A method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource circulation

Abstract

The invention discloses a method for preparing industrial manganese carbonate and high-purity manganese sulfate based on the circulation of ammonium sulfate resources. The invention uses low-grade rhodochrosite powder as raw material, adopts ammonium sulfate roasting and leaching, and the roasting gas is captured to prepare a manganese precipitant; the roasted ore sand is leached by water, and a manganese sulfate mother liquor is prepared after preliminary impurity removal; the manganese sulfate mother liquor is combined with the manganese precipitant for reaction, and the solid phase product is a composite manganese salt, and the liquid phase is evaporated and crystallized to obtain ammonium sulfate powder, which is reused for roasting and leaching; the composite manganese salt is slurried with water, heated and stirred continuously, and air is introduced, and the solid phase is dried after filtering to obtain industrial-grade manganese carbonate, and the liquid phase is evaporated and crystallized to obtain high-purity manganese sulfate. The invention realizes the ammonia-sulfur substance cycle of the manganese-based material preparation process, and effectively reduces the reagent input cost. The invention can simultaneously prepare industrial manganese carbonate and high-purity manganese sulfate, so as to achieve efficient utilization of manganese resources. Compared with the traditional process, it has the characteristics of low cost, simple operation, stable products, etc.

Description

Technical Field

[0001] The invention belongs to the field of manganese ore metallurgy and high-purity manganese-based material preparation, and specifically relates to a method for preparing industrial manganese carbonate and high-purity manganese sulfate based on the circulation of ammonium sulfate resources. Background Art

[0002] Ammonium salts are often used as basic raw materials in the technical production of the manganese industry, and a large amount of impure ammonium sulfate is produced. These impure ammonium sulfates have not been widely used in agriculture due to quality issues. At the same time, the large amount of stockpiling of impure ammonium sulfate also affects the local ecological environment. The best way to dispose of impure ammonium sulfate is to reuse it as a production material in the front-end process. Some researchers use wet deammoniation to add calcium oxide to the ammonium sulfate solution. In an alkaline environment, ammonium ions combine with hydroxide ions, and ammonia is released under heating. It is then captured in the liquid phase to make ammonia water; some researchers directly mix ammonium sulfate powder with metal oxide solids and roast them. A large amount of ammonia is generated through high-temperature reaction, and metal sulfates are used for other purposes, among which calcium oxide and magnesium oxide have the best conversion effect. However, the above method is prone to produce solid wastes such as ammonia-containing gypsum slag, which will increase disposal costs and have potential environmental pollution risks.

[0003] The above risks can be avoided by using ammonium sulfate as a leaching agent. Under high temperature conditions, ammonium sulfate can convert the target metal in the mineral into soluble metal sulfate, which is beneficial to the extraction and purification of the target metal. Some researchers mixed ammonium sulfate with rhodochrosite and roasted it. Under the appropriate ratio, the manganese sulfate conversion rate reached more than 85%. Under ideal conditions, the roasting gas produced is ammonia and carbon dioxide, but usually because of the difficulty of solid-liquid reaction mass transfer process, ammonium sulfate self-thermolysis produces sulfur dioxide, sulfur trioxide, nitrogen and ammonia, which increases the cost of tail gas treatment. Because of this problem, there are currently no industrial cases in the industry regarding the roasting and leaching of rhodochrosite with ammonium sulfate. Summary of the invention

[0004] In view of the technical problems such as the generation of secondary by-products during the disposal of the impurity ammonium sulfate and the generation of mixed waste gas during the roasting and leaching of ammonium sulfate, the present invention provides a method for preparing industrial manganese carbonate and high-purity manganese sulfate based on the recycling of ammonium sulfate resources. The roasting gas is captured and recovered to prepare an ammonium bicarbonate / ammonium sulfite mixed solution, which is used as a manganese precipitant. The precipitated composite manganese salt is then thermally oxidized to obtain industrial manganese carbonate and high-purity manganese sulfate. This method can not only solve the problem of the disposal of the gas generated during the roasting and leaching of ammonium sulfate, but also the prepared manganese-based material meets the product standards and has great industrialization potential.

