CN110760700A - Clean production method for zero discharge of wastewater in ammonium molybdate production process - Google Patents

Clean production method for zero discharge of wastewater in ammonium molybdate production process Download PDF

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CN110760700A
CN110760700A CN201911063385.5A CN201911063385A CN110760700A CN 110760700 A CN110760700 A CN 110760700A CN 201911063385 A CN201911063385 A CN 201911063385A CN 110760700 A CN110760700 A CN 110760700A
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leaching
ammonium molybdate
solution
molybdenum
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肖超
陈宁
许明臣
琚成新
李清伟
何亚清
肖连生
车文芳
候凯
田永红
徐森民
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China Molybdenum Co Ltd
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Abstract

A clean production method for zero discharge of wastewater in the process of producing ammonium molybdate comprises the steps of leaching a molybdenum raw material by using an excessive leaching agent, filtering to obtain a leaching solution and leaching residues, wherein the leaching residues are waste residues; then, reacting a molybdenum raw material and a purifying agent with the leaching solution to achieve the purposes of simultaneously consuming residual leaching agent and removing impurities, filtering to obtain a purified liquid and purified slag, and returning the purified slag to the pressure leaching process; extracting the purified solution at a pH value of 4.5-0.5 by adopting an amine extractant, and performing back extraction by adopting ammonia water to obtain a pure ammonium molybdate solution and raffinate; adding a conversion agent and carbon dioxide into the raffinate, and filtering to obtain a calcium sulfate solution and a sodium bicarbonate solution; the sodium bicarbonate is returned to the pressure leaching, and the leaching agent is regenerated. The whole process has low material consumption and high molybdenum recovery rate, and realizes zero discharge of wastewater.

Description

Clean production method for zero discharge of wastewater in ammonium molybdate production process
Technical Field
The invention belongs to the field of molybdenum smelting, and particularly relates to a clean production method with zero discharge of wastewater in the process of producing ammonium molybdate.
Technical Field
Ammonium molybdate as an important chemical product is widely applied to the fields of catalysts, fire retardants, pigments, agricultural micro-fertilizers, chemical drugs and the like, is also an important intermediate product for producing molybdenum powder and metal molybdenum products thereof, and plays an important role in national economy.
At present, the mainstream process for smelting ammonium molybdate comprises the steps of molybdenum concentrate roasting, acid washing, ammonia leaching, purification, acid precipitation, ammonia solution crystallization and the like. Because the process has the problems of complex process, high cost, high labor intensity, serious environmental pollution, low recovery rate of molybdenum in the ammonia leaching slag and the like, a metallurgical method with lower development cost and more environmental protection is urgently needed to replace the traditional process.
The solvent extraction method adopted in China at present can effectively shorten the process flow, but still has the defects of large consumption of the leaching agent, high cost, high salt content in the raffinate, incapability of recycling and discharge, large wastewater discharge amount and the like.
Disclosure of Invention
Aiming at the problems that the consumption of a leaching agent is high, the cost is high, the salt content in raffinate is high, the raffinate cannot be recycled and needs to be discharged, and the discharge amount of wastewater is large in the existing ammonium molybdate production process, the invention provides a clean production method with zero wastewater discharge in the ammonium molybdate production process.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a clean production method with zero discharge of wastewater in the process of producing ammonium molybdate comprises the following specific steps:
1) firstly, leaching a molybdenum raw material by using a leaching agent with the theoretical amount of 1.02-5.0 times at the temperature of 120-200 ℃, filtering to obtain a leaching solution and leaching residues, wherein the leaching solution is used for later use, and the leaching residues are waste residues;
2) reacting a molybdenum raw material and a purifying agent with the leachate obtained in the step 1) to consume the residual leaching agent and simultaneously remove impurities such as phosphorus, silicon, iron and copper, wherein the reaction temperature in the process is 30-95 ℃, the reaction time is 0.5-24h, the final pH value is 6.5-10.5, filtering is carried out to obtain a purified liquid and purified slag, the purified liquid is reserved, and the purified slag is returned to the pressure leaching process;
3) adjusting the pH value of the purified solution to 4.5-0.5 by using sulfuric acid, extracting by using an amine extractant, and performing back extraction by using ammonia water to obtain a pure ammonium molybdate solution and raffinate;
4) adding a regenerant and excessive carbon dioxide into the raffinate, and filtering to obtain waste residues and regenerated liquid; the regenerated liquid can return to the pressure leaching process to serve as a leaching agent;
5) the strip liquor ammonium molybdate is firstly concentrated to 30 percent, and then crystallized and filtered to obtain the ammonium molybdate product.
