CN114350983A - Method for recovering molybdenum from ammonium molybdate acidic wastewater - Google Patents
Method for recovering molybdenum from ammonium molybdate acidic wastewater Download PDFInfo
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 117
- 239000011733 molybdenum Substances 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 55
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 title claims abstract description 35
- 229940010552 ammonium molybdate Drugs 0.000 title claims abstract description 35
- 235000018660 ammonium molybdate Nutrition 0.000 title claims abstract description 35
- 239000011609 ammonium molybdate Substances 0.000 title claims abstract description 35
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 32
- 239000002351 wastewater Substances 0.000 title claims abstract description 32
- 238000000605 extraction Methods 0.000 claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000003916 acid precipitation Methods 0.000 claims abstract description 39
- 238000005406 washing Methods 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000012074 organic phase Substances 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 44
- 239000012452 mother liquor Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- 239000011550 stock solution Substances 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 230000005514 two-phase flow Effects 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 229940093635 tributyl phosphate Drugs 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- 239000008394 flocculating agent Substances 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000021506 Ipomoea Nutrition 0.000 description 1
- 241000207783 Ipomoea Species 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention belongs to the technical field of wet metallurgy, and particularly relates to a method for recovering molybdenum from ammonium molybdate acidic wastewater. The invention comprises the following steps: step 1, pretreating ore pulp after molybdenum ore acid leaching; step 2, extracting the pretreated solution; step 3, back extraction of the solution treated in the step 2; step 4, acid precipitation is carried out on the solution treated in the step 3; step 5, adjusting the pH value of the solution after acid precipitation; step 6, carrying out secondary extraction on the solution after the acid adjustment; and 7, washing the solution treated in the step 6 with water. The invention can realize the high-efficiency separation and recovery of molybdenum, the recovery rate of the molybdenum can reach more than 99 percent, the process flow is shortened, and the reagent cost is saved.
Description
Technical Field
The invention belongs to the technical field of wet metallurgy, and particularly relates to a method for recovering molybdenum from ammonium molybdate acidic wastewater.
Background
The molybdenum is less in the earth, and the content of the molybdenum only accounts for 0.1 percent of the earth crust mass, and the molybdenum belongs to rare noble metals. Meanwhile, molybdenum is a non-renewable resource and a strategic resource, and is widely applied to the fields of steel industry, nonferrous metals, chemical industry and the like due to small expansion coefficient, high electric conductivity and good heat conductivity, so that molybdenum becomes an irreplaceable strategic material in national economy. China has the advantages of molybdenum resources, and the reserves of molybdenum ores live in the 2 nd position of the world. However, with the continuous expansion and development of the application of molybdenum resources in high-tech and other fields, the demand of molybdenum and metal products thereof is increased year by year, so that molybdenum production enterprises can see the recovery rate of molybdenum very well, thereby showing the strength of the enterprises and creating greater benefits.
With the increase of molybdenum demand, molybdic acid extraction processes are rapidly developed and developed, and separation and purification methods thereof include precipitation methods, ion exchange methods, extraction methods, activated carbon adsorption methods and the like. The separated molybdenum-containing solution is subjected to a traditional acid precipitation process and a concentration crystallization process to obtain a molybdenum product, the acidic wastewater after the precipitates are separated by the two precipitation processes contains a large amount of molybdenum metal and heavy metal impurities such as Cu, Pb and the like, the precipitates can block pipelines in the circulation process of the wastewater, equipment corrosion is caused, and if the precipitates are not treated, environmental pollution is caused, and resources are seriously wasted. Therefore, the method has certain economic benefits and obvious social benefits for the treatment of the acid wastewater and the recovery of the molybdenum in the molybdenum hydrometallurgy.
