manganese slag, employing the aforementioned ammonium sulfate slag and rhodochrosite synergistic mineral phase transformation system, is carried out according to the following steps:

[0014] Step 1: Preparation

[0015] Ammonium sulfate residue and rhodochrosite are fed to the feed bin (3) from the first feed belt (1) and the second feed belt (2) respectively. The material is fed to the screw feeder (5) through the loss-in-weight feeder (4), and the material is fed into the Venturi dryer (6) by the screw feeder (5). The temperature of the outlet of the Venturi dryer (6) is controlled to be above 100°C.

[0016] Step 2, Drying and Mixing

[0017] Start the induced draft fan (32) to generate negative pressure inside the system; under the action of negative pressure, the dried material enters the first cyclone separator (7) for material and flue gas separation, and the flue gas enters the dust collector (28). The material at the bottom of the first cyclone separator (7) is discharged from the bottom outlet of the first cyclone separator (7); the discharged material and the hot air flow from the top outlet of the third cyclone separator (10) enter the second cyclone separator (8) together; the hot air flow separated from the second cyclone separator (8) returns to the air inlet pipe of the Venturi dryer (6), and the material separated from the second cyclone separator (8) enters the suspension mixing bin (9) from the bottom outlet of the second cyclone separator (8);

[0018] Step 3: Co-conversion of mineral phases

[0019] Air is introduced into the suspension mixing bin (9) to fully mix the materials. The mixed materials enter the third cyclone separator (10) tangentially from the top outlet of the suspension mixing bin (9) for gas-solid separation. The airflow containing particles in the third cyclone separator (10) enters the second cyclone separator (8) for gas-solid separation. The material at the bottom of the third cyclone separator (10) first enters the first flow sealing valve (11) and then enters the suspension mineral phase co-conversion furnace (12). Inert gas (36) is introduced into the suspension mineral phase co-conversion furnace (12) to make the material in the suspension mineral phase co-conversion furnace (12) suspended. After roasting, roasted products are obtained.

[0020] Step 4: Cooling

[0021] The roasted product is fed into the first cooling cyclone (15), and the separated gas from the first cooling cyclone (15) is returned to the air inlet of the suspension mixing bin (9). The material coming out of the bottom outlet of the first cooling cyclone (15) is cooled by the second cooling cyclone (16) and the third cooling cyclone (17) in a step-by-step cooling system, so that the material temperature is reduced to below 150°C.

[0022] Step 5: Grinding

[0023] After cooling, the material enters the collection bin (18) and is fed into the feed inlet of the ball mill (20) via the third feed belt (19). The grinding product is fed into the feed inlet of the spiral classifier (21) for classification to obtain the classified product. The undercooked sand is returned to the ball mill (20) for regrinding, and the overflow is fed into the water immersion tank (22). The proportion of particles with a size of -0.074 mm in the overflow reaches more than 75%.

[0024] Step 6, Leaching

[0025] The overflow from the graded product is fed into the water leaching tank (22) for water leaching to obtain the water leached product. The water leached product is fed into the first filter press (23) for filter pressing. The leachate is fed into the precious liquor collector (26). The leaching residue is fed into the acid leaching tank (24) for acid leaching to obtain the acid leached product. The acid leached product is fed into the second filter press (25) for filter pressing. The leaching residue is fed into the filter residue collector (27). The leachate is fed into the precious liquor collector (26), which contains the final manganese leachate.

[0026] Furthermore, the roasting temperature in step 3 is 400~650℃, and the time is 10~70min.

[0027] Furthermore, in the suspension phase co-conversion furnace (12) described in step 3, the main reaction is as follows:

[0028] (NH4)2SO4+ MnCO3=MnSO4+2NH3+CO2+H2O (1)

[0029] MnCO3=MnO+CO2 (2).

[0030] Furthermore, the roasted product described in step 3 enters the second flow sealing valve (14) from the discharge port of the suspension phase co-conversion furnace (12). The cyclone separator (13) above the discharge port of the suspension phase co-conversion furnace (12) collects the inert gas that has not been fully reacted and the gas generated by the reaction into the second tail gas absorber (35). The separated dust is returned to the suspension phase co-conversion furnace (12).

[0031] Furthermore, in step 6, the water immersion temperature is 50℃~80℃, and the immersion time is 1 h~4 h; the hydrochloric acid concentration for acid immersion is 5 mol / L~15 mol / L, the immersion temperature is 60 ℃~100 ℃, and the immersion time is 1 h~4 h.

