CN101780979B - Method for recycling ammonium molybdate solution from molybdenum contained ammonia leaching residues - Google Patents

Abstract

The invention belongs to a method for recycling ammonium molybdate solution from molybdenum contained ammonia leaching residues produced in the molybdenum smelting process, which comprises the steps of mixing and pulping the molybdenum contained ammonia leaching residues, pyrolusite powder, water and phosphoric acid; undergoing ammonia compression reaction under the condition of controlling the pH value of material pulp; and then carrying out solid-liquid separation and cleaning to obtain the ammonium molybdate solution. In the method, the reaction can be carried out at the temperature of 120 DEG C to 140 DEG C and under an ammonia compression condition by taking the pyrolusite powder as an oxidizer and phosphoric acid as a disintegrant of insoluble molybdate, thus more than 60% of molybdenum can be recycled from the ammonia leaching residues in a form of ammonium molybdate solution so that the invention has the characteristics of simple and convenient recycling, high efficiency, low recycling cost and no waste water exhaust.

Description

Reclaim the method for ammonium molybdate solution in the molybdenum contained ammonia leaching residues

Technical field

The invention belongs to a kind of method that from the molybdenum contained ammonia leaching residues that the molybdenum wet smelting process produces, reclaims ammonium molybdate solution.

Background technology

The hydrometallurgy of molybdenum calcining mainly is divided into ammonia leaching process and alkaline leaching both at home and abroad, but no matter adopts which kind of process method, all that output is a large amount of molybdenum-containing leached residues.The main existence form of molybdenum is the molybdenum dioxide that roasting process takes off the halfway moly-sulfide of S, oxygen debtization generation in the slag; And insoluble molybdate such as lead molybdate, calcium molybdate etc.

In the leached mud there be the main recovery method of molybdenum: the yellow soda ash sintering process; This method is the molybdenum that utilizes in the further oxidation sludge of airborne oxygen; And then under-oxidized molybdenum is become dissolve in the alkaline solution; Soda decomposes molybdate and oxide compound down at 700～750 ℃ and generates Sodium orthomolybdate, and this method leaching yield is high, but energy consumption is high, reagent consumption is big; Soda ash directly leaches, and this method is to utilize soda ash to leach down directly at 90～95 ℃, can leached mud in CaMoO ₄, Fe (MoO ₄) ₃The molybdenum that form exists, but product form is a Sodium orthomolybdate, and also need make the transition is ammonium molybdate; Acid decomposition, this method are to utilize 20%～30% hydrochloric acid to decompose leached mud, and there is the volatility of hydrochloric acid in this method and corrodes comparatively serious; And need molybdenum (" molybdenum metallurgy ", press of Central South University, Xiang Tiegen in the recovered acid salt decomposed solution; 2002, P132～136); Also can decompose indissoluble molybdate (" utilizing ammonia leaching residue manufacture Sodium orthomolybdate ", China molybdenum industry, 2003.4, P32～35) with hydrochlorate earlier before, above method mainly reclaims the molybdenum that exists with insoluble molybdate form, to MoS ₂And MoO ₂Effect is little.Hypochlorite decomposition method, or hypochlorite and soda associating lixiviation process, these class methods are to MoS ₂And MoO ₂Leaching effect is better, but the auxiliary material hypochlorite is more expensive, and brings certain chlorine root into, and subsequent processing device is caused corrosion (" the hypochlorite decomposition technique of molybdenum-containing waste slag ", China molybdenum industry, 2002.10, P20～23) easily.

Summary of the invention

The technical problem that the present invention will solve provides in a kind of molybdenum contained ammonia leaching residues the method that reclaims ammonium molybdate solution, and this recovery method is easy, efficient, cost is low, non-wastewater discharge, equipment is not had corrosion.

For solving the problems of the technologies described above, the present invention includes following steps:

A. prepare burden, size mixing: dried slag charge of said molybdenum contained ammonia leaching and the pyrolusite powder and the water that account for this dried slag charge weight 30～50wt% are added in the dosing vessel, and said pyrolusite powder contains MnO ₂Be 60wt%; The ratio adding concentration of soaking dried slag charge interpolation 3～5ml in the said ammonia of every 100g is the phosphoric acid of 85wt%, and mixing is stirred and is made into density is 1.1～1.4g/cm ³Slip, add ammoniacal liquor then and stir, control slip pH value between 9 ~ 10;

B. reacting by heating: the steps A gained slip of preparing burden is added airtight ammonia indent internal heating and stirs, and between temperature 120 ~ 140oC, ammonia is pressed reaction 1～3 hour, is cooled to normal pressure then;

C. solid-liquid separation: gained material after the step B reacting by heating is carried out solid-liquid separation, and filtrating is ammonium molybdate solution; Filter residue is used water washing again, its washings or merge with said ammonium molybdate solution, or return the water of A step as the allotment slip.