The technology for recovering molybdenum from the domestic ammonium molybdate production wastewater commonly comprises activated carbon adsorption, extraction, ion exchange, inorganic salt process and the like.Adding (NH) into ammonium molybdate acidic wastewater by some foreign ammonium molybdate production enterprises4)2Stirring S at about 70 ℃ for 30min, and precipitating to separate out MoS2The recovery rate of molybdenum is more than 90%. In the examination by Ipomoea corporation of Japan, pH1.46 was adjusted with sulfuric acid in a 2g/L molybdenum solution, and the solution was adsorbed on activated carbon at 25 ℃ to obtain a molybdenum residue of 30%.
The acid waste liquid is adjusted by alkali to precipitate Cu, Zn and other ions, and the precipitates adsorb and wrap MoO4 2-Coprecipitation is formed to make molybdenum sink into the slag, and 95% of molybdenum can be recovered. Tanglisa and the like adopt a nanofiltration membrane system to treat the acidic wastewater discharged from ammonium molybdate production, and the molybdenum rejection rate reaches more than 80-95%. Acid wastewater of the Jiin and the like is dynamically treated by DK resin and HA resin, and 86-92% of molybdenum and 98% of copper can be recovered.
However, the methods have high treatment cost and complex process, the recovery rate of molybdenum is concentrated between 70 and 90 percent, and the molybdenum is not efficiently recycled. Therefore, it is necessary to develop a new process for recovering molybdenum from ammonium molybdate acidic wastewater.
Disclosure of Invention
The invention aims to provide a method for recovering molybdenum from ammonium molybdate acidic wastewater, and provides a new way with low cost, short flow, cleanness and environmental protection for molybdenum product preparation.
The technical scheme adopted by the invention is as follows:
a method for recovering molybdenum from ammonium molybdate acidic wastewater comprises the following steps:
step 1, pretreating ore pulp after molybdenum ore acid leaching; step 2, extracting the pretreated solution; step 3, back extraction of the solution treated in the step 2; step 4, acid precipitation is carried out on the solution treated in the step 3; step 5, adjusting the pH value of the solution after acid precipitation; step 6, carrying out secondary extraction on the solution after the acid adjustment; and 7, washing the solution treated in the step 6 with water.
In the step 1, the ore pulp after the molybdenum ore is subjected to acid leaching is subjected to solid-liquid separation, a flocculating agent is added into the obtained leachate for thickening and settling, an oxidizing agent is added into the clear liquid for adjusting the potential of the solution, the clear liquid is stood for clarification to reduce the content of suspended solid in the solution, the supernatant after standing is subjected to deep filtration by using a filter aid, the turbidity of the solution is further reduced, and the turbidity of the solution is controlled to be less than 50 ppm.
In the step 2, the solution obtained in the step 1 is subjected to molybdenum extraction by using a mixture of tri-aliphatic amine, tributyl phosphate and sulfonated kerosene, and the molybdenum-loaded organic phase is subjected to acid washing and water washing processes and then enters the next molybdenum back extraction step.
And in the step 2, the molybdenum-containing organic phase after being washed by the acid washing water in the step 2 is subjected to back extraction of molybdenum after being washed by the water, wherein the two-phase flow ratio A/O of a back extraction agent to the organic phase is 1: 3-1: 10, the back extraction temperature is 20-35 ℃, and the mixing contact time is 3-10 min.
The back-extraction agent is 10-30 wt% ammonia water, finally, qualified molybdenum liquid with the molybdenum concentration of 100-140 g/L is obtained, and the extraction process is carried out after organic phase acidification and transformation after back extraction.
In the step 4, the strip liquor obtained by the back extraction in the step 3 is heated to 50-70 ℃, magnesium salt is added, stirring is carried out for 1h, then primary impurity removal is carried out by filtration, the obtained solution is purified again by adding 1-10% of active carbon, and the solution enters a precipitation process to obtain a qualified molybdenum product.
In the step 5, the pH value of the acid precipitation mother liquor obtained in the step 4 is adjusted to 6-8 by adding 10-30% ammonia water, then the solution is kept stand at normal temperature for 16-24 hours and then filtered, and the pH value of the solution is adjusted to 4-5 by using 98% sulfuric acid to obtain the secondary pH-adjusted acid precipitation mother liquor.