[0032] Furthermore, the dust-laden flue gas separated by the first cyclone separator (7) is purified by the dust collector (28) and becomes purified gas. The purified gas enters the chimney (33) through the induced draft fan (32) and is discharged. The dust falls into the air chute (29) and enters the pneumatic conveying pump (30), and finally returns to the third cyclone separator (10).

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] 1. The electrolytic manganese slag and rhodochrosite co-conversion system and method of the present invention have the advantages of low leaching acid consumption, good environmental protection effect, compliance with national green environmental protection requirements, and suitability for large-scale industrial production compared with the traditional beneficiation process for processing rhodochrosite ore.

[0035] 2. This invention uses a suspension roasting process of ammonium sulfate residue and rhodochrosite powder for sulfur fixation and deammonium removal, which has high efficiency in sulfur fixation and deammonium removal and good production continuity.

[0036] 3. Suspended synergistic mineral phase conversion technology has advantages over traditional roasting technology, such as the ability to achieve low-temperature and high-efficiency conversion, good heat and mass transfer efficiency, and lower required reaction time and temperature.

[0037] 4. After being treated with suspension mineral phase transformation technology, ore particles can develop internal cracks, which is beneficial for grinding operations, can achieve better individual particle dissociation, and can achieve energy saving and consumption reduction to a certain extent.

[0038] This invention provides a highly efficient solution for the harmless disposal of electrolytic manganese slag and the efficient utilization of rhodochrosite. By thoroughly mixing rhodochrosite with ammonium sulfate slag, a synergistic mineral phase transformation technology is employed to induce a chemical reaction between the ammonium sulfate slag and rhodochrosite powder. This not only achieves the purpose of sulfur fixation and deammonium removal but also effectively alleviates the supply and demand imbalance of manganese ore resources, solves problems such as land occupation and environmental pollution caused by ammonium sulfate slag, and ultimately creates significant economic benefits. Attached Figure Description

[0039] Figure 1 This is a schematic diagram of the structure of the electrolytic manganese slag and mineral powder co-conversion device of the present invention;

[0040] In the diagram, 1. First feeding belt; 2. Second feeding belt; 3. Feed hopper; 4. Loss-in-weight feeder; 5. Screw feeder; 6. Venturi dryer; 7. First cyclone separator; 8. Second cyclone separator; 9. Suspension mixing bin; 10. Third cyclone separator; 11. First flow sealing valve; 12. Suspension mineral phase co-conversion furnace; 13. Fourth cyclone separator; 14. Second flow sealing valve; 15. First cooling cyclone; 16. Second cooling cyclone; 17. 18. Third cooling cyclone, 19. Collection bin, 20. Third feeding belt, 21. Ball mill, 22. Spiral classifier, 23. Water immersion tank, 24. First filter press, 25. Acid immersion tank, 26. Second filter press, 27. Preservative liquid collector, 28. Filter residue collector, 29. Dust collector, 30. Air chute, 31. Pneumatic conveying pump, 32. First tail gas absorber, 33. Exhaust fan, 34. Chimney, 35. Exhaust gas, 36. Second tail gas absorber, 37. Inert gas. Detailed Implementation

[0041] The device for the synergistic transformation of ammonium sulfate slag and rhodochrosite in electrolytic manganese slag of this invention is constructed entirely according to the structure and process described in the foregoing invention. The technical solution in the implementation of this patent is clearly and completely described below with reference to embodiments and accompanying drawings. It should be noted that the embodiments described in this invention are only for further explanation and illustration, and not for limiting its scope of application. Based on this invention, all other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this patent.

[0042] Example 1

[0043] A system for the synergistic mineral phase transformation of ammonium sulfate residue and rhodochrosite in electrolytic manganese slag, such as... Figure 1 As shown, it includes a feed bin (3), a venturi dryer (6), a first cyclone separator (7), a second cyclone separator (8), a suspension mixing bin (9), a third cyclone separator (10), a first flow sealing valve (11), a suspension mineral phase co-conversion furnace (12), a fourth cyclone separator (13), a second flow sealing valve (14), a first cooling cyclone (15), a second cooling cyclone (16), a third cooling cyclone (17), a ball mill (20), a spiral classifier (21), a water immersion tank (22), a first filter press (23), an acid leaching tank (24), a second filter press (25), a precious liquor collector (26), and a filter residue collector (27).

