CN101070565A

CN101070565A - Method for extracting high-valence manganese from manganese carbonate ore

Info

Publication number: CN101070565A
Application number: CN 200710078621
Authority: CN
Inventors: 陶长元; 曹渊; 刘作华; 杜军; 唐金晶
Original assignee: Chongqing University
Current assignee: Chongqing University
Priority date: 2007-06-14
Filing date: 2007-06-14
Publication date: 2007-11-14
Anticipated expiration: 2027-06-14
Also published as: CN100491549C

Abstract

This invention has provided one kind of method to leach high price manganese from manganese carbonateore, which belongs to the hydrometallurgy domain. It takes the glucose or the plant biomass and sulfuric acid as reducing agent of high pricemanganese in manganese carbonate ore, adopting microwave radiation glucose to promote high price manganese to revert, the concrete step includes: Takes 1 copy 100-200 sieve manganese carbonateore, add 10 -20 copy water to modulate the pulp; Again add 60% density sulfuric acid to pulp, the load ratio of mineral powder and sulfuric acid is 1: 6 -9; Simultaneously, add glucose or plant biomass, the load ratio of mineral powder and glucose or plant biomass is 10 -15: 1, stir evenly; radiate under 500 -1000W microwave, stir and respond for 4-10min, leach temperature is controlled at 50degree C-60 degree C, then get lixivium by filtering. This invention has the merits of lower reaction temperature, reducing acid consume and reduce leaching time of the manganese ore, high thermal using and respond rapidly.

Description

The method of extracting high-valence manganese from manganese carbonate ore

Technical field

The method of reduction high price manganese belongs to the hydrometallurgy field when the present invention relates to leach manganese ore.

Background technology

Along with rapid growth of economy, China has become maximum electrolytic manganese production export State in the whole world and consumption big country.Though domestic manganese ore reserves for industrial utilization reach 300,000,000 tons, are poor manganese ore more than 80%, ore on average contains manganese only about 20%.Usually the manganese ore chemical processing technology is divided into acid system and alkaline process two classes, and operational path is mainly determined according to the exist form and the products made thereby kind of manganese in the ore.Valence state as manganese in the manganese ore exists with positive divalence, then acid systems of using more; If exist with positive tetravalence attitude, then many with alkaline process or be reduced into positive divalence earlier, adopt acid system again.What the manganese ore ore type was maximum is that manganese carbonate ore (rhodochrosite) is main, account for 73% of total reserves, and acid system is adopted in the processing of rhodochrosite more, but owing to the existence form of manganic compound in the manganese ore is various, as Manganse Dioxide, manganous silicate etc.Wherein Manganse Dioxide not only itself is insoluble to hot dilute sulphuric acid, also hinders the leaching of other form manganese.In addition, the Fe in order to contain in the leach liquor that will have technology now ²⁺Remove, generally all add a large amount of excessive manganese dioxide powders (pyrolusite), add-on is about 7%～10% of used rhodochrosite ore weight.And excessive Manganse Dioxide usually with rhodochrosite in high price manganese enter slag mutually, make the slag phase high price manganese content higher, caused the significant wastage of resource.Therefore, from manganous carbonate, extract manganese metal and normally obtain manganous sulfate by the method for leaching earlier, and then electrolysis obtains high price manganese.

For raising contains the leaching rate of high price manganese in the carbonic acid manganese ore (rhodochrosite) and the utilization ratio of oxygenant (pyrolusite), people have studied different reductive agents.In national inventing patent CN1940098A, propose with trade waste cane molasses alcohol slops as reductive agent as the Wen Yanxuan of Guangxi University etc., stirring reaction 0.5h～4h obtains reacting leach liquor under 98 ℃ of temperature, and the leaching yield of manganese is greater than 93% in the pyrolusite.National inventing patent CN89105118.X adopts rice husk as reductive agent.Yang Ming equality has been studied chaff-sulfuric acid and has directly been soaked the preparation of manganese condition.National inventing patent CN85103874A adds 100 kilograms of straw powder, 130 kg of water in 500 kilograms of pyrolusites, 2.5 kilograms of starters and 600 kilograms of industrial sulphuric acids, and 75 ℃ leach 1.5h down, and the leaching rate of manganese ore reaches 99.83%.Do in the method for reductive agent at plant biomass such as above-mentioned cane molasses, chaff, rice husks, have raw material advantage cheap and easy to get, but have biomass powder hydrolysis saccharogenesis difficulty, need the problem of the consumption increase of higher temperature of reaction and acid.

Summary of the invention

At the prior art above shortcomings, the purpose of this invention is to provide a kind of temperature of reaction lower, reduce acid and consume and shorten the leaching manganese ore time and the method for extracting high-valence manganese from manganese carbonate ore of inventing.

The object of the present invention is achieved like this: a kind of from manganese carbonate ore the method for extracting high-valence manganese, it is characterized in that, as the reductive agent of the high price manganese in the manganese carbonate ore, adopt microwave radiation glucose to promote the reduction of high price manganese with glucose or plant biomass and sulfuric acid, concrete steps comprise:

Get 1 part in 100 orders～200 purpose manganese carbonate ores, add 10～20 parts of water and be modulated into ore pulp; Past again ore pulp adding concentration is 60% sulfuric acid, and breeze and vitriolic weight ratio are 1: 6～9: add glucose or plant biomass simultaneously, the weight ratio of breeze and glucose or plant biomass is 10～15: 1 stirs; Under 500W～1000W microwave radiation, stirring reaction 4min～10min, the control leaching temperature is 50 ℃～60 ℃, obtains leach liquor after filtration.

