阅读说明：本技术 一种高硫碳酸锰贫矿生产电解金属锰的溶液净化方法 (Solution purification method for producing electrolytic manganese metal from high-sulfur manganese carbonate lean ore ) 是由 邓宗瑜 朱应峰 石跃 于 2020-11-17 设计创作，主要内容包括：本发明公开了一种高硫碳酸锰贫矿生产电解金属锰的溶液净化方法,与常规工艺对比,本方法在化合桶中只进行酸浸、中和操作,不进行氧化除铁,然后进行第一次过滤,充分利用锰矿石中的含铁杂质在后续工序形成的Fe(OH)_3的强吸附作用,对硫化后的硫酸锰溶液进行深度净化后进行第二次过滤,通过添加吸附剂、降温结晶、静置沉降等方式,再次对溶液进行净化后进行第三次过滤；添加电解添加剂,获得满足电解工艺条件的硫酸锰溶液,回调溶液的pH值,送电解槽正常电解；通过上述处理,可有效避免高硫碳酸锰贫矿生产电解锰过程中出现的槽液返碱、锰积板发黑、产品倒溶、硫含量超标以及溶液严重结晶导致生产无法进行等问题。(The invention discloses a solution purification method for producing electrolytic manganese metal from high-sulfur manganese carbonate lean ore, which is compared with the conventional process, only carries out acid leaching and neutralization operations in a chemical combination barrel, does not carry out oxidation and iron removal, then carries out primary filtration, and fully utilizes Fe (OH) formed by iron-containing impurities in manganese ore in the subsequent process 3 The strong adsorption effect of the method is that the vulcanized manganese sulfate solution is deeply purified and then is filtered for the second time, and the solution is purified again and then is filtered for the third time by adding an adsorbent, cooling crystallization, standing sedimentation and other modes; additive electrolysisAdding an additive to obtain a manganese sulfate solution meeting the electrolysis process conditions, adjusting the pH value of the solution back, and conveying the solution to an electrolytic cell for normal electrolysis; through the treatment, the problems of alkali return of bath solution, blackening of manganese plates, product reverse dissolution, over-standard sulfur content, serious solution crystallization, incapability of production and the like in the process of producing electrolytic manganese from high-sulfur manganese carbonate lean ores can be effectively avoided.)

1. A solution purification method for producing electrolytic manganese metal from high-sulfur manganese carbonate lean ore is characterized by comprising the following steps: the method comprises the following steps:

the method comprises the following steps: grinding manganese carbonate ore, feeding the ground manganese carbonate ore into a chemical combination barrel with a stirrer, adding concentrated sulfuric acid and anolyte returned by electrolysis to fully react with the manganese ore for 3-5 hours according to the acid consumption rate of the ore powder, and measuring the residual acid content at the end of the reaction;

step two: adding calcium carbonate powder into the combination barrel according to the content of residual acid in the ore pulp in the step one, fully reacting until the pH value of the ore pulp is more than or equal to 4.5, then sending the ore pulp into a high-pressure membrane filter press for primary filtration, and sending filter residues into a residue field for temporary storage;

step three: sending the filtrate obtained in the step two into a vulcanizing barrel with a stirrer and an air pipe, starting stirring, and adjusting the pH value of the filtrate to be within the range of 6.5-7.5 by using dilute ammonia water with the concentration of 10%;

step four: according to the heavy metal ion content of the solution in the vulcanizing barrel, a heavy metal precipitator sodium ferbamate solution with the concentration of 10-20% is added, and S is also added for the heavy metal ions which can not be effectively precipitated and removed by the sodium ferbamate^2-The inorganic vulcanization precipitator is added into a vulcanization barrel to fully react to ensure that the content of heavy metal ions in the solution in the vulcanization barrel meets the process requirement of electrolytic manganese metal production;

step five: continuously maintaining the stirring operation of the vulcanizing barrel, introducing compressed air into the vulcanizing barrel, and utilizing oxygen in the compressed air to remove Fe in the filtrate²⁺Oxidation to Fe³⁺Trace amount of Fe not oxidized by air in the vulcanizing barrel²⁺Oxidizing with hydrogen peroxide, and maintaining pH in the vulcanizing barrel with ammonia water to 6.5 or above to make iron ion be fully dissolvedCarrying out secondary filtration after hydrolysis and precipitation, and conveying filter residues to a residue field for temporary storage;

step six: adding an adsorbent into the filtrate obtained in the fifth step, cooling and settling the filtrate by a turbulence deflection chute, allowing the filtrate to enter a storage tank for standing, adding a composite flocculant into the storage tank, standing for more than 24 hours, carrying out third filtration, and conveying filter residues to a residue field for temporary storage;

step seven: and (4) sending the filtrate obtained in the sixth step to an electrolytic head tank, adding selenium dioxide with specified concentration and an auxiliary electrolytic additive into the head tank, adjusting the pH value of the solution back to weak acidity by using concentrated sulfuric acid or anolyte, and sending the solution to an electrolytic tank for normal electrolysis.