[0044] The feeding bin (3) is provided with a first feeding belt (1) and a second feeding belt (2) above it for conveying materials to the feeding bin; a loss-in-weight feeder (4) is provided between the feeding bin (3) and the screw feeder (5), the outlet of the loss-in-weight feeder (4) is connected to the inlet of the screw feeder (5) through a pipe, and the outlet of the screw feeder (5) is connected to the inlet of the Venturi dryer (6);

[0045] The top outlet of the Venturi dryer (6) is connected to the inlet of the first cyclone separator (7) via a pipe; the bottom outlet of the first cyclone separator (7) is connected to the top outlet of the third cyclone separator (10) and the inlet of the second cyclone separator (8) via a pipe; the top outlet of the cyclone separator (8) is connected to the bottom air inlet of the Venturi dryer (6) via a pipe; and the bottom outlet of the cyclone separator (8) is connected to the suspended mixing bin (9) via a pipe. The discharge port of the suspended mixer (9) is connected to the inlet of the third cyclone separator (10) through a pipe, and the discharge port at the bottom of the third cyclone separator (10) is connected to the inlet of the first flow sealing valve (11) through a pipe; the discharge port of the first flow sealing valve (11) is connected to the first inlet of the suspended mineral phase co-conversion furnace (12) through a pipe, and the discharge port on the side of the fourth cyclone separator (13) is connected to the second inlet of the suspended mineral phase co-conversion furnace (12) through a pipe.

[0046] The upper part of the discharge port of the suspended mineral phase co-conversion furnace (12) is connected to the bottom inlet of the fourth cyclone separator (13) via a pipe; the discharge port of the suspended mineral phase co-conversion furnace (12) is connected to the inlet of the second flow sealing valve (14) via a pipe, and the discharge port of the second flow sealing valve (14) is connected to the inlet of the first cooling cyclone (15) via a pipe; the top discharge port of the first cooling cyclone (15) is connected to the bottom air inlet of the suspended mixing bin (9) via a pipe, and the bottom discharge port of the first cooling cyclone (15) is connected to the top of the third cooling cyclone (17) via a pipe. The discharge port at the end and the inlet of the second cooling cyclone (16) are connected by a pipe; the discharge port at the top of the second cooling cyclone (16) is connected by a pipe to the inlet of the cooling cyclone (15), and the discharge port at the bottom of the second cooling cyclone (16) is connected by a pipe to the inlet of the third cooling cyclone (17); the discharge port at the bottom of the third cooling cyclone (17) is connected by a pipe to the inlet of the collection bin (18), the discharge port of the collection bin (18) is connected by a pipe to the third feeding belt (19), and the third feeding belt (19) is connected by a pipe to the inlet of the ball mill (20);

[0047] Among them, the discharge port of the ball mill (20) is connected to the feed port of the spiral classifier (21) through a pipe, the discharge port of the spiral classifier (21) is connected to the ball mill (20) through a pipe, and the overflow discharge port of the spiral classifier (21) is connected to the feed port of the water immersion tank (22) through a pipe; the discharge port of the water immersion tank (22) is connected to the feed port of the first filter press (23), the liquid discharge port of the first filter press (23) is connected to the feed port of the precious liquid collector (26), and the solid discharge port of the first filter press (23) is connected to the feed port of the acid leaching tank (24) through a pipe; the discharge port of the acid leaching tank (24) is connected to the feed port of the second filter press (25), the liquid discharge port of the second filter press (25) is connected to the feed port of the precious liquid collector (26), and the solid discharge port of the second filter press (25) is connected to the feed port of the filter residue collector (27).

[0048] Furthermore, in the electrolytic manganese slag and rhodochrosite co-conversion system, the top outlet of the fourth cyclone separator (13) is connected to the second tail gas absorber (35) through a pipe, the second tail gas absorber (35) is connected to the induced draft fan (32), the top outlet of the first cyclone separator (7) is connected to the inlet of the dust collector (28) through a pipe, the outlet of the dust collector (28) is connected to the inlet of the induced draft fan (32) through a pipe, the outlet of the dust collector (28) is connected to the inlet of the air chute (29) through a pipe, the outlet of the air chute (29) is connected to the inlet of the pneumatic conveying pump (30) through a pipe; the outlet of the pneumatic conveying pump (30) is connected to the inlet of the third cyclone separator (10) through a pipe; the exhaust gas (34) purified by the induced draft fan (32) is discharged into the atmosphere through the chimney (33).