Optimum condition is: microwave power is 700W, and be 5min heat-up time, and temperature of reaction is controlled at about 55 ℃.Described plant biomass is any in rice bran, solvability starch, wood chip, stalk or the straw.

Compared to existing technology, the present invention has following beneficial effect:

(1) glucose, starch and other contain the biomass wide material sources, with low cost of reductibility carbohydrate, starch and other contain the biomass of reductibility carbohydrate under the effect of leaching agent vitriolic, can hydrolysis become reductive monosaccharide (glucose etc.), and the insoluble xylogen in the material can adsorb the detrimental impurity such as phosphorus in heavy metal and the manganese ore, reaches the purpose of comprehensive utilization of resources.

(2) adopt microwave that biomass by hydrolyzation and high price manganese reduction process are heated, utilize the heat effect and the non-thermal effect that exist in the microwave heating process, improve the speed that the sulfuric acid catalysis cellulose hydrolysis becomes reductibility carbohydrate materials such as glucose, make the high price manganese in the ore change into manganese at a low price rapidly, thereby reduce the manganese content in the leaching slag, improve the leaching rate of manganese, reach the purpose that reduces temperature of reaction and shorten the leaching manganese ore time.

(3) microwave heating has the characteristics of whole heating, and it is fast to have heating speed, and no thermograde reduces the energy expenditure of reacting, and the heat utilization ratio height, is swift in response, thereby reaches the purpose of save energy.

Embodiment

Embodiment 1: get manganese carbonate ore (being rhodochrosite, manganese content 20.6%) 10g, be crushed to 100 orders, add 200g water and be modulated into ore pulp; Add the vitriol oil (quality percentage composition 60%) 150g and glucose 1g toward ore pulp again, under the 500W microwave radiation, stirring reaction 10min, the control leaching temperature is 50 ℃, obtains the manganous sulfate leach liquor of high price manganese, reaches 92.1% through surveying the manganese leaching yield.

Embodiment 2: get manganese carbonate ore (being rhodochrosite) 100g, be crushed to 120 orders, add 1000g water and be modulated into ore pulp; Add the vitriol oil (quality percentage composition 60%) 1000g and solvability starch 10g toward ore pulp again, under the 600W microwave radiation, stirring reaction 8min, the control leaching temperature is 60 ℃, obtains the manganous sulfate leach liquor of high price manganese; Reach 98.7% through surveying the manganese leaching yield.

Embodiment 3: get manganese carbonate ore (being rhodochrosite) 15g, be crushed to 200 orders, add 210g water and be modulated into ore pulp; Add the vitriol oil (weight percentage 60%) 200g and wood chip 1.3g toward ore pulp again, under the 700W microwave radiation, stirring reaction 8min, the control leaching temperature is 60 ℃, obtains the manganous sulfate leach liquor, reaches 99.2% through surveying the manganese leaching yield.

Embodiment 4: get manganese carbonate ore (being rhodochrosite) 150g (manganese content 20.6%), be crushed to 180 orders, add 2000g water and be modulated into ore pulp; Add the vitriol oil (quality percentage composition 60%) 2000g and rice husk 10g toward ore pulp again, under the 1000W microwave radiation, stirring reaction 4min, the control leaching temperature is 50 ℃, obtains the manganous sulfate leach liquor, reaches 98.8% through surveying the manganese leaching yield.

Embodiment 5: get manganese carbonate ore rhodochrosite 150g, be crushed to 200 orders, add 1500g water and be modulated into ore pulp; Add the vitriol oil (quality percentage composition 60%) 2000g and rice husk 15g toward ore pulp again, under the 800W microwave radiation, stirring reaction 5min, the control leaching temperature is 55 ℃, obtains the manganous sulfate leach liquor, the manganese leaching yield reaches 99.1%.

Claims

1, the method for extracting high-valence manganese from manganese carbonate ore is characterized in that concrete steps comprise:

Get 1 part in 100 orders～200 purpose manganese carbonate ores, add 10～20 parts of water and be modulated into ore pulp; Toward the sulfuric acid of ore pulp adding 60%, breeze and vitriolic weight ratio are 1: 6～9: add glucose or plant biomass simultaneously, the weight ratio of breeze and glucose or plant biomass is 10～15: 1 stirs again; Under 500W～1000W microwave radiation, stirring reaction 4min～10min, the control leaching temperature is 50 ℃～60 ℃, obtains leach liquor after filtration.

2, according to claim 1 from manganese carbonate ore the method for extracting high-valence manganese, the weight ratio that it is characterized in that breeze and water is 1: 14.

3, according to claim 1 from manganese carbonate ore the method for extracting high-valence manganese, it is characterized in that breeze and vitriolic weight ratio are 1: 8.

4, according to claim 1 from manganese carbonate ore the method for extracting high-valence manganese, it is characterized in that microwave power is 700W, be 5min heat-up time, temperature of reaction is controlled at about 55 ℃.

5, according to claim 1 from manganese carbonate ore the method for extracting high-valence manganese, it is characterized in that described plant biomass is any in rice bran, solvability starch, wood chip, stalk or the straw.