[0005] The technical solution adopted by the present invention is specifically as follows:

[0006] A method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource recycling comprises the following steps:

[0007] S1. The low-grade rhodochrosite powder is mixed with ammonium sulfate and then roasted to obtain roasted ore, and the roasted gas is captured by dilute ammonia water to prepare a manganese precipitant;

[0008] S2. The roasted ore obtained in S1 is mixed with water to form a slurry, and the leaching is continuously stirred to obtain a manganese sulfate mother liquor after preliminary impurity removal;

[0009] S3. The manganese precipitant obtained in S1 is input into the manganese sulfate mother liquor obtained in S2 for precipitation reaction to obtain a composite manganese salt and an ammonium sulfate solution, and the ammonium sulfate solution is evaporated and crystallized and then reused in S1;

[0010] S4. The composite manganese salt obtained in S3 is slurried with water, continuously heated and stirred, and air is introduced for thermal oxidation, followed by solid-liquid separation, and the solid phase is dried to obtain industrial-grade manganese carbonate, and the liquid phase is a high-purity manganese sulfate solution;

[0011] S5. The high-purity manganese sulfate solution obtained in S4 is evaporated and crystallized to obtain high-purity manganese sulfate.

[0012] The high-purity manganese sulfate is manganese sulfate having a calcium and magnesium content of less than 150 ppm.

[0013] Furthermore, in S1, the mass ratio of low-grade rhodochrosite to ammonium sulfate is 2~5:1, the roasting temperature is 400~500°C, the roasting time is 2~4h, the roasting uses inert gas as carrier gas, the carrier gas flow rate is 2~4 m³ / h, and the concentration of dilute ammonia water is 9%~10.5%.

[0014] Furthermore, in S2, the mass ratio of water to roasted ore is 2.5~5.0, the stirring rate is 50~120 r / min, the leaching time is 4~6h, and the leaching temperature is 80~90℃.

[0015] Furthermore, in S2, the impurity remover used for preliminary impurity removal is a mixture of manganese dioxide powder, calcium carbonate and sodium fumei, and the mass ratios of manganese dioxide powder, calcium carbonate, sodium fumei and roasted ore are 0.1~0.2, 0.1~0.3, and 0.006~0.01, respectively. The impurity removal is carried out under stirring conditions, the stirring rate is 50~120 Hz, and the impurity removal temperature is 70~80°C.

[0016] Furthermore, in S3, the input time of manganese precipitant is controlled at 1~1.5 h, the reaction stirring rate is 600~800 r / min, the reaction pH is stabilized at 6.5~7.5, the reaction time is 2~2.5 h, and aging is carried out after the reaction for 2~3 h.

[0017] Furthermore, in S4, the mass ratio of the complex manganese salt to water is 0.8-1.0, the heating temperature is 60-80°C, the air flow rate is 80-100 L / min, the thermal oxidation time is 6-8h, and the drying temperature of the solid phase is 100-120°C.

[0018] Furthermore, in S5, the temperature of evaporation crystallization is 100-120°C; and the pH is adjusted to 3.5-4.0 before evaporation crystallization.

[0019] The present invention uses a composite manganese salt as an intermediate product and then prepares industrial-grade manganese carbonate and high-purity manganese sulfate by thermal oxidation. To further illustrate the basic chemical principle of the present invention, the main chemical formulas involved are as follows:

[0020] Roasting process:

[0021]

[0022] Gas capture process:

[0023]

[0024] Manganese precipitation process:

[0025]

[0026] Thermal oxidation process:

[0027]

[0028] The beneficial effects of the present invention are:

[0029] (1) The present invention uses the by-product ammonium sulfate as a rhodochrosite leaching agent, which effectively reduces the amount of sulfuric acid input into the system.

[0030] (2) The present invention uses the mixed solution of ammonium carbonate / ammonium sulfite prepared after the gas produced by leaching as a manganese precipitant, which can reduce the reagent cost.

[0031] (3) The present invention uses a composite manganese salt as an intermediate product to simultaneously prepare industrial-grade manganese carbonate and high-purity manganese sulfate, thereby achieving efficient utilization of manganese resources.