In the said steps A, add ammoniacal liquor again behind the adding phosphoric acid, the pH value of control slip is between 9 ~ 10; At last the density of slip is transferred to 1.1～1.4g/cm ³

In the said steps A, the add-on of said pyrolusite powder promptly adds 5.5～7.0g by the insoluble molybdenum of every gram and contains MnO by the weight that contains insoluble molybdenum in the dried slag charge of said molybdenum contained ammonia leaching ₂Pyrolusite powder for 60wt%;

Among the said step C, adopt B or centrifuging to carry out solid-liquid separation; Said filter residue adopts the water washing of 1～3 times of amount of filtrate volume.

The present invention adopts pyrolusite powder as oxygenant, and phosphoric acid is the ammonia press strip spare operation down of 120 ~ 140oC as the decomposition agent of the insoluble molybdate of part in temperature; Can the molybdenum of the overwhelming majority in the ammonia leaching residue be recycled with the form of ammonium molybdate solution, its technical process is easy, and energy consumption is low; Ammoniacal liquor consumes low, and molybdenum recovery is high, and cost recovery is low; Since the waste water reclamation utilization, non-wastewater discharge, and environmental pollution is little.

Embodiment

Below in conjunction with embodiment the present invention is done further explain.But should this be interpreted as that the scope of above-mentioned theme of the present invention only limits to following embodiment.

Embodiment 1: the method steps that reclaims ammonium molybdate solution in the molybdenum contained ammonia leaching residues is following:

A. prepare burden, size mixing: the dried slag charge of molybdenum contained ammonia leaching (the insoluble molybdenum: 6.84wt%) and MnO that at first 364g is contained molybdenum 20.77wt% ₂Content is that the pyrolusite powder 145.5g of 60wt% sends in the reactive tank; Add then after 3 liters of (3000g) water mix, add concentration and be after 85% phosphatase 11 1ml stirs, add ammoniacal liquor; The pH value of its slip is controlled at 10, and final slip proportion is 1.1g/cm ³, the gained slip is for use;

B. ammonia is pressed reaction: steps A gained slip is added in the ammonia indent, and temperature control 130oC heated and stirred treats that its temperature is to pick up counting behind the 120oC, and ammonia is pressed reaction 1.0 hours; Reaction finishes, and adds the cooling jacket cooling, treats that the still internal pressure reduces at 0 o'clock, and slip is for use in its groove;

C. solid-liquid separation: will put into the beaker more than 5 liters through the reacted material of step B, after pour the B inner filtration into, molybdenum concentration is 3.6 liters of the ammonium molybdate solutions that rise of 16.74g/; And then adopt 10.5 liters of pure water washing filter residues, and getting molybdenum concentration is 10.2 liters of the ammonium molybdate solutions (wash water) that 0.2g/ rises, this wash water and aforementioned filtrating merge to such an extent that molybdenum concentration is the ammonium molybdate solution that 4.53g/ rises; This solution can be used as the liquid stock of subsequent production and uses.

Present embodiment tailings dry weight 469g, wherein contain molybdenum and be merely 2.81%, the recovery of molybdenum reaches 82.6%.

Embodiment 2: the method steps that reclaims ammonium molybdate solution in the molybdenum contained ammonia leaching residues is following:

A. prepare burden, size mixing: (insoluble molybdenum: dried slag charge 520g of molybdenum contained ammonia leaching 7.36wt%) and 260g contain MnO will to contain molybdenum 14.28wt% ₂The pyrolusite powder of 60wt% places in the reactive tank; Adding 2.6 liters of residue washing liquid and the concentration contain after the solid-liquid separation that molybdenum 1.6g/ rises again is after 85% phosphoric acid 20.8ml mixes; Add ammoniacal liquor, the pH value of control slip is between 9.0-9.5, and batching gained slip proportion is 1.32g/cm ³, the gained slip is for use;

B. reacting by heating: above-mentioned gained slip is added airtight ammonia press the reaction kettle internal heating to stir, temperature control is to 135oC, and ammonia is pressed reaction 2.0 hours, then cooling;

C. solid-liquid separation: centrifuging promptly gets molybdenum concentration and is 3.6 liters of the ammonium molybdate solutions that 13.53g/ rises; Filter residue washs with 4.0 liters of pure water, and getting molybdenum concentration is that 1.2g/ rises 4.0 liters of ammonium molybdate solutions (washings), and this washings returns steps A in order to the modulation slip.

The recovery of present embodiment molybdenum is 75.1%, tailings dry weight 769g, wherein contains molybdenum 3.24%.

