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Method for producing manganese sulfate monohydrate crystal using pyrolusite and waste acid as raw material

A technology of manganese sulfate and pyrolusite, applied in the direction of manganese sulfate, etc., can solve the problems of waste of resources, low utilization rate of manganese, strong corrosion of equipment, etc., and achieve the effect of stable product quality, simple production process and high manganese recovery rate

Inactive Publication Date: 2009-01-07
广西远辰新能源材料有限责任公司 +4
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Problems solved by technology

Manganese sulfate manufacturing process includes: 1. High-temperature roasting method, using pyrolusite as raw material. Although this method is mature, it has disadvantages such as long process, high labor intensity, serious environmental pollution, high energy consumption, low manganese utilization rate, and waste of resources. ; 2, acid leaching method, with rhodochrosite as raw material, this method needs to consume a large amount of sulfuric acid, strong corrosion to equipment, and the filtrate needs to remove the associated alkaline earth metal impurities in the ore, which increases the production cost; 3, other methods , For example, methods such as sulfur dioxide method, ferrous sulfate method, manganese monoxide method, hydrocarbon method, using biogas, rice husk, sugar cane molasses alcohol waste liquid, etc. are still in theoretical discussion and small-scale experimental exploration, and the technology is not yet mature. 4. The two-mine acid leaching method, which is gradually adopted by manganese sulfate manufacturers, has the advantages of eliminating the high-temperature reduction roasting process, improving the operating environment, reducing the consumption of raw materials and fuels, and leaching, neutralizing and removing iron , The removal of heavy metals is completed in the same reaction tank at one time, and the solid-liquid separation is easy
However, in actual production, especially when low-lean pyrolusite is selected as raw material, it is difficult to produce qualified manganese sulfate monohydrate simply by two-mine acid leaching
In the actual production of the existing two-mine acid leaching method, manganese ore with high manganese content is added to the low-poor pyrolusite raw material to supplement the manganese content of the raw material, otherwise qualified manganese sulfate monohydrate cannot be produced

Method used

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  • Method for producing manganese sulfate monohydrate crystal using pyrolusite and waste acid as raw material
  • Method for producing manganese sulfate monohydrate crystal using pyrolusite and waste acid as raw material
  • Method for producing manganese sulfate monohydrate crystal using pyrolusite and waste acid as raw material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] ①The Guangxi Guipingsong soft manganese ore (MnO 2 ) (manganese content 16.10%), ground to -0.074mm, Yunfu pyrite (FeS 2 ) (sulfur content 30.51%), grind to -0.074mm, take titanium dioxide (TiO 2 ) plant waste acid {diluted H 2 SO 4 Contains FeSO 4 , ρ(H 2 SO 4 )=168g / L};

[0021] ②Take the above-mentioned titanium dioxide (TiO 2 ) industrial waste acid 0.39M 3 Inject into the manganese immersion barrel with stirring, and put -0.074mm fineness pyrolusite (MnO 2 ) 187Kg (dry basis) and -0.074mm fineness of pyrite (FeS 2 ) 30Kg (dry basis) powder into the manganese immersion tank, steamed and heated to 90°C for 2 hours of manganese immersion. At this point, the pH of the manganese (Mn) leaching solution was determined to be 1.05, and limestone (CaCO 3 ) powder to make the solution PH=3.51, add 0.62Kg of barium sulfide (BaS) to precipitate heavy metals, react for 20min, then add limestone (CaCO 3 ) powder to adjust the pH value to 5.2, the reaction time is 40mi...