The leaching agent is one or a mixture of sodium carbonate, sodium bicarbonate, sodium hydroxide and regenerated liquid.
The molybdenum raw material is one or a mixture of molybdenum calcine obtained by roasting molybdenum minerals and molybdenum secondary resources.
The purifying agent is one or a mixture of magnesium chloride, magnesium oxide, magnesium sulfate, aluminum chloride, aluminum oxide and aluminum sulfate.
The regenerant is one or a mixture of calcium oxide and calcium bicarbonate.
By adopting the technical scheme, the invention has the following advantages:
according to the clean production method with zero wastewater discharge in the ammonium molybdate production process, the salt content in the raffinate can be kept relatively low in the ammonium molybdate production process, the raffinate is regenerated to generate regenerated liquid, and the regenerated liquid can serve as a leaching agent in a leaching process, so that no waste liquid is discharged in the whole ammonium molybdate production process, a large amount of cost is saved for enterprises, meanwhile, impurities in raw materials can be removed by the method, and the obtained ammonium molybdate completely meets the national standard.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to illustrate the invention but not to limit it further.
The molybdenum calcines used in the leaching step in the following examples 1 to 6 are all molybdenum calcine raw materials, and the main components and the proportions thereof are Mo48.94%, Cu 3.3%, Fe 0.758%, K0.254%, Na 0.155%, and SiO212.5 percent and P0.012 percent, the purification link also adopts the molybdenum calcine raw material, and the purificant respectively adopts magnesium sulfate, magnesium oxide, aluminum oxide and aluminum sulfate; the regenerated liquid prepared by regenerating raffinate in the embodiment 1 is divided into 4 parts to be carried out in the embodiments 2-5; the leaching agent used in the leaching in example 6 is sodium carbonate.
Example 1:
the molybdenum raw material is ground molybdenum calcine, the leaching temperature is 140 ℃, the mass of the added sodium bicarbonate solid is 120 percent of the mass of the molybdenum calcine, the solid-to-solid ratio of pure water to the molybdenum calcine and the solid sodium bicarbonate solution is 5:1, the leaching time is 3 hours, the rotating speed is 300r/min, the leaching rate of molybdenum reaches 98.6 percent, and the main element contents in the obtained leaching solution are respectively 96.5g/L, Si 0.56.56 g/L of Mo and 0.36g/L, Na of P0.36g/L, Na2CO326g/L, when the pH value of the leaching solution is 9.8, the iron element and the copper element in the raw materials are already mixed with each otherThe leaching agent sodium bicarbonate reacts to form leaching slag, which also comprises silicate existing in a stable form in the raw material.
Magnesium sulfate is used as a purifying agent and the ground molybdenum calcine is added into the leachate, the using amount of the magnesium sulfate and the molybdenum calcine is respectively 2% and 20% of the mass of the leachate, the temperature of the reaction solution is 90 ℃, the reaction time is 3 hours, the residual sodium bicarbonate serving as a leaching agent in the first step can enable the molybdenum calcine serving as a neutralizing agent to be continuously leached, meanwhile, iron and copper elements in the neutralizing agent form precipitates, the magnesium sulfate serving as the purifying agent reacts with a small amount of free Si and P in the leachate to produce precipitates, and finally, purifying slag is formed, but the molybdenum calcine serving as the neutralizing agent is possibly excessive, so the molybdenum calcine possibly exists in the final purifying slag, and the purifying slag needs to be returned to a leaching process to prevent raw materials from being wasted.