2. The method for purifying the solution for producing the electrolytic manganese metal from the high-sulfur manganese carbonate lean ore according to claim 1, characterized in that: in the first step, the grinding fineness of the manganese carbonate ore is more than 90 percent, and the manganese carbonate ore passes through a 100-mesh sieve.

3. The method for purifying the solution for producing the electrolytic manganese metal from the high-sulfur manganese carbonate lean ore according to claim 1, characterized in that: and in the second step, the fineness of the calcium carbonate powder is more than or equal to 100 meshes, and the calcium carbonate powder is sent to the bottom of the chemical combination barrel through a stainless steel pipeline by using compressed air.

4. The method for purifying the solution for producing the electrolytic manganese metal from the high-sulfur manganese carbonate lean ore according to claim 1, characterized in that: the pressure of the compressed air in the step five is 48kPa-78kPa, and the flow rate of the compressed air entering each vulcanizing barrel is more than or equal to 15m³And min, delivering the compressed air to the bottom of the vulcanizing barrel through a steel pipe arranged in the vulcanizing barrel, wherein the outlet of the compressed air pipe is 30-60 cm away from the bottom of the vulcanizing barrel.

5. The method for purifying the solution for producing the electrolytic manganese metal from the high-sulfur manganese carbonate lean ore according to claim 1, characterized in that: the adsorbent added in the sixth step is activated carbon, diatomite or a mixture of the activated carbon and the diatomite; the composite flocculant added into the storage tank is polyacrylamide and polyaluminium sulfate, and in the standing process, harmful impurities in the solution are further reduced through full adsorption of the adsorbent and cooling crystallization of the solution.

Technical Field

The invention belongs to the technical field of wet smelting, and particularly relates to a solution purification method for producing electrolytic manganese metal from high-sulfur manganese carbonate lean ores.

Background

At present, the production of metal manganese is mainly carried out by wet leaching and electrolytic method production, the main components of electrolyte are manganese sulfate, ammonium sulfate, selenium dioxide and the like, the components of the electrolyte must be strictly controlled, the electrolyte is required to contain no harmful impurities as far as possible, the electrolytic production can be smoothly carried out, otherwise, the problems of alkali return of the electrolyte of an electrolytic cell, blackening of manganese plates, product reverse dissolution, over-standard sulfur content, serious crystallization of the solution and the like can be caused, and the production can not be carried out.

At present, the production of domestic electrolytic manganese metal is mainly based on manganese carbonate ore, and the grade of manganese carbonate ore resources is low although the reserves are rich in China. The low-grade manganese carbonate lean ore has more impurity elements, and brings a plurality of process problems for the economic utilization of the ore. Sulfur is one of main impurity elements in manganese carbonate ore, and because general iron and manganese in the manganese ore coexist, iron in the manganese ore can be leached out simultaneously with manganese in the leaching process, and the conventional iron removal process at present generally comprises the steps of adding an oxidant after the ore is fully leached out, and adding Fe²⁺Oxidation to Fe³⁺Then adjusting the pH value of the reaction mass to enable Fe³⁺Hydrolysis to form Fe (OH)₃And removing after precipitation. If the sulfur content in the manganese ore is too high, the conventional production process can cause certain metal sulfides in the ore and the added oxidant to generate colloidal sulfur and sulfur ions which are difficult to remove in the subsequent purification process and solid-liquid separation, and if the content of the sulfur-containing impurities in the electrolyte cannot be effectively controlled, the normal production of the electrolysis process can be seriously influenced.

On the other hand, along with the large-scale exploitation of manganese ore resources in China, the quality of ores is continuously reduced at present, the content of various impurities in the ores is rapidly increased, and for high-sulfur manganese carbonate lean ores, if the traditional impurity removal and purification processes are still adopted, the strict requirements of electrolytic manganese metal production on the quality of electrolyte can not be ensured, so that the serious problems of reduction of current efficiency, poor production stability, unqualified product quality and even abnormal production in the production process are caused.

Disclosure of Invention

In order to overcome the problems, the invention provides a solution purification method for producing electrolytic manganese metal from high-sulfur manganese carbonate lean ores.