[0049] Furthermore, the outer wall of the suspended mineral phase co-conversion furnace (12) is equipped with an electric heating device and a heat preservation device, which can ensure that the temperature inside the suspended mineral phase co-conversion furnace (12) is the set temperature; the Venturi dryer (6) and the interior of the suspended mineral phase co-conversion furnace (12) are both equipped with thermocouple temperature measuring devices, which can monitor the temperature of each temperature measuring point in real time through a computer.

[0050] A method for the synergistic mineral phase transformation of ammonium sulfate slag and rhodochrosite in electrolytic manganese slag, employing the aforementioned ammonium sulfate slag and rhodochrosite synergistic mineral phase transformation system, is carried out according to the following steps:

[0051] Step 1: Preparation

[0052] The main mineral grades of ammonium sulfate slag are: total manganese: 4.09%, ammonium sulfate: 35.02%; the main mineral grades of manganese carbonate ore powder are: total manganese: 22.77%, tetravalent manganese: 0.14%; when ammonium sulfate slag and manganese carbonate ore powder are mixed in a ratio of 1:1.3, a mixture is obtained, whose main mineral grades are: total manganese: 14.65%, tetravalent manganese: 0.13%, ammonium sulfate: 14.13%, sulfate: 18.12%.

[0053] The mixed materials are fed to the feeding bin (3) via the material belt (1) and the feeding belt (2), respectively. The material is fed to the screw feeder (5) via the loss-in-weight feeder (4), and the screw feeder (5) feeds the material into the Venturi dryer (6). The temperature of the outlet of the Venturi dryer (6) is controlled to be above 100°C.

[0054] Step 2, Drying and Mixing

[0055] Start the induced draft fan (32) to generate negative pressure inside the system. Under the action of negative pressure, the material to be dried in the Venturi dryer (6) enters the first cyclone separator (7) for material and flue gas separation. The flue gas enters the dust collector (28), and the material is discharged from the bottom outlet of the first cyclone separator (7). The discharged material and the hot air flow from the top outlet of the third cyclone separator (10) enter the second cyclone separator (8). The hot air flow separated from the second cyclone separator (8) returns to the air inlet pipe of the Venturi dryer (6). The material separated from the second cyclone separator (8) enters the suspension mixing bin (9) from the bottom outlet of the second cyclone separator (8).

[0056] Step 3: Co-conversion of mineral phases

[0057] Air is introduced into the suspension mixing bin (9) to fully mix the materials. The mixed materials then enter the third cyclone separator (10) tangentially from the top outlet of the suspension mixing bin (9) for gas-solid separation. The airflow mixed with particles in the third cyclone separator (10) enters the second cyclone separator (8) for gas-solid separation. The material at the bottom of the third cyclone separator (10) enters the first flow sealing valve (11) and then enters the suspension mineral phase co-conversion furnace (12). Inert gas (36) is introduced into the bottom of the first flow sealing valve (11) to make the material enter the suspension mineral phase co-conversion furnace (12) evenly. Inert gas (36) is introduced into the suspension mineral phase co-conversion furnace (12), and the flow rate of the inert gas is adjusted to make the material in the suspension mineral phase co-conversion furnace (12) in a suspended state. The temperature of the material is controlled at 470~500℃ and the residence time is 30~50 min. Under these conditions, the ammonium sulfate slag reacts with rhodochrosite to obtain the roasted product.

[0058] The roasted product enters the flow seal (14) from the discharge port of the suspension phase co-conversion furnace (12). The cyclone separator (13) above the discharge port of the suspension phase co-conversion furnace (12) collects the inert gas that has not been fully reacted and the gas generated by the reaction into the second tail gas absorber (35). The separated dust is returned to the suspension phase co-conversion furnace (12).

[0059] Step 4: Cooling

[0060] The roasted product is fed into the first cooling cyclone (15), and the air separated by the first cooling cyclone (15) is returned to the air inlet of the suspension mixing bin (9). The material coming out of the bottom outlet of the first cooling cyclone (15) is cooled by the second cooling cyclone (16) and the third cooling cyclone (17) in a step-by-step cooling system, so that the material temperature is reduced to below 150°C.

[0061] Step 5: Grinding

[0062] After cooling, the material enters the collection bin (18) and is fed into the feed inlet of the ball mill (20) via the third feed belt (19). The ground product is fed into the feed inlet of the spiral classifier (21) for classification. The classified sand is returned to the ball mill (20) for re-grinding, and the overflow is fed into the water immersion tank (22). The proportion of material with a particle size of -0.074 mm in the overflow reaches 85%.