Finally, the neutralization purification liquid is obtained, and the main elements and components of the purification liquid are Mo105g/L and Si0.08g/L, P0.02.02 g/L, Na respectively2CO30.5g/L and the pH of the purified solution is 7.2. The magnesium sulfate can realize the neutralization and purification of the leaching solution in one step.
Adding sulfuric acid to adjust the pH value of the purified solution to 4.5, extracting by adopting an amine extractant, and performing back extraction by adopting ammonia water to obtain pure ammonium molybdate solution and raffinate, wherein the raffinate is sodium sulfate solution;
the raffinate component is Na2SO4120.2g/L, the pH value of the solution is 4.5, and the regenerant is calcium oxide. Adding calcium oxide 2 times of physiological theoretical amount of raffinate, introducing carbon dioxide at flow rate of 1L/min, reacting at 30 deg.C for 5 hr, filtering to obtain regenerated liquid component NaHCO3142g/L, and the waste residues are calcium sulfate and calcium carbonate for standby. Shows that the raffinate (sodium sulfate solution) is regenerated to obtain NaHCO3The solution can be effectively returned to be leached for use, and the wastewater discharge is avoided.
The concentration of molybdenum in the strip liquor reaches 209.40g/L, the strip liquor ammonium molybdate is firstly concentrated to 30%, then ammonium molybdate products are obtained through crystallization and filtration, and the product quality is listed in Table 1. The result shows that the ammonium dimolybdate product meets the requirements of national standard MSA-0 of GB/T3460-2017.
TABLE 1 ammonium molybdate crystalline product
Substance(s) Na K Mg Cu Fe Mo Ti
Sample (I) 0.0005 0.0008 0.0002 0.0003 0.0003 56.42 0.0002
MSA-0 0.0005 0.0060 0.0003 0.0003 0.0005 56.4 0.0005
Substance(s) Cd Sb Bi Ni Mn Cr W
Sample (I) 0.0005 0.0005 0.0005 0.0003 0.0003 0.0001 0.005
MSA-0 0.0005 0.0005 0.0005 0.0003 0.0003 0.0002 0.010
Substance(s) As Sn Pb P Si Al Ca
Sample (I) 0.0004 0.0003 0.0003 0.0003 0.0005 0.0005 0.0005
MSA-0 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005
Example 2:
the molybdenum raw material is molybdenum calcine after grinding, the leaching temperature is 160 ℃, and the regeneration liquid of the raffinate in the example 1, namely NaHCO is added3The content of the molybdenum is 142g/L, the solid-to-solid ratio of the regenerated solution to the molybdenum calcine solution is 5:1, the leaching time is 6 hours, the rotating speed is 380r/min, and the contents of main elements in the obtained leaching solution are respectively 96.9g/L, Si 0.56g/L, P0.36.36 g/L, Na2CO326g/L, the pH value of the leaching solution is 9.8, and the leaching rate of molybdenum reaches 99.0%. The regenerated solution can be returned to the leaching link to be used as a leaching agent, and the zero-discharge clean production of the ammonium molybdate wastewater is realized.
Adding aluminum sulfate as purifying agent and ground molybdenum calcine into the leachate, wherein the usage amounts of the aluminum sulfate and the molybdenum calcine are respectively 2% and 20% of the mass of the leachate, the temperature of the reaction solution is 90 ℃, the reaction time is 3h, and a neutralized purifying solution is finally obtained, and the main elements and components of the purifying solution are respectively Mo106.3g/L, Si 0.07.07 g/L, P0.01.01 g/L, Na2CO30.5g/L and the pH of the purified solution is 7.2. The use of aluminum sulfate in the process can be one stepThe neutralization and purification of the leaching solution are realized.