The technical scheme adopted by the invention is as follows:

a solution purification method for producing electrolytic manganese metal from high-sulfur manganese carbonate lean ore comprises the following steps:

the method comprises the following steps: grinding manganese carbonate ore to the fineness of more than 90 percent and passing through a 100-mesh sieve, feeding the powder into a chemical combination barrel with a stirrer, adding concentrated sulfuric acid and anolyte returned by electrolysis to fully react with the manganese ore for 3-5 hours according to the acid consumption rate of the ore powder, and measuring the residual acid content at the end of the reaction;

step two: according to the content of residual acid in the ore pulp obtained in the step one, feeding calcium carbonate powder with the fineness of more than or equal to 100 meshes into the middle bottom of a chemical combination barrel through a stainless steel pipeline by using compressed air, fully reacting until the pH value of the ore pulp is more than or equal to 4.5, feeding the ore pulp into a high-pressure membrane filter press for primary filtration, and feeding filter residues into a residue field for temporary storage;

step three: sending the filtrate obtained in the step two into a vulcanizing barrel with a stirrer and an air pipe, starting stirring, and adjusting the pH value of the filtrate to be within the range of 6.5-7.5 by using dilute ammonia water with the concentration of 10%;

step four: according to the heavy metal ion content of the solution in the vulcanizing barrel, a heavy metal precipitator sodium ferbamate solution with the concentration of 10-20% is added, and S is also added for the heavy metal ions which can not be effectively precipitated and removed by the sodium ferbamate^2-The inorganic vulcanization precipitator is added into a vulcanization barrel to fully react to ensure that the content of heavy metal ions in the solution in the vulcanization barrel meets the process requirement of electrolytic manganese metal production;

step five: continuously maintaining the stirring operation of the vulcanizing barrel, introducing compressed air into the vulcanizing barrel, and utilizing oxygen in the compressed air to remove Fe in the filtrate²⁺Oxidation to Fe³⁺Trace amount of Fe not oxidized by air in the vulcanizing barrel²⁺Oxidizing by using hydrogen peroxide, and always maintaining the pH value in the vulcanizing barrel to be more than 6.5 by using ammonia water so as to facilitate the generation of new ecological Fe (OH) in the oxidation process₃Further adsorbing and purifying harmful heavy metal ions and non-metal ions in the solution obtained in the step four, wherein air for oxidation and iron removal is from a high-pressure fan, iron ions are subjected to secondary filtration after being sufficiently hydrolyzed and precipitated, and filter residues are conveyed to a residue field for temporary storage;

step six: adding an adsorbent into the filtrate obtained in the fifth step, cooling and settling the filtrate by a turbulence deflection chute, allowing the filtrate to enter a storage tank for standing, adding a composite flocculant into the storage tank, standing for more than 24 hours, carrying out third filtration, and conveying filter residues to a residue field for temporary storage;

step seven: and (4) sending the filtrate obtained in the sixth step to an electrolytic head tank, adding selenium dioxide with specified concentration and an auxiliary electrolytic additive into the head tank, adjusting the pH value of the solution back to weak acidity by using concentrated sulfuric acid or anolyte, and sending the solution to an electrolytic tank for normal electrolysis.

Preferably, the pressure of the compressed air in the fifth step is 48kPa-78kPa, and the flow rate of the compressed air entering each vulcanizing barrel is more than or equal to 15m³And min, delivering the compressed air to the bottom of the vulcanizing barrel through a steel pipe arranged in the vulcanizing barrel, wherein the outlet of the compressed air pipe is 30-60 cm away from the bottom of the vulcanizing barrel.

The adsorbent added in the sixth step is activated carbon, diatomite or a mixture of the activated carbon and the diatomite; the composite flocculant added into the storage tank is polyacrylamide and polyaluminium sulfate, and in the standing process, harmful impurities in the solution are further reduced through full adsorption of the adsorbent and cooling crystallization of the solution.

The invention has the following advantages:

the invention fully utilizes the nascent state Fe (OH) formed in the purification process of the symbiotic iron in the low-grade manganese ores by optimizing the acid leaching and purification operations of manganese ores, adjusting the sequence of the operations of removing iron and heavy metals in a chemical combination barrel and a vulcanizing barrel and optimizing the process conditions of purification and impurity removal₃The strong adsorption effect of the colloid can adsorb and remove heavy metal ions, colloid sulfur, sulfur ions, harmful non-metal ions, organic matters and the like in the solution, and the manganese sulfate solution is deeply purified; adding adsorbent, cooling and crystallizing by a turbulent flow baffling chute, adding composite flocculant, fully standing and aging the solution and the like to ensure that the solution is in the solutionThe calcium and magnesium ions are fully separated out before entering the electrolytic cell, and by the measures, the problems that the cell liquor returns alkali, the manganese plate is blackened, the product is dissolved upside down, the sulfur content exceeds the standard, the solution is seriously crystallized, the production cannot be carried out and the like easily occurring in the process of producing electrolytic manganese metal by using high-sulfur poor manganese ore are greatly improved.