[0032] In summary, the present invention realizes the ammonia-sulfur material cycle in the manganese-based material preparation process, effectively reducing the reagent input cost. The present invention can simultaneously prepare industrial manganese carbonate and high-purity manganese sulfate, achieving efficient utilization of manganese resources. Compared with the traditional process, it has the characteristics of low cost, simple operation, stable products, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a process flow chart of the method of the present invention;

[0034] Figure 2 is a flow chart of the equipment of the method of the present invention;

[0035] Figure 3 This is the XRD pattern of the high-purity manganese sulfate obtained in Example 1;

[0036] Figure 4 The XRD pattern of the industrial-grade manganese carbonate obtained in Example 1;

[0037] Among them, 1. tubular atmosphere furnace, 2. leaching tank, 3. plate and frame filter press I, 4. liquid storage tank I, 5. reactor I, 6. plate and frame filter press II, 7. reactor II, 8. plate and frame filter press III, 9. evaporator I, 10. drying oven, 11. evaporator II, 12. liquid storage tank II, 13. liquid storage tank III, 14. ammonia absorption tower, 15. captured liquid storage tank, 16. induced draft fan, A. mixed powder of rhodochrosite and ammonium sulfate, B. manganese slag, C. ammonium sulfate, D. high-purity manganese sulfate, E. industrial manganese carbonate, F. impurity remover, and G. tail gas. DETAILED DESCRIPTION

[0038] In order to better understand the present invention, the present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments, but the present invention is not limited thereto.

[0039] The process flow diagram of the method of the present invention is as follows: Figure 1 As shown, the equipment flow chart of the method of the present invention is as follows Figure 2 As shown, the equipment specifically includes a tubular atmosphere furnace 1, a leaching tank 2, a plate-frame filter press I 3, a liquid storage tank I 4, a reactor I 5, a plate-frame filter press II 6, a reactor II 7, a plate-frame filter press III 8, an evaporator I 9, a drying box 10, an evaporator II 11, a liquid storage tank II 12, a liquid storage tank III 13, an ammonia absorption tower 14, a captured liquid storage tank 15, and an induced draft fan 16. The tubular atmosphere furnace 1 is provided with a mixing device, a feeding hopper, and a discharge bin. The lower end of the leaching tank 2 is provided with a liquid outlet valve, and the slurry is pumped into the plate filter press I through a diaphragm pump. The liquid outlet of the plate-frame filter press I is connected to the liquid storage tank I. A valve is provided at the bottom of the liquid storage tank I, and the solution is input into the reactor I through a centrifugal pump. The reactor I is provided with a stirring motor and a heating interlayer, and the bottom end of the reactor I is provided with a liquid outlet valve connected to the plate-frame filter press II. The solid phase product produced by the plate and frame filter press II is manually transported to the reactor II, while the liquid phase product is transported to the evaporator II. The reactor II is equipped with a stirring motor and a heating interlayer, and the bottom of the reactor II is equipped with a liquid outlet valve connected to the plate and frame filter press III. The solid phase product produced by the plate and frame filter press III is manually transported to the drying box, while the liquid phase product is transported to the evaporator I.

[0040] The tubular atmosphere furnace 1 is provided with a gas production collection pipe connected to the ammonia absorption tower 14, and a draft fan 16 is provided at the rear end. The lower end of the ammonia absorption tower 14 is connected to the captured liquid storage tank 15, and the captured liquid is input into the sprayer through a centrifugal pump. The lower end of the captured liquid storage tank 15 is connected to a centrifugal pump to input the captured liquid into the reactor 15.

[0041] Valves should be installed on all connecting pipes in the system. Example 1

[0042] (1) Ammonium sulfate roasting of rhodochrosite and manganese ore leaching process

[0043] Rhodochrosite from a manganese mine in Hunan Province was used as the raw material, and its main components are shown in Table 1. 50 kg of rhodochrosite and 10 kg of ammonium sulfate were weighed, mixed thoroughly, and placed in a tubular atmosphere furnace. The heating rate was controlled at 5 °C / min, and the mixture was calcined at 450 °C for 2 h. Nitrogen was used as the carrier gas, and the nitrogen flow rate was 4 m 3 / h, and after cooling, 46.5kg of roasted ore was taken out, and the produced gas was captured by dilute ammonia water to obtain manganese precipitant.

[0044] Table 1 Main elements and contents of rhodochrosite

[0045]

[0046] The roasted ore and 130L water were placed in a reactor, 2.5kg of concentrated sulfuric acid was added, and the temperature was raised to 80°C. The mixture was leached for 4h, and then solid-liquid separation was performed to obtain a manganese sulfate solution. 5kg of manganese dioxide powder, 5kg of calcium carbonate powder, and 500g of sodium fumer were added to the manganese sulfate solution, and the reaction was continued for 2h. During the impurity removal process, the stirring frequency was maintained at 50Hz and the slurry temperature was maintained at 70°C. After the slurry was cooled, it was filtered to obtain 110L of manganese sulfate mother liquor, the main components of which are shown in Table 2, and the manganese leaching rate was 89.4%.