Adding sulfuric acid to adjust the pH value of the purified solution to 4.4, extracting by adopting an amine extractant, and performing back extraction by adopting ammonia water to obtain pure ammonium molybdate solution and raffinate, wherein the raffinate is sodium sulfate solution;
the raffinate component is Na2SO4119.5g/L, pH 4.4.4, and the regenerant is calcium oxide. Adding calcium oxide 2 times of physiological theoretical amount of raffinate, introducing carbon dioxide at flow rate of 1L/min, reacting at 30 deg.C for 5 hr, filtering to obtain regenerated liquid component NaHCO3139.8g/L, and the waste residue is calcium sulfate and calcium carbonate. The raffinate is regenerated, and can effectively return to leaching, so that the wastewater discharge is avoided.
The concentration of molybdenum in the strip liquor reaches 213.60g/L, the strip liquor ammonium molybdate is firstly concentrated to 30 percent, then ammonium molybdate products are obtained through crystallization and filtration, and the product quality is listed in Table 2. The result shows that the ammonium dimolybdate product meets the requirements of national standard MSA-0 of GB/T3460-2017.
TABLE 2 ammonium molybdate crystalline product
Substance(s) Na K Mg Cu Fe Mo Ti
Sample (I) 0.0005 0.0008 0.0002 0.0003 0.0003 56.44 0.0002
MSA-0 0.0005 0.0060 0.0003 0.0003 0.0005 56.4 0.0005
Substance(s) Cd Sb Bi Ni Mn Cr W
Sample (I) 0.0005 0.0005 0.0005 0.0003 0.0003 0.0001 0.005
MSA-0 0.0005 0.0005 0.0005 0.0003 0.0003 0.0002 0.010
Substance(s) As Sn Pb P Si Al Ca
Sample (I) 0.0004 0.0003 0.0003 0.0003 0.0005 0.0005 0.0005
MSA-0 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005
Example 3:
the molybdenum raw material is molybdenum calcine after grinding, the leaching temperature is 160 ℃, and the regeneration liquid of the raffinate in the example 1, namely NaHCO is added3The content is 142g/L, the solid-to-solid ratio of the regenerated solution to the molybdenum calcine is 5:1, the leaching time is 6 hours, the rotating speed is 380r/min, and the leaching rate of molybdenum reaches 98.95 percent. The regenerated solution can be returned to the leaching link to be used as a leaching agent.
Adding magnesium oxide as purifying agent and ground molybdenum calcine into the leachate, wherein the use amount of magnesium oxide and molybdenum calcine is 2% and 20% of the leachate respectively, the reaction temperature is 90 deg.C, the reaction time is 3h, and the main elements and components in the purified solution are Mo105.2g/L, Si 0.08.08 g/L, P0.013.013 g/L, Na respectively2CO30.44g/L, pH of the purified solution is 7.1. The magnesium oxide is used in the process to realize the neutralization and purification of the leachate in one step.
The raffinate component is Na2SO4122g/L, pH 4.5.5, and the regenerant is calcium oxide. Adding calcium oxide 2 times of physiological theoretical amount of raffinate, introducing carbon dioxide at flow rate of 1L/min, reacting at 30 deg.C for 5 hr, filtering to obtain regenerated liquid component NaHCO3140.5g/L, and the waste residue is calcium sulfate and calcium carbonate. The raffinate is regenerated, and can effectively return to leaching, so that the wastewater discharge is avoided.
The concentration of molybdenum in the strip liquor reaches 206.0g/L, the strip liquor ammonium molybdate is firstly concentrated to 30 percent, then ammonium molybdate products are obtained through crystallization and filtration, and the product quality is listed in Table 3. The result shows that the ammonium dimolybdate product meets the requirements of national standard MSA-0 of GB/T3460-2017.