[0063] Step 6, Leaching

[0064] The material that has completed the grading process is put into the water leaching tank (22) for water leaching. The water leaching temperature is 50℃ and the leaching time is 2 h to obtain the water leaching product. The water leaching product is fed into the first filter press for filter pressing. The leachate is fed into the precious liquid collector (26) and the leachate residue is fed into the acid leaching tank (24) for acid leaching. The concentration of the acid leaching hydrochloric acid is 10 mol / L, the leaching temperature is 60℃ and the leaching time is 1.5 h to obtain the acid leaching product. The leachate residue is fed into the filter residue collector (27) and the leachate is fed into the precious liquid collector (26). The precious liquid collector (26) is the final manganese leachate. Finally, the manganese leaching rate is 96.11%, the deammoniation rate is 97.32%, and the sulfur fixation rate is 100%, which are good indicators.

[0065] Example 2

[0066] The system structure is the same as in Example 1; the method is the same as in Example 1, except that:

[0067] The main mineral grades of ammonium sulfate slag are: total manganese: 4.09%, ammonium sulfate: 35.02%; the main mineral grades of manganese carbonate ore powder are: total manganese: 22.77%, tetravalent manganese: 0.14%. A mixture of ammonium sulfate slag and manganese carbonate ore powder in a 1:1.3 ratio has the following main mineral grades: total manganese: 14.65%, tetravalent manganese: 0.13%, ammonium sulfate: 14.13%, sulfate: 18.12%.

[0068] In step 3, the material temperature in the suspension phase co-conversion furnace (12) is controlled at 460~480℃ and the residence time is 30~40min;

[0069] The final results achieved a good manganese leaching rate of 96.33%, a deammoniation rate of 96.89%, and a sulfur fixation rate of 100%.

[0070] Example 3

[0071] The system structure is the same as in Implementation Example 1;

[0072] The method is the same as in Example 1, except that:

[0073] The main mineral grades of ammonium sulfate slag are: total manganese: 4.18%, ammonium sulfate: 35.71%; the main mineral grades of manganese carbonate ore powder are: total manganese: 23.27%, tetravalent manganese: 0.12%. A mixture of ammonium sulfate slag and manganese carbonate ore powder in a 1:1.4 ratio has the following main mineral grades: total manganese: 15.31%, tetravalent manganese: 0.17%, ammonium sulfate: 14.06%, sulfate: 18.15%.

[0074] In step 3, the material temperature in the suspension phase co-conversion furnace (12) is controlled at 550~600℃ and the residence time is 30~40 min;

[0075] In step 5, the proportion of material particles with a diameter of -0.074 mm in the overflow reaches 90%;

[0076] In step 6, the concentration of hydrochloric acid used for acid leaching is 9.5 mol / L, the leaching temperature is 60℃, and the leaching time is 1.6 h.

[0077] The final results achieved a good manganese leaching rate of 97.11%, a deammoniation rate of 96.93%, and a sulfur fixation rate of 100%.

[0078] Example 4

[0079] The system structure is the same as in Implementation Example 1;

[0080] The method is the same as in Example 1, except that:

[0081] The main mineral grades of ammonium sulfate slag are: total manganese: 3.84%, ammonium sulfate: 35.10%; the main mineral grades of manganese carbonate ore powder are: total manganese: 24.66%, tetravalent manganese: 0.18%. A mixture of ammonium sulfate slag and manganese carbonate ore powder in a 1:1.5 ratio has the following main mineral grades: total manganese: 16.33%, tetravalent manganese: 0.20%, ammonium sulfate: 13.71%, sulfate: 17.83%.

[0082] In step 3, the material temperature in the suspension phase co-conversion furnace (12) is controlled at 520~550℃ and the residence time is 30~40 min;

[0083] In step 5, the proportion of material particles with a diameter of -0.074 mm in the overflow reaches 90%;

[0084] In step 6, the concentration of hydrochloric acid used for acid leaching is 11 mol / L, the leaching temperature is 60℃, and the leaching time is 1.6 h.

[0085] The final results achieved a good manganese leaching rate of 97.54%, a deammoniation rate of 96.41%, and a sulfur fixation rate of 100%.