Drawings

FIG. 1 is a schematic flow chart of the solution purification method for producing electrolytic manganese metal from high-sulfur manganese carbonate lean ore according to the invention.

Detailed Description

The present invention will be further described below, but the present invention is not limited to these.

Examples

A solution purification method for producing electrolytic manganese metal from high-sulfur manganese carbonate lean ore comprises the following steps:

the method comprises the following steps: in an effective volume of 300m³The chemical combination reactor is added with 100m³Electrolyzing the anolyte (the composition analysis is shown in Table 1), starting the reactor to stir, putting 55 tons of manganese carbonate ore (the composition analysis is shown in Table 2) with the manganese content of 14.33 percent and the total sulfur content of 6.21 percent into the chemical combination reactor, adding 14.5 tons of 98 percent concentrated sulfuric acid, replenishing the anolyte 150m after the reaction is stable³At the moment, the temperature of the ore pulp is 50 ℃, after 4 hours of reaction, the content of the residual acid in the ore pulp is measured to be 5.21g/l, 3.5 tons of calcium carbonate powder are added, and after 1 hour of reaction, the pH value of the ore pulp is measured to be 4.85;

step two: carrying out solid-liquid separation on ore pulp in the chemical combination reactor through a high-pressure membrane filter press, conveying filter residues to a residue field for temporary storage, feeding filtrate into a vulcanizing barrel with stirring and air pipes, wherein the effective volume of the vulcanizing barrel is 150m³；

Step three: starting a vulcanizing barrel stirrer, adding 10% ammonia water into the vulcanizing barrel to adjust the pH value of the filtrate to 6.85, then adding 10% sodium dimethyl dithiocarbamate solution until the heavy metal ions in the solution are completely removed (the qualified legal qualitative detection of dimethylglyoxime is adopted, and the interference of iron ions needs to be eliminated in the qualitative detection process), and determining that the pH value in the vulcanizing barrel is 6.93 at the moment;

step four: opening an air valve at the upper part of the vulcanizing tank for supplying air from the vulcanizing tankThe hot air of the Roots blower is subjected to air oxidation deferrization through air pipes uniformly distributed in the vulcanizing barrel, ammonia water is supplemented at any time, the pH value of the solution is maintained to be more than 6.5, and when Fe is contained in the solution²⁺Adding 27.5% hydrogen peroxide solution into the solution through hydrogen peroxide water pipe arranged in the purifying barrel when the concentration is less than or equal to 0.5g/l, and adding Fe²⁺Total oxidation to Fe³⁺Continuously blowing hot air for 0.5 hour, carrying out secondary solid-liquid separation, and conveying filter residues to a residue field for temporary storage;

step five: adding active carbon and diatomite into the solution obtained by the second solid-liquid separation, wherein the adding amount is 0.1-0.5kg/m³Feeding the solution into a standing tank through a turbulence chute, adding a polyacrylamide and polyaluminium sulfate composite flocculant solution into the standing tank in a dropwise manner, standing the solution in the standing tank for 24 hours, filtering for the third time, wherein the components of the solution after purification are shown in table 3, and feeding filter residues into a residue field for temporary storage;

step six: and (3) delivering the solution obtained by the third solid-liquid separation to an electrolytic head tank, adding selenium dioxide and an auxiliary electrolytic additive according to the conventional concentration, returning the anolyte by concentrated sulfuric acid or electrolysis, returning the anolyte to adjust the pH value of the solution in the head tank to be within the range of 2-6, delivering the solution to an electrolytic cell for normal electrolysis, and enabling the components of the solution entering the electrolytic cell to be shown in table 3.

Electrolytic anolyte composition meter (Table 1)

Component (A)	H2SO4	Mn2+	(NH4)2SO4
				Content (g/l)	40.0	14.5	85.0

Manganese carbonate ore composition table (Table 2)

Component (A)	Mn	TFe	TS	SiO2	Al2O3	CaO	MgO
								Content (%)	14.33	6.8	6.21	13.7	7.8	9.1	3.5

Purified solution Components (Table 3)

It is noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.