In the step 6, the secondary pH value-adjusted acid precipitation mother liquor is used as a secondary extraction stock solution, molybdenum in the mother liquor is extracted and separated by an N235 extraction agent, the extraction temperature is controlled to be 20-30 ℃, the flow ratio O/A is 1-5:1, the ratio O/A is 1-2:1, the organic phase is continuous, the extraction stage is 3-5 stages, a molybdenum-containing organic phase enters a water washing process, and the raffinate water enters a water treatment process.
In the step 6, the N235 extracting agent refers to an organic mixture of trioctylamine with the concentration range of 5-10%, tributylphosphate with the concentration range of 10-20% and sulfonated kerosene with the concentration range of 75-85%.
In the step 7, after the molybdenum-containing organic phase in the step 6 is washed by water, the loaded organic phase enters a back extraction process, and the washing liquid enters a water treatment process; the temperature of washing is controlled to be 20-30 ℃, the flow ratio O/A is 1-7:1, the flow ratio O/A is 1-2:1, the water phase is continuous, and the washing stages are 2-5 stages.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method for recovering molybdenum from ammonium molybdate acidic wastewater, provided by the invention, the solution precipitate is not separated out through the pretreatment of the acid precipitation mother liquor, so that the pipeline is ensured to be smooth in the solution flowing process;
(2) the method for recovering molybdenum from ammonium molybdate acidic wastewater provided by the invention has the advantages that the molybdenum recovery rate can reach more than 99% by efficiently separating and recovering molybdenum through secondary extraction of the ammonium molybdate acidic wastewater, the process flow is shortened, and the reagent cost is saved.
Drawings
FIG. 1 is a flow chart of a method for recovering molybdenum from ammonium molybdate acidic wastewater provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
The Mo concentration in the acid precipitation mother liquor in the acid precipitation process of a certain ore mountain enterprise is 9.3 g/L. As shown in the figure, the method for recovering molybdenum from ammonium molybdate acidic wastewater provided by the invention comprises the following specific steps:
step 1, adding 15% ammonia water 8L/m into acid precipitation mother liquor3(amount of ammonia water added/amount of acid-precipitated mother liquor) adjusting pH of the solution to 6-8, standing at room temperature for 24 hours, filtering, and adding 98% sulfuric acid to the filtrate to obtain 2L/m3Adjusting the pH value of the solution to 4-5 (adding amount of sulfuric acid/amount of acid precipitation mother liquor) to obtain secondary pH-adjusted acid precipitation mother liquor.
And 2, taking the acid precipitation mother liquor with the secondary pH value as a secondary extraction stock solution, extracting and separating molybdenum in the mother liquor by using an organic mixture extracting agent of 5% of N235+ 15% of TBP + 80% of sulfonated kerosene, controlling the extraction temperature to be 25-30 ℃, controlling the flow ratio O/A to be 1:1-1.5, controlling the ratio O/A to be 1:1, extracting for 5min, continuing the organic phase, carrying out extraction for 5 stages, washing the molybdenum-containing organic phase with water, loading the concentration of the organic phase molybdenum to be 9-14 g/L, and treating the raffinate water with the concentration of the molybdenum in the raffinate water being 0.016 g/L.
And 3, after the molybdenum-containing organic phase is washed by water, the loaded organic phase enters a back extraction process, and the water washing liquid enters a water treatment process. The temperature of water washing is controlled to be 25-30 ℃, the flow ratio O/A is 5:1, the flow ratio O/A is 1-2:1, the water phase is continuous, and the water washing stages are 3 stages.
And 4, the two-phase flow ratio A/O of the back-extraction agent to the organic phase is 1: 8, the back-extraction temperature is 30-35 ℃, the mixing contact time is 3min, the number of the back-extraction stages is 3, the back-extraction agent is 16 wt% ammonia water, finally, qualified molybdenum liquid with the molybdenum concentration of 120-140 g/L is obtained, the lean molybdenum concentration after back extraction is less than 0.100g/L, and the organic phase is acidified and transformed and then extracted.