[0086] Example 5

[0087] The system structure is the same as in Implementation Example 1;

[0088] The method is the same as in Example 1, except that:

[0089] The main mineral grades of ammonium sulfate slag are: total manganese: 4.55%, ammonium sulfate: 36.22%; the main mineral grades of manganese carbonate ore powder are: total manganese: 24.74%, tetravalent manganese: 0.19%. A mixture of ammonium sulfate slag and manganese carbonate ore powder in a 1:1.6 ratio has the following main mineral grades: total manganese: 16.97%, tetravalent manganese: 0.24%, ammonium sulfate: 14.71%, sulfate: 18.66%.

[0090] In step 3, the material temperature in the suspension phase co-conversion furnace (12) is controlled at 580~600 ℃ and the residence time is 30~40 min;

[0091] In step 5, the proportion of material particles with a diameter of -0.074 mm in the overflow reached 88.44%.

[0092] In step 6, the concentration of hydrochloric acid used for acid leaching is 9.5 mol / L, the leaching temperature is 55℃, and the leaching time is 1.7 h.

[0093] The final results achieved a good manganese leaching rate of 98.10%, a deammoniation rate of 97.24%, and a sulfur fixation rate of 100%.

[0094] Example 6

[0095] The system structure is the same as in Implementation Example 1;

[0096] The method is the same as in Example 1, except that:

[0097] The main mineral grades of ammonium sulfate slag are: total manganese: 4.38%, ammonium sulfate: 37.71%; the main mineral grades of manganese carbonate ore powder are: total manganese: 25.16%, tetravalent manganese: 0.12%. A mixture of ammonium sulfate slag and manganese carbonate ore powder in a 1:1.5 ratio has the following main mineral grades: total manganese: 16.85%, tetravalent manganese: 0.17%, ammonium sulfate: 14.88%, sulfate: 19.41%.

[0098] In step 3, the material temperature in the suspension phase co-conversion furnace (12) will be controlled at 540~560℃ and the residence time will be 30~40 min;

[0099] In step 5, the proportion of material particles with a diameter of -0.074 mm in the overflow reached 92.35%;

[0100] In step 6, the concentration of hydrochloric acid used for acid leaching is 12 mol / L, the leaching temperature is 50℃, and the leaching time is 2.2 h.

[0101] The final results achieved a good manganese leaching rate of 98.12%, a deammoniation rate of 97.88%, and a sulfur fixation rate of 100%.

[0102] The solutions described in the embodiments are not intended to limit the scope of patent protection of this invention. All equivalent implementations or modifications that do not depart from the scope of this invention are included in the patent scope of this case.