TABLE 3 ammonium molybdate crystalline product
Substance(s) Na K Mg Cu Fe Mo Ti
Sample (I) 0.0005 0.0008 0.0002 0.0003 0.0003 56.42 0.0002
MSA-0 0.0005 0.0060 0.0003 0.0003 0.0005 56.4 0.0005
Substance(s) Cd Sb Bi Ni Mn Cr W
Sample (I) 0.0005 0.0005 0.0005 0.0003 0.0003 0.0001 0.005
MSA-0 0.0005 0.0005 0.0005 0.0003 0.0003 0.0002 0.010
Substance(s) As Sn Pb P Si Al Ca
Sample (I) 0.0004 0.0003 0.0003 0.0003 0.0004 0.0005 0.0005
MSA-0 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005
Example 4:
the molybdenum raw material is molybdenum calcine after grinding, the leaching temperature is 160 ℃, and the regeneration liquid of the raffinate in the example 1, namely NaHCO is added3The content is 142g/L, the solid-to-solid ratio of the regenerated solution to the molybdenum calcine is 5:1, the leaching time is 6 hours, the rotating speed is 380r/min, and the leaching rate of molybdenum reaches 99.12 percent. The regenerated solution can be returned to the leaching link to be used as a leaching agent.
Adding alumina as purifying agent and ground molybdenum calcine into the leachate, wherein the use amount of alumina and molybdenum calcine is 2% and 20% of the leachate respectively, the reaction solution temperature is 90 deg.C, and the reaction time is 3h, to obtain neutralized purifying solution, and the purifying solution contains main elements and components of Mo106.6g/L, Si 0.07.07 g/L, P0.01.01 g/L, Na2CO30.47g/L, pH of the purified solution 7.2. The aluminum oxide is used in the process to realize neutralization and purification of the leachate in one step.
The raffinate component is Na2SO4118.2g/L, pH 4.5.5, and the regenerant is calcium oxide. Adding calcium oxide 2 times of physiological theoretical amount of raffinate, introducing carbon dioxide at flow rate of 1L/min, reacting at 30 deg.C for 5 hr, filtering to obtain regenerated liquid component NaHCO3139.7g/L, and the waste residue is calcium sulfate and calcium carbonate. The raffinate is regenerated, and can effectively return to leaching, so that the wastewater discharge is avoided.
The concentration of molybdenum in the strip liquor reaches 211g/L, the strip liquor ammonium molybdate is firstly concentrated to 30 percent, then ammonium molybdate products are obtained through crystallization and filtration, and the product quality is listed in Table 4. The result shows that the ammonium dimolybdate product meets the requirements of national standard MSA-0 of GB/T3460-2017.
TABLE 4 ammonium molybdate crystalline product
Substance(s) Na K Mg Cu Fe Mo Ti
Sample (I) 0.0005 0.0007 0.0002 0.0003 0.0003 56.44 0.0002
MSA-0 0.0005 0.0060 0.0003 0.0003 0.0005 56.4 0.0005
Substance(s) Cd Sb Bi Ni Mn Cr W
Sample (I) 0.0005 0.0005 0.0005 0.0003 0.0003 0.0001 0.005
MSA-0 0.0005 0.0005 0.0005 0.0003 0.0003 0.0002 0.010
Substance(s) As Sn Pb P Si Al Ca
Sample (I) 0.0004 0.0003 0.0003 0.0003 0.0004 0.0005 0.0005
MSA-0 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005
Example 5:
the leaching condition is molybdenum calcine after grinding, and raffinate regeneration liquid NaHCO is added3The content is 142g/L, the leaching temperature is 160 ℃, the regenerated liquid and the molybdenum calcine have the liquid-solid ratio of 5:1, the leaching time is 6 hours, the rotating speed is 380r/min, and the leaching rate of molybdenum reaches 98.88 percent. The regenerated solution can be returned to the leaching link to be used as a leaching agent.
Adding aluminum chloride as a purifying agent and ground molybdenum calcine into the leachate, wherein the using amounts of the aluminum chloride and the molybdenum calcine are respectively 2% and 20% of the mass of the leachate, the temperature of the reaction solution is 90 ℃, the reaction time is 3 hours, and finally obtaining a neutralized purifying solution, wherein the main elements and components of the purifying solution are respectively Mo105.4g/L, Si 0.06g/L, P0.015.015 g/L, Na2CO30.5g/L, pH of the purified solution 7.3. The aluminum chloride used in the process can realize neutralization and purification of the leachate in one step.