The final effect is as follows: the molybdenum extraction efficiency of the ammonium molybdate acidic waste liquid is more than 99.83 percent, and the back extraction efficiency is more than 99.3 percent.
Example 2
The Mo concentration in the acid precipitation mother liquor in the acid precipitation process of certain molybdenum concentrate processing enterprises is 5.21 g/L. As shown in the figure, the method for recovering molybdenum from ammonium molybdate acidic wastewater provided by the invention comprises the following specific steps:
step 1, adding 20% ammonia water 3L/m into acid precipitation mother liquor3(amount of ammonia water added/amount of mother liquor precipitated) adjusting pH of the solution to 6-8, standing at room temperature for 16 hr, filtering, and adding 98% sulfuric acid to the filtrate to obtain 2.5L/m3Adjusting the pH value of the solution to 4-5 (adding amount of sulfuric acid/amount of acid precipitation mother liquor) to obtain secondary pH-adjusted acid precipitation mother liquor.
And 2, taking the acid precipitation mother liquor with the secondary pH value as a secondary extraction stock solution, extracting and separating molybdenum in the mother liquor by using an organic mixture extracting agent of 6.5% of N235+ 12% of TBP + 81.5% of sulfonated kerosene, controlling the extraction temperature to be 20-25 ℃, controlling the flow ratio O/A to be 1:2-3, controlling the ratio O/A to be 1-1.5:1, extracting for 4min, continuously extracting the organic phase, performing extraction stage 3, allowing the molybdenum-containing organic phase to enter a water washing process, allowing the molybdenum concentration of the loaded organic phase to be 10-13 g/L, allowing the raffinate water to enter a water treatment process, and allowing the molybdenum in the raffinate water to be 0.015 g/L.
And 3, after the molybdenum-containing organic phase is washed by water, the loaded organic phase enters a back extraction process, and the water washing liquid enters a water treatment process. The temperature of water washing is controlled to be 25-30 ℃, the flow ratio O/A is 7:1, the flow ratio O/A is 1-2:1, the water phase is continuous, and the water washing stages are 5 stages.
And 4, carrying out a back-extraction process on the organic phase after acidification and transformation, wherein the two-phase flow ratio A/O of the back-extraction agent to the organic phase is 1: 10, the back-extraction temperature is 20-25 ℃, the mixing contact time is 3min, the back-extraction agent is 20 wt% ammonia water, finally, a qualified molybdenum solution with the molybdenum concentration of 100-130 g/L is obtained, the lean molybdenum concentration after back extraction is less than 0.050g/L, and the organic phase after back extraction is subjected to acidification and transformation.
The final effect is as follows: the molybdenum extraction efficiency of the ammonium molybdate acidic waste liquid is more than 99.71 percent, and the back extraction efficiency is more than 99.57 percent.
Example 3
The Mo concentration in the acid precipitation mother liquor in the acid precipitation process of certain ammonium molybdate production enterprises is 13.2 g/L. As shown in the figure, the method for recovering molybdenum from ammonium molybdate acidic wastewater provided by the invention comprises the following specific steps:
step 1, adding 10% ammonia water to the acid precipitation mother liquor to obtain 7L/m3(amount of ammonia water added/amount of acid-precipitated mother liquor) adjusting pH of the solution to 6-8, standing at room temperature for 8 hours, filtering, and adding 98% sulfuric acid to the filtrate to obtain 3L/m3Adjusting the pH value of the solution to 4-5 (adding amount of sulfuric acid/amount of acid precipitation mother liquor) to obtain secondary pH-adjusted acid precipitation mother liquor.
And 2, taking the acid precipitation mother liquor with the secondary pH value as a secondary extraction stock solution, extracting and separating molybdenum in the mother liquor by using an organic mixture extracting agent of 5.5% of N235+ 14% of TBP + 80.5% of sulfonated kerosene, controlling the extraction temperature to be 25-30 ℃, controlling the flow ratio O/A to be 1:1, controlling the ratio O/A to be 1-1.5:1, extracting for 4min, continuously extracting the organic phase, controlling the extraction stage to be 5 stages, washing the molybdenum-containing organic phase with water to obtain a molybdenum-loaded organic phase with the concentration of 13g/L, treating the raffinate with water, and treating the raffinate with the molybdenum content of 0.025 g/L.