Claims

1. A system for the co-mineral phase conversion of ammonium sulfate residue and rhodochrosite in electrolytic manganese residue, characterized by, Includes a feed hopper (3), a venturi dryer (6), a first cyclone separator (7), a second cyclone separator (8), a suspension mixing hopper (9), a third cyclone separator (10), a first flow sealing valve (11), a suspension mineral phase co-conversion furnace (12), a fourth cyclone separator (13), a second flow sealing valve (14), a first cooling cyclone (15), a second cooling cyclone (16), a third cooling cyclone (17), a ball mill (20), a spiral classifier (21), a water immersion tank (22), a first filter press (23), an acid leaching tank (24), a second filter press (25), a precious liquor collector (26), and a filter residue collector (27); The feeding bin (3) is provided with a first feeding belt (1) and a second feeding belt (2) above it for conveying materials to the feeding bin; a loss-in-weight feeder (4) is provided between the feeding bin (3) and the screw feeder (5), the outlet of the loss-in-weight feeder (4) is connected to the inlet of the screw feeder (5) through a pipe, and the outlet of the screw feeder (5) is connected to the inlet of the Venturi dryer (6); The top outlet of the Venturi dryer (6) is connected to the inlet of the first cyclone separator (7) via a pipe. The bottom outlet of the first cyclone separator (7) is connected to the top outlet of the third cyclone separator (10) and the inlet of the second cyclone separator (8) via a pipe. The top outlet of the second cyclone separator (8) is connected to the bottom air inlet of the Venturi dryer (6) via a pipe. The bottom outlet of the second cyclone separator (8) is connected to the suspended mixing bin (9) via a pipe. The discharge port of the suspended mixing bin (9) is connected to the inlet of the third cyclone separator (10) through a pipe, and the discharge port at the bottom of the third cyclone separator (10) is connected to the inlet of the first flow sealing valve (11) through a pipe; the discharge port of the first flow sealing valve (11) is connected to the first inlet of the suspended mineral phase co-conversion furnace (12) through a pipe, and the discharge port on the side of the fourth cyclone separator (13) is connected to the second inlet of the suspended mineral phase co-conversion furnace (12) through a pipe; The upper part of the discharge port of the suspended mineral phase co-conversion furnace (12) is connected to the bottom inlet of the fourth cyclone separator (13) through a pipe; the discharge port of the suspended mineral phase co-conversion furnace (12) is connected to the inlet of the second flow sealing valve (14) through a pipe, and the discharge port of the second flow sealing valve (14) is connected to the inlet of the first cooling cyclone (15) through a pipe; the top discharge port of the first cooling cyclone (15) is connected to the bottom air inlet of the suspended mixing bin (9) through a pipe, and the bottom discharge port of the first cooling cyclone (15) is connected to the top discharge port of the third cooling cyclone (17) through a pipe. The feed inlet and the feed inlet of the second cooling cyclone (16) are connected by a pipe; the top outlet of the second cooling cyclone (16) is connected by a pipe to the feed inlet of the first cooling cyclone (15), and the bottom outlet of the second cooling cyclone (16) is connected by a pipe to the feed inlet of the third cooling cyclone (17); the bottom outlet of the third cooling cyclone (17) is connected by a pipe to the feed inlet of the collection bin (18), the outlet of the collection bin (18) is connected by a pipe to the third feeding belt (19), and the third feeding belt (19) is connected by a pipe to the feed inlet of the ball mill (20); The discharge port of the ball mill (20) is connected to the inlet of the spiral classifier (21) via a pipe. The sand discharge port of the spiral classifier (21) is connected to the ball mill (20) via a pipe. The overflow discharge port of the spiral classifier (21) is connected to the inlet of the water immersion tank (22) via a pipe. The discharge port of the water immersion tank (22) is connected to the inlet of the first filter press (23). The liquid discharge port of the first filter press (23) is connected to the inlet of the precious liquid collector (26). The solid discharge port of the first filter press (23) is connected to the inlet of the acid leaching tank (24) via a pipe. The discharge port of the acid leaching tank (24) is connected to the inlet of the second filter press (25). The liquid discharge port of the second filter press (25) is connected to the inlet of the precious liquid collector (26). The solid discharge port of the second filter press (25) is connected to the inlet of the filter residue collector (27). In the electrolytic manganese slag and rhodochrosite co-conversion system, the top outlet of the fourth cyclone separator (13) is connected to the second tail gas absorber (35) through a pipe, the second tail gas absorber (35) is connected to the induced draft fan (32), the top outlet of the first cyclone separator (7) is connected to the inlet of the dust collector (28) through a pipe, the outlet of the dust collector (28) is connected to the inlet of the induced draft fan (32) through a pipe, the outlet of the dust collector (28) is connected to the inlet of the air chute (29) through a pipe, the outlet of the air chute (29) is connected to the inlet of the pneumatic conveying pump (30) through a pipe, the outlet of the pneumatic conveying pump (30) is connected to the inlet of the third cyclone separator (10) through a pipe, and the exhaust gas (34) purified by the induced draft fan (32) is discharged into the atmosphere through the chimney (33).

2. The system for the synergistic mineral phase transformation of ammonium sulfate residue and rhodochrosite in electrolytic manganese residue according to claim 1, characterized in that, The outer wall of the suspended mineral phase co-conversion furnace (12) is equipped with an electric heating device and a heat preservation device, which can ensure that the temperature inside the suspended mineral phase co-conversion furnace (12) is the set temperature; the Venturi dryer (6) and the interior of the suspended mineral phase co-conversion furnace (12) are both equipped with thermocouple temperature measuring devices, which can monitor the temperature of each temperature measuring point in real time through a computer.