Raffinate fraction Na2SO4119.7g/L, pH 4.5.5, and the regenerant is calcium oxide. Adding calcium oxide 2 times of physiological theoretical amount of raffinate, introducing carbon dioxide at flow rate of 1L/min, reacting at 30 deg.C for 5 hr, and filtering to obtain regenerated liquid component NaHCO3141.0g/L, and the waste residue is calcium sulfate and calcium carbonate. The raffinate is regenerated, and can effectively return to leaching, so that the wastewater discharge is avoided.
The concentration of molybdenum in the strip liquor reaches 208.8g/L, the strip liquor ammonium molybdate is firstly concentrated to 30 percent, then ammonium molybdate products are obtained through crystallization and filtration, and the product quality is listed in Table 5. The result shows that the ammonium dimolybdate product meets the requirements of national standard MSA-0 of GB/T3460-2017.
TABLE 5 ammonium molybdate crystalline product
Substance(s) Na K Mg Cu Fe Mo Ti
Sample (I) 0.0005 0.0007 0.0002 0.0003 0.0003 56.42 0.0002
MSA-0 0.0005 0.0060 0.0003 0.0003 0.0005 56.4 0.0005
Substance(s) Cd Sb Bi Ni Mn Cr W
Sample (I) 0.0005 0.0005 0.0005 0.0003 0.0003 0.0001 0.005
MSA-0 0.0005 0.0005 0.0005 0.0003 0.0003 0.0002 0.010
Substance(s) As Sn Pb P Si Al Ca
Sample (I) 0.0004 0.0003 0.0003 0.0003 0.0004 0.0005 0.0005
MSA-0 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005
Example 6:
the leaching conditions are that the ground molybdenum calcine is leached at the temperature of 140 ℃, the mass of the added sodium carbonate solid is 56 percent of that of the molybdenum calcine, the solid sodium carbonate is added into the pure water and the molybdenum calcine, the liquid-solid ratio is 5:1, the leaching time is 3 hours, the rotating speed is 300r/min, the leaching rate of molybdenum reaches 98.9 percent, and a leaching solution is obtained, so that the molybdenum calcine is obtainedContains main elements of Mo 96.1g/L, Si 0.55.55 g/L and P0.35g/L, Na2CO323g/L and the pH value of the leaching solution is 9.8, which indicates that the molybdenum can be dissolved out in the leaching process by using sodium carbonate.
Adding magnesium chloride as purifying agent and ground molybdenum calcine into the leachate, wherein the usage amount of magnesium chloride and molybdenum calcine is 2% and 20% of the leachate respectively, the reaction solution temperature is 90 deg.C, and the reaction time is 3h, to obtain neutralized purifying solution, the main elements and components of the purifying solution are Mo106.1g/L, Si 0.06g/L, P0.014.014 g/L, Na respectively2CO30.44g/L, pH of the purified solution 7.2. The magnesium chloride can realize the neutralization and purification of the leachate in one step.
The raffinate component is Na2SO4118.8g/L, pH 4.5.5, and the regenerant is calcium bicarbonate. Adding calcium bicarbonate 2 times of physiological theoretical amount of raffinate, introducing carbon dioxide at flow rate of 1L/min, reacting at 30 deg.C for 5 hr, filtering to obtain regenerated liquid component NaHCO3140.5g/L, and the waste residue is calcium sulfate and calcium carbonate. The raffinate is regenerated, and can be effectively returned to leaching for use, so that the wastewater discharge is avoided.
The concentration of molybdenum in the strip liquor reaches 212.60g/L, the strip liquor ammonium molybdate is firstly concentrated to 30 percent, then ammonium molybdate products are obtained through crystallization and filtration, and the product quality is listed in Table 6. The result shows that the ammonium dimolybdate product meets the requirements of national standard MSA-0 of GB/T3460-2017.