And 3, after the molybdenum-containing organic phase is washed by water, the loaded organic phase enters a back extraction process, and the water washing liquid enters a water treatment process. The temperature of water washing is controlled to be 25-30 ℃, the flow ratio O/A is 3:1, the flow ratio O/A is 1-2:1, the water phase is continuous, and the water washing stages are 3 stages.
And 4, carrying out a step of extraction after acidification and transformation of the organic phase after back extraction, wherein the two-phase flow ratio A/O of the back extraction agent to the organic phase is 1: 10, the back extraction temperature is 20-25 ℃, the mixing contact time is 3min, the back extraction agent is 10 wt% ammonia water, finally, qualified molybdenum liquid with the molybdenum concentration of 110-130 g/L is obtained, the lean molybdenum concentration after back extraction is less than 0.080 g/L.
The final effect is as follows: the molybdenum extraction efficiency of the ammonium molybdate acidic waste liquid is more than 99.81 percent, and the back extraction efficiency is more than 99.38 percent.
Example 4
The Mo concentration in the acid precipitation mother liquor in the acid precipitation process of certain ammonium molybdate production enterprises is 7.36 g/L. As shown in the figure, the method for recovering molybdenum from ammonium molybdate acidic wastewater provided by the invention comprises the following specific steps:
step 1, adding 25% ammonia water into the acid precipitation mother liquor to form 3L/m3(ammonia water addition amount/acid precipitation mother liquor amount) adjusting pH of the solution to 6-8, standing at normal temperature for 12 hours, filtering, and adding 98% sulfur into the filtrateAcid about 2L/m3Adjusting the pH value of the solution to 4-5 (adding amount of sulfuric acid/amount of acid precipitation mother liquor) to obtain secondary pH-adjusted acid precipitation mother liquor.
And 2, taking the acid precipitation mother liquor with the secondary pH value as a secondary extraction stock solution, extracting and separating molybdenum in the mother liquor by using an organic mixture extracting agent of 6% of N235+ 15% of TBP + 79% of sulfonated kerosene, controlling the extraction temperature to be 20-30 ℃, controlling the flow ratio O/A to be 1:1-1.5, controlling the ratio O/A to be 1-1.5:1, extracting for 3min, continuously extracting the organic phase, performing extraction stage 4, washing the molybdenum-containing organic phase with water, loading the concentration of the organic phase molybdenum to be 10-12g/L, and treating the raffinate water with 0.018g/L of molybdenum in the raffinate water.
And 3, after the molybdenum-containing organic phase is washed by water, the loaded organic phase enters a back extraction process, and the water washing liquid enters a water treatment process. The temperature of washing is controlled to be 20-25 ℃, the flow ratio O/A is 4:1, the flow ratio O/A is 1-2:1, the water phase is continuous, and the washing stages are 5 stages.
Step 4, the flow ratio A/O of the back extractant to the organic phase is 1: and 9, back-extraction temperature is 20-25 ℃, mixing and contacting time is 3min, the back-extraction agent is 25 wt% of ammonia water, finally, qualified molybdenum liquid with the molybdenum concentration of 100-110 g/L is obtained, the lean molybdenum concentration after back extraction is less than 0.060g/L, and the extraction process is carried out after organic phase acidification and transformation after back extraction.
The final effect is as follows: the molybdenum extraction efficiency of the ammonium molybdate acidic waste liquid is more than 99.76 percent, and the back extraction efficiency is more than 99.45 percent.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A method for recovering molybdenum from ammonium molybdate acidic wastewater is characterized by comprising the following steps: the method comprises the following steps:
pretreating ore pulp after molybdenum ore acid leaching; step (2), extracting the pretreated solution; step (3) carrying out back extraction on the solution treated in the step (2); step (4), acid precipitation is carried out on the solution treated in the step (3); step (5), adjusting the pH value of the solution after acid precipitation; step (6), carrying out secondary extraction on the solution after the acid exchange; and (7) washing the solution treated in the step (6) with water.