3. A method for the simultaneous mineral phase transformation of ammonium sulfate residue and rhodochrosite in electrolytic manganese residue, using the simultaneous mineral phase transformation system of ammonium sulfate residue and rhodochrosite in electrolytic manganese residue according to any one of claims 1-2, characterized in that, Follow these steps: Step 1: Preparation Ammonium sulfate residue and rhodochrosite are fed to the feed bin (3) via the first feed belt (1) and the second feed belt (2) respectively. The material is fed to the screw feeder (5) via the loss-in-weight feeder (4), and the screw feeder (5) feeds the material into the Venturi dryer (6). The temperature of the Venturi dryer (6) outlet is controlled to be above 100°C. Step 2, Drying and Mixing Start the induced draft fan (32) to generate negative pressure inside the system; under the action of negative pressure, the dried material enters the first cyclone separator (7) for material and flue gas separation, and the flue gas enters the dust collector (28). The material at the bottom of the first cyclone separator (7) is discharged from the bottom outlet of the first cyclone separator (7); the discharged material and the hot air flow from the top outlet of the third cyclone separator (10) enter the second cyclone separator (8) together; the hot air flow separated from the second cyclone separator (8) returns to the air inlet pipe of the Venturi dryer (6), and the material separated from the second cyclone separator (8) enters the suspension mixing bin (9) from the bottom outlet of the second cyclone separator (8); Step 3: Co-conversion of mineral phases Air is introduced into the suspension mixing bin (9) to fully mix the materials. The mixed materials enter the third cyclone separator (10) tangentially from the top outlet of the suspension mixing bin (9) for gas-solid separation. The airflow containing particles in the third cyclone separator (10) enters the second cyclone separator (8) for gas-solid separation. The material at the bottom of the third cyclone separator (10) first enters the first flow sealing valve (11) and then enters the suspension mineral phase co-conversion furnace (12). Inert gas (36) is introduced into the suspension mineral phase co-conversion furnace (12) to make the material in the suspension mineral phase co-conversion furnace (12) suspended. After roasting, the roasted product is obtained. Step 4: Cooling The roasted product is fed into the first cooling cyclone (15), and the separated gas from the first cooling cyclone (15) is returned to the air inlet of the suspension mixing bin (9). The material coming out of the bottom outlet of the first cooling cyclone (15) is cooled by the second cooling cyclone (16) and the third cooling cyclone (17) in a step-by-step cooling system, so that the material temperature is reduced to below 150°C. Step 5: Grinding After cooling, the material enters the collection bin (18) and is fed into the feed inlet of the ball mill (20) via the third feeding belt (19). The grinding product is fed into the feed inlet of the spiral classifier (21) for classification to obtain the classified product. The undercooked sand is returned to the ball mill (20) for regrinding, and the overflow is fed into the water immersion tank (22). The proportion of particles with a size of -0.074 mm in the overflow reaches more than 75%. Step 6, Leaching The overflow from the graded product is fed into the water leaching tank (22) for water leaching to obtain the water leached product. The water leached product is fed into the first filter press (23) for filter pressing. The leachate is fed into the precious liquor collector (26). The leaching residue is fed into the acid leaching tank (24) for acid leaching to obtain the acid leached product. The acid leached product is fed into the second filter press (25) for filter pressing. The leaching residue is fed into the filter residue collector (27). The leachate is fed into the precious liquor collector (26), which contains the final manganese leachate.

4. The method for the phase transformation of ammonium sulfate residue in electrolytic manganese residue and rhodochrosite in cooperation according to claim 3, characterized in that, In step 3, the roasting temperature is 400~650℃ and the time is 10~70min.

5. The method for the phase transformation of ammonium sulfate residue in electrolytic manganese residue and rhodochrosite in coordination according to claim 3, characterized in that, The roasted product described in step 3 enters the second flow sealing valve (14) from the discharge port of the suspension phase co-conversion furnace (12). The fourth cyclone separator (13) above the discharge port of the suspension phase co-conversion furnace (12) introduces the inert gas that has not been fully reacted and the gas generated by the reaction into the second tail gas absorber (35) for collection. The separated dust is returned to the suspension phase co-conversion furnace (12).

6. The method for the synergic mineral phase conversion of ammonium sulfate residue in electrolytic manganese residue and rhodochrosite according to claim 3, characterized in that, In step 6, the water immersion temperature is 50℃~80℃, and the immersion time is 1 h~4 h; the hydrochloric acid concentration for acid immersion is 5 mol / L~15 mol / L, the immersion temperature is 60 ℃~100 ℃, and the immersion time is 1 h~4 h.

7. The method for the synergic mineral phase conversion of ammonium sulfate residue in electrolytic manganese residue and rhodochrosite according to claim 3, characterized in that, The dust-laden flue gas separated by the first cyclone separator (7) becomes purified gas after being removed by the dust collector (28). The purified gas enters the chimney (33) through the induced draft fan (32) and is discharged. The dust enters the pneumatic conveying pump (30) through the air chute (29) and finally returns to the third cyclone separator (10).

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