Embodiment 3: the method steps that reclaims ammonium molybdate solution in the molybdenum contained ammonia leaching residues is following:

A. prepare burden, size mixing: (insoluble molybdenum: ammonia 8.28wt%) soaks dried slag 800g, MnO at first will to contain molybdenum 13.49wt% ₂Content be 60wt% pyrolusite powder 400g, contain molybdenum be 1.2g/ to rise 3.5 liters of wash waters and concentration be that 85% phosphatase 24 0ml and ammoniacal liquor add in the dosing vessel, the pH value of final slip is controlled between the 9.5-10, its proportion is 1.4g/cm ³

B. reacting by heating: slip adds in the ammonia indent, and temperature control 125oC reacts 3 hours postcooling;

C. solid-liquid separation: cross through solid-liquid separation that to filter molybdenum concentration be 3.3 liters of the ammonium molybdate solutions that rise of 19.53g/; Filter residue is through the washing of 4.8 liters of pure water, molybdenum concentration is 4.6 liters of the ammonium molybdate solutions that rise of 0.8g/.The liquid stock that this solution can be used as subsequent production uses.

The recovery of present embodiment molybdenum is 60.76%, and tailings dry weight 1073g wherein contains molybdenum 4.1%.

Embodiment 4: the method steps that reclaims ammonium molybdate solution in the molybdenum contained ammonia leaching residues is following:

A. prepare burden, size mixing: (insoluble molybdenum: ammonia 7.36wt%) soaks dried slag 800g, MnO at first will to contain molybdenum 16.52wt% ₂Content be 60wt% pyrolusite powder 360g, contain molybdenum be 0.8g/ to rise 4.0 liters of wash waters and concentration be that 85% phosphatase 11 6ml and ammoniacal liquor add in the dosing vessel, the pH value of final slip is controlled at 10, its proportion is 1.38g/cm ³

B. reacting by heating: then add in the ammonia indent, temperature control 130oC reacts 3 hours postcooling;

C. solid-liquid separation: cross through solid-liquid separation that to filter molybdenum concentration be 3.8 liters of the ammonium molybdate solutions that rise of 23.32g/; Filter residue is through the washing of 8 liters of pure water, molybdenum concentration is 7.8 liters of the ammonium molybdate solutions that rise of 0.6g/.The liquid stock that this solution can be used as subsequent production uses.

The recovery of present embodiment molybdenum is 63.46%, and tailings dry weight 998g wherein contains molybdenum 4.21%.

Need to prove: though the foregoing description has been described step of the present invention and technology in detail, the present invention is not limited to the foregoing description, all can be along with wherein contained MnO like weight, the phosphoric acid amount of pyrolusite powder ₂With the ratio of phosphate radical and adjust.The substitute mode that every those skilled in the art just can expect without creative work from the foregoing description all belongs to protection scope of the present invention.

Claims (4)

1. reclaim the method for ammonium molybdate solution in the molybdenum contained ammonia leaching residues, it is characterized in that, comprise the steps:

A. prepare burden, size mixing: dried slag charge of molybdenum contained ammonia leaching and the pyrolusite powder and the water that account for this dried slag charge weight 30～50wt% are added in the dosing vessel, and said pyrolusite powder contains MnO ₂Be 60 wt%; The ratio adding concentration of adding 3～5ml in the dried slag charge of the said molybdenum contained ammonia leaching of every 100g is the phosphoric acid of 85wt%, and mixing is stirred and is made into density is 1.1～1.4g/cm ³Slip, add ammoniacal liquor then and stir, control slip the pH value between 9 ~ 10;

B. reacting by heating: the steps A gained slip of preparing burden is added airtight ammonia indent internal heating and stirs, and between temperature 120 ~ 140oC, ammonia is pressed reaction 1～3 hour, is cooled to normal pressure then;

C. solid-liquid separation: gained material after the step B reacting by heating is carried out solid-liquid separation, and filtrating is ammonium molybdate solution; Filter residue is used water washing again, its washings or merge with said ammonium molybdate solution, or return the water of A step as the allotment slip.

2. according to the method that reclaims ammonium molybdate solution in the described molybdenum contained ammonia leaching residues of claim 1, it is characterized in that:

In the said steps A, add ammoniacal liquor again behind the adding phosphoric acid, the pH value of control slip is between 9 ~ 10; At last the density of slip is transferred to 1.1～1.4g/cm ³

3. according to the method that reclaims ammonium molybdate solution in claim 1 or the 2 described molybdenum contained ammonia leaching residues, it is characterized in that:

In the said steps A, the add-on of said pyrolusite powder promptly adds 5.5～7.0 g by the insoluble molybdenum of every gram and contains MnO by the weight that contains insoluble molybdenum in the dried slag charge of said molybdenum contained ammonia leaching ₂It is the pyrolusite powder of 60 wt%.

4. according to the method that reclaims ammonium molybdate solution in claim 1 or the 2 described molybdenum contained ammonia leaching residues, it is characterized in that:

Among the said step C, adopt B or centrifuging to carry out solid-liquid separation; Said filter residue adopts the water washing of 1～3 times of amount of filtrate volume.