TABLE 6 ammonium molybdate crystalline product
Substance(s) Na K Mg Cu Fe Mo Ti
Sample (I) 0.0005 0.0006 0.0002 0.0003 0.0003 56.43 0.0002
MSA-0 0.0005 0.0060 0.0003 0.0003 0.0005 56.4 0.0005
Substance(s) Cd Sb Bi Ni Mn Cr W
Sample (I) 0.0005 0.0005 0.0005 0.0003 0.0003 0.0001 0.005
MSA-0 0.0005 0.0005 0.0005 0.0003 0.0003 0.0002 0.010
Substance(s) As Sn Pb P Si Al Ca
Sample (I) 0.0004 0.0003 0.0003 0.0003 0.0005 0.0005 0.0005
MSA-0 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005
As can be seen from the above examples, the leaching agent selected in the leaching process is used to leach molybdenum from the raw material while removing a portion of impurities, such as copper and iron, so that when the leaching agent is selected, sodium hydroxide, or a mixture of any combination of sodium carbonate, sodium bicarbonate and sodium hydroxide, may be used in addition to sodium carbonate and sodium bicarbonate.
The molybdenum raw material can also be molybdenum calcine obtained by roasting, or secondary molybdenum resource, or a mixture of the molybdenum calcine and the secondary molybdenum resource.
The regenerant is calcium oxide and/or calcium bicarbonate, calcium ions can be fully reflected with sulfate ions in the raffinate to form waste residues, and redundant calcium ions can finally form the waste residues in the form of calcium carbonate precipitation under the condition of excessive carbon dioxide.
While the method of the present invention has been described in detail in connection with the exemplary embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments without departing from the spirit and scope as defined by the claims.

Claims (5)

1. A clean production method with zero discharge of wastewater in the process of producing ammonium molybdate is characterized by comprising the following specific steps:
1) firstly, leaching a molybdenum raw material by using a leaching agent with the theoretical amount of 1.02-5.0 times at the temperature of 120-200 ℃, filtering to obtain a leaching solution and leaching residues, wherein the leaching solution is used for later use, and the leaching residues are waste residues;
2) reacting a molybdenum raw material and a purifying agent with the leachate obtained in the step 1) to consume the residual leaching agent and simultaneously remove impurities such as phosphorus, silicon, iron and copper, wherein the reaction temperature in the process is 30-95 ℃, the reaction time is 0.5-24h, the final pH value is 6.5-10.5, filtering is carried out to obtain a purified liquid and purified slag, the purified liquid is reserved, and the purified slag is returned to the pressure leaching process;
3) adjusting the pH value of the purified solution to 4.5-0.5 by using sulfuric acid, extracting by using an amine extractant, and performing back extraction by using ammonia water to obtain a pure ammonium molybdate solution and raffinate;
4) adding a regenerant and excessive carbon dioxide into the raffinate, and filtering to obtain waste residues and regenerated liquid; the regenerated liquid can return to the pressure leaching process to serve as a leaching agent;
5) the strip liquor ammonium molybdate is firstly concentrated to 30 percent, and then crystallized and filtered to obtain the ammonium molybdate product.
2. The clean production method with zero wastewater discharge in the ammonium molybdate production process according to claim 1, characterized in that: the leaching agent is one or a mixture of sodium carbonate, sodium bicarbonate, sodium hydroxide and regenerated liquid.
3. The clean production method with zero wastewater discharge in the ammonium molybdate production process according to claim 1, characterized in that: the molybdenum raw material is one or a mixture of molybdenum calcine obtained by roasting molybdenum minerals and molybdenum secondary resources.
4. The clean production method with zero wastewater discharge in the ammonium molybdate production process according to claim 1, characterized in that: the purifying agent is one or a mixture of magnesium chloride, magnesium oxide, magnesium sulfate, aluminum chloride, aluminum oxide and aluminum sulfate.
5. The clean production method with zero wastewater discharge in the ammonium molybdate production process according to claim 1, characterized in that: the regenerant is one or a mixture of calcium oxide and calcium bicarbonate.
CN201911063385.5A 2019-10-31 2019-10-31 Clean production method for zero discharge of wastewater in ammonium molybdate production process Withdrawn CN110760700A (en)

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