[0047] Table 2 Main components of manganese sulfate mother liquor

[0048]

[0049] (2) Preparation of high-purity manganese sulfate and industrial-grade manganese carbonate

[0050] The pH of the manganese sulfate mother liquor was adjusted to 6.5, and 50 L of manganese precipitant was input at a flow rate of 25 L / h. The reaction time was 2.5 h, the stirring rate was maintained at 600 r / min, and the aging time was 3 h. After the reaction was completed, the filter cake was pressed and dried at 120°C to obtain 8.8 kg of composite manganese salt. 139 L of the filtrate was used as ammonium sulfate solution for evaporation and concentration to obtain 10.5 kg of ammonium sulfate powder.

[0051] 8.8 kg of composite manganese salt was mixed with 10 kg of condensed water, heated and stirred at 80 ° C for 6 hours, and then filtered. The solid phase was dried at 120 ° C to obtain industrial grade manganese carbonate (its XRD spectrum is as follows Figure 4 As shown in the figure), the liquid phase was evaporated and crystallized at 120°C to obtain high-purity manganese sulfate (its XRD spectrum is shown in the figure). Figure 3 The product related index parameters are shown in Table 3.

[0052] Table 3 Product parameters of industrial grade manganese carbonate and high purity manganese sulfate

[0053] Example 2

[0054] (1) Ammonium sulfate roasting of rhodochrosite and manganese ore leaching process

[0055] Rhodochrosite from a manganese mine in Hunan Province was used as the raw material, and its main components are shown in Table 1. 50 kg of rhodochrosite and 10.5 kg of ammonium sulfate prepared in Example 1 were weighed, mixed thoroughly, and placed in a tubular atmosphere furnace, the heating rate was controlled to be 5°C / min, and the mixture was calcined at 500°C for 3 h, nitrogen was used as the carrier gas, and the nitrogen flow rate was 4 m 3 / h, and after cooling, 45.9 kg of roasted ore was taken out, and the produced gas was captured by dilute ammonia water to obtain a manganese precipitant.

[0056] The roasted ore and 130L water were placed in a reactor, 3kg of concentrated sulfuric acid was added, and the temperature was raised to 90°C. The mixture was leached for 6h, and then solid-liquid separation was performed to obtain a manganese sulfate solution. 5kg of manganese dioxide powder, 5kg of calcium carbonate powder, and 500g of sodium fumei were added to the manganese sulfate solution, and the reaction was continued for 2h. During the impurity removal process, the stirring frequency was maintained at 50Hz and the slurry temperature was maintained at 70°C. After the slurry was cooled, it was filtered to obtain 113L of manganese sulfate mother liquor, the main components of which are shown in Table 4, and the manganese leaching rate was 88.4%.

[0057] Table 4 Main components of manganese sulfate mother liquor

[0058]

[0059] (2) Preparation of high-purity manganese sulfate and industrial-grade manganese carbonate

[0060] The pH of the manganese sulfate mother liquor was adjusted to 7, and 50 L of manganese precipitant was input at a flow rate of 25 L / h. The reaction time was 2.5 h, the stirring rate was maintained at 800 r / min, and the aging time was 3 h. After the reaction was completed, the filter cake was pressed and dried at 120°C to obtain 8.7 kg of composite manganese salt. 140 L of the filtrate was used as ammonium sulfate solution for evaporation and concentration to obtain 10.1 kg of ammonium sulfate powder.

[0061] 8.7 kg of composite manganese salt was mixed with 10 kg of condensed water, heated and stirred at 80 ° C for 6 hours, and then filtered. The solid phase was dried at 120 ° C to obtain industrial-grade manganese carbonate, and the liquid phase was evaporated and concentrated at 120 ° C to obtain high-purity manganese sulfate. The relevant product index parameters are shown in Table 5.