Embodiment 2

[0027] ①The Guangxi Guipingsong soft manganese ore (MnO 2 ) (manganese content 17.2%), ground to -0.074mm, Yunfu pyrite (FeS 2 ) (sulfur content 30.51%), grind to -0.074mm, take Fuji County titanium dioxide (TiO 2 ) powder mill waste acid {(diluted H 2 SO 4 Contains FeSO4 ), ρ(H 2 SO 4 )=168g / L};

[0028] ②Take the above-mentioned titanium dioxide (TiO 2 ) industrial waste acid 0.36M 3 Inject into the manganese immersion barrel with stirring, and put -0.074mm fineness pyrolusite (MnO 2 ) 160Kg (dry basis) and pyrite (FeS 2 ) powder 30Kg (dry basis) into the manganese immersion bucket, soak manganese (Mn) at 95°C for 2 hours. At this time, the pH of the manganese (Mn) leaching solution was determined to be 1.43, and limestone (CaCO 3 ) powder to make the solution PH=2.53, add 0.6Kg of barium sulfide (BaS) to precipitate heavy metals, the reaction time is 30min, then add limestone (CaCO 3 ) powder to adjust the pH to 6.2, the reaction time is 35 minutes, precipitate i...

Embodiment 3

[0034] ①The Guangxi Guipingsong soft manganese ore (MnO 2 ) (manganese content 22.01%), ground to -0.074mm, Yunfu pyrite (FeS 2 ) (sulfur content 30.51%), grind to -0.074mm, take Fuji County titanium dioxide (TiO 2 ) Plant waste acid {(diluted H 2 SO 4 Contains FeSO 4 ), ρ(H 2 SO 4 )=168g / L}.

[0035] ②Take the above-mentioned titanium dioxide (TiO 2 ) industrial waste acid 0.42M 3 Inject -0.074mm fineness pyrolusite (MnO 2 ) 164Kg (dry basis) and pyrite powder (FeS 2 ) 36Kg (dry basis) into the manganese immersion barrel, and soak manganese (Mn) at 98°C for 2 hours. At this time, the pH of the manganese (Mn) leaching solution was determined to be 1.96, and limestone (CaCO 3 ) powder to make the solution PH = 3.0, add 0.6Kg barium sulfide (BaS) to react for 30 minutes to precipitate heavy metals [such as lead (Pb), zinc (Zn), cobalt (Co), nickel (Ni)]. Then adjust the pH value to 5.25, react for 40 minutes to precipitate iron (Fe), aluminum (Al), arsenic (As), anti...

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Abstract

A method for producing monohydrate manganous sulfate crystals comprises the steps of (1) finely grinding pyrolusite and iron pyrites; (2) using industrial acid sludge of titanium white as a manganese leaching agent; (3) leaching manganese; (4) adjusting the pH value of a suspension liquid after leaching manganese, adding barium sulfide to deposit heavy metal; (5) adjusting the pH value of the suspension liquid after the deposition of the heavy metal, depositing iron, aluminum, arsenic, and stibium, and filtering; (6) conducting hydro-thermal reaction for a filtrate after filtering to obtain a solution containing coarse particles of manganous sulfate crystals; filtering the solution; and adjusting the pH value of the filtrate; (9) enabling the filtrate to conduct standing, seasoning and filtering; (10) adjusting the pH value of the filtrate to conduct hydro-thermal reaction to obtain a coarse particle manganous sulfate crystal solution; removing a supernatant fluid to obtain crystal mush containing coarse particles of manganous sulfate crystals; (11) separating the crystal mush to obtain the monohydrate manganous sulfate crystals.

Description

technical field [0001] The invention relates to a production process of manganese sulfate monohydrate, in particular to a production process for preparing manganese sulfate monohydrate by using low-lean, fine-doped pyrolusite and titanium white industrial waste acid as raw materials by a hydrothermal reaction method. Background technique [0002] Manganese sulfate is an important chemical product and also a main chemical and metallurgical raw material, which can be used in medicine, papermaking, ceramics, catalysts, ore flotation, production of electrolytic manganese and other manganese salts. Manganese sulfate manufacturing process includes: 1. High-temperature roasting method, using pyrolusite as raw material. Although this method is mature, it has disadvantages such as long process, high labor intensity, serious environmental pollution, high energy consumption, low manganese utilization rate, and waste of resources. ; 2, acid leaching method, with rhodochrosite as raw mat...

Claims

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Application Information

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IPC IPC(8): C01G45/10
Inventor 马尧卓长生黄志军
Owner 广西远辰新能源材料有限责任公司
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