[0062] Table 5 Product parameters of industrial grade manganese carbonate and high purity manganese sulfate

[0063]

[0064] Industrial manganese carbonate and high-purity manganese sulfate can also be prepared by changing some experimental conditions within the parameter range. Example 3

[0065] (1) Ammonium sulfate roasting of rhodochrosite and manganese ore leaching process

[0066] Rhodochrosite from a manganese mine in Hunan Province was used as the raw material, and its main components are shown in Table 1. 50 kg of rhodochrosite and 10.1 kg of ammonium sulfate prepared in Example 2 were weighed, mixed thoroughly, and placed in a tubular atmosphere furnace, the heating rate was controlled at 5 ° C / min, and roasted at 400 ° C for 2 h, nitrogen was used as the carrier gas, and the nitrogen flow rate was 4m 3 / h, and after cooling, 46.2kg of roasted ore was taken out, and the produced gas was captured by dilute ammonia water to obtain a manganese precipitant.

[0067] The roasted ore and 150L water were placed in a reactor, 3kg of concentrated sulfuric acid was added, and the temperature was raised to 90°C. The mixture was leached for 6h, and then solid-liquid separation was performed to obtain a manganese sulfate solution. 5kg of manganese dioxide powder, 5kg of calcium carbonate powder, and 500g of sodium fumer were added to the manganese sulfate solution, and the mixture was reacted for 2h. During the impurity removal process, the stirring frequency was maintained at 50Hz and the slurry temperature was maintained at 80°C. After the slurry was cooled, it was filtered to obtain 129L of manganese sulfate mother liquor, the main components of which are shown in Table 6, and the manganese leaching rate was 88.0%.

[0068] Table 6 Main components of manganese sulfate mother liquor

[0069]

[0070] (2) Preparation of high-purity manganese sulfate and industrial-grade manganese carbonate

[0071] The pH of the manganese sulfate mother liquor was adjusted to 7, and 50 L of manganese precipitant was input at a flow rate of 25 L / h. The reaction time was 2.5 h, the stirring rate was maintained at 800 r / min, and the aging time was 3 h. After the reaction was completed, the filter cake was pressed and dried at 120°C to obtain 8.2 kg of composite manganese salt. 119 L of the filtrate was used as ammonium sulfate solution for evaporation and concentration to obtain 10.0 kg of ammonium sulfate powder.

[0072] 8.2 kg of composite manganese salt was mixed with 10 kg of condensed water, heated and stirred at 80 ° C for 6 hours, and then filtered. The solid phase was dried at 120 ° C to obtain industrial-grade manganese carbonate, and the liquid phase was evaporated and concentrated at 120 ° C to obtain high-purity manganese sulfate. The relevant index parameters of the product are shown in Table 7.

[0073] Table 7 Product parameters of industrial grade manganese carbonate and high purity manganese sulfate

[0074]

[0075] Industrial manganese carbonate and high-purity manganese sulfate can also be prepared by changing some experimental conditions within the parameter range. Comparative Example 1

[0076] The difference from Example 1 is that manganese sulfate is prepared by evaporating and crystallizing manganese sulfate mother liquor, and manganese carbonate is prepared by precipitating manganese sulfate mother liquor and ammonium bicarbonate.

[0077] Weigh 50 kg of rhodochrosite and 10 kg of ammonium sulfate, mix them thoroughly and place them in a tubular atmosphere furnace. Control the heating rate to 5 °C / min and roast them at 450 °C for 2 h. After cooling, take out 46.5 kg of roasted ore.

[0078] The roasted ore and 130L water were placed in a reactor, 2.5kg of concentrated sulfuric acid was added, and the temperature was raised to 80°C. The mixture was leached for 4h, and then solid-liquid separation was performed to obtain a manganese sulfate solution. 5kg of manganese dioxide powder, 5kg of calcium carbonate powder, and 500g of sodium fumer were added to the manganese sulfate solution, and the reaction was continued for 2h. During the impurity removal process, the stirring frequency was maintained at 50Hz and the slurry temperature was maintained at 70°C. After the slurry was cooled, it was filtered to obtain 112L of manganese sulfate mother liquor, the main components of which are shown in Table 8, and the manganese leaching rate was 88.5%.

[0079] Table 8 Main components of manganese sulfate mother liquor

[0080]

[0081] 50L of manganese sulfate mother liquor was directly evaporated and crystallized at 120°C, filtered and dried to obtain manganese sulfate powder, and its relevant index parameters are shown in Table 9.

[0082] Table 9 Index parameters of manganese sulfate in Comparative Example 1

[0083]

[0084] 5.5 kg of ammonium bicarbonate powder was added to 50 L of manganese sulfate mother liquor. The reaction time was 2.5 h. The stirring rate was maintained at 600 r / min. The aging time was 3 h. After the reaction was completed, the filter was pressed and the filter cake was dried at 120 ° C to obtain 3.8 kg of manganese carbonate. The relevant index parameters are shown in Table 10.

[0085] Table 10 Index parameters of manganese carbonate in Comparative Example 1

[0086]

[0087] By comparing the manganese sulfate test results in Table 3 and Table 9, it can be seen that the present invention uses composite manganate as an intermediate product and can produce high-purity manganese sulfate after thermal oxidation and evaporation crystallization. The manganese carbonate test results in Table 3 and Table 10 show that the manganese carbonate prepared by the method of the present invention has lower calcium impurities.

Claims

1. A method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource recycling, characterized in that: The steps include: S1. The low-grade rhodochrosite powder is mixed with ammonium sulfate and then roasted to obtain roasted ore, and the roasted gas is captured by dilute ammonia water to prepare a manganese precipitant; S2. The roasted ore obtained in S1 is mixed with water to form a slurry, concentrated sulfuric acid is added, and the mixture is continuously stirred and leached to obtain a manganese sulfate mother liquor after preliminary impurity removal. The impurity remover used in the preliminary impurity removal is a mixture of manganese dioxide powder, calcium carbonate and sodium fumei, and the mass ratios of manganese dioxide powder, calcium carbonate, sodium fumei and roasted ore are 0.1~0.2, 0.1~0.3, and 0.006~0.01, respectively; S3. The manganese precipitant obtained in S1 is input into the manganese sulfate mother liquor obtained in S2 for precipitation reaction to obtain a composite manganese salt and an ammonium sulfate solution, and the ammonium sulfate solution is evaporated and crystallized and then reused in S1; S4. The composite manganese salt obtained in S3 is slurried with water, continuously heated and stirred, and air is introduced for thermal oxidation, followed by solid-liquid separation, and the solid phase is dried to obtain industrial-grade manganese carbonate, and the liquid phase is a high-purity manganese sulfate solution; S5. The high-purity manganese sulfate solution obtained in S4 is evaporated and crystallized to obtain high-purity manganese sulfate.

2. The method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource recycling according to claim 1, characterized in that: In S1, the mass ratio of low-grade rhodochrosite powder to ammonium sulfate is 2~5:

1.

3. The method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource recycling according to claim 1, characterized in that: In S1, the calcination temperature is 400~500℃, the calcination time is 2~4h, the calcination uses inert gas as carrier gas, the carrier gas flow rate is 2~4 m³ / h, and the concentration of dilute ammonia water is 9~10.5%.

4. The method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource recycling according to claim 1, characterized in that: In S2, the mass ratio of water to roasted ore is 3.5~5.0, the stirring rate is 50~120 r / min, the leaching time is 4~6h, and the leaching temperature is 80~90℃.

5. The method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource recycling according to claim 1, characterized in that: In S2, impurity removal is carried out under stirring conditions, the stirring rate is 50~120 Hz, and the impurity removal temperature is 70~80℃.

6. The method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource recycling according to claim 1, characterized in that: In S3, the input time of manganese precipitant is controlled at 1~1.5 h, the reaction stirring rate is 600~800 r / min, the reaction pH is stabilized at 6.5~7.5, the reaction time is 2~2.5 h, aging is carried out after the reaction, the aging time is 2~3 h, and the evaporation crystallization temperature of ammonium sulfate solution is 100~120℃.

7. The method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource recycling according to claim 1, characterized in that: In S4, the mass ratio of the complex manganese salt to water is 0.8~1.0, the heating temperature is 60~80°C, the air flow rate is 80~100L / min, the thermal oxidation time is 6~8h, and the drying temperature of the solid phase is 100~120°C.

8. The method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource recycling according to claim 1, characterized in that: In S5, the temperature of evaporation crystallization is 100-120°C.

9. The method for preparing industrial manganese carbonate and high-purity manganese sulfate based on ammonium sulfate resource recycling according to claim 1, characterized in that: In S5, the pH is adjusted to 3.5-4.0 before evaporation and crystallization.

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