2. The method for recovering molybdenum from ammonium molybdate acidic wastewater according to claim 1, which is characterized in that: in the step (1), the ore pulp after the molybdenum ore is subjected to acid leaching is subjected to solid-liquid separation, a flocculating agent is added into the obtained leachate for thickening and settling, an oxidizing agent is added into the clear liquid to adjust the potential of the solution, the clear liquid is stood for clarification to reduce the content of suspended solid in the solution, the supernatant after standing is subjected to deep filtration by using a filter aid to further reduce the turbidity of the solution, and the turbidity of the solution is controlled to be less than 50 ppm.
3. The method for recovering molybdenum from ammonium molybdate acidic wastewater as claimed in claim 2, which is characterized in that: in the step (2), the solution obtained in the step (1) is subjected to molybdenum extraction by using a mixture of tri-aliphatic amine, tributyl phosphate and sulfonated kerosene, and a molybdenum-loaded organic phase is subjected to acid washing and water washing processes and then subjected to the next molybdenum back extraction.
4. The method for recovering molybdenum from ammonium molybdate acidic wastewater according to claim 3, which is characterized in that: and (2) carrying out back extraction on the molybdenum-containing organic phase subjected to acid washing and water washing in the step (2), wherein the two-phase flow ratio A/O of a back extraction agent to the organic phase is 1: 3-1: 10, the back extraction temperature is 20-35 ℃, and the mixing contact time is 3-10 min.
5. The method for recovering molybdenum from ammonium molybdate acidic wastewater according to claim 4, which is characterized in that: the back-extraction agent is 10-30 wt% ammonia water, finally, qualified molybdenum liquid with the molybdenum concentration of 100-140 g/L is obtained, and the extraction process is carried out after organic phase acidification and transformation after back extraction.
6. The method for recovering molybdenum from ammonium molybdate acidic wastewater according to claim 4, which is characterized in that: in the step (4), the strip liquor obtained by the back extraction in the step (3) is heated to 50-70 ℃, magnesium salt is added, stirring is carried out for 1h, then primary impurity removal is carried out by filtration, the obtained solution is purified again by adding 1-10% of active carbon, and the solution enters a precipitation process to obtain a qualified molybdenum product.
7. The method for recovering molybdenum from ammonium molybdate acidic wastewater according to claim 6, which is characterized in that: in the step (5), the pH of the acid precipitation mother liquor obtained in the step (4) is adjusted to 6-8 by adding 10-30% ammonia water, then the solution is kept stand at normal temperature for 16-24 hours and then filtered, and the pH of the filtrate is adjusted to 4-5 by using 98% sulfuric acid, so that the acid precipitation mother liquor with the secondary pH adjustment is obtained.
8. The method for recovering molybdenum from ammonium molybdate acidic wastewater according to claim 7, which is characterized in that: in the step (6), the secondary pH value-adjusted acid precipitation mother liquor is used as a secondary extraction stock solution, molybdenum in the mother liquor is extracted and separated by an N235 extraction agent, the extraction temperature is controlled to be 20-30 ℃, the flow ratio O/A is 1-5:1, the phase ratio O/A is 1-2:1, the organic phase is continuous, the extraction stage is 3-5, the molybdenum-containing organic phase enters a water washing process, and the extraction residual water enters a water treatment process.
9. The method for recovering molybdenum from ammonium molybdate acidic wastewater according to claim 8, which is characterized in that: in the step (6), the N235 extracting agent refers to an organic mixture of trioctylamine with the concentration range of 5-10%, tributylphosphate with the concentration range of 10-20% and sulfonated kerosene with the concentration range of 75-85%.
10. The method for recovering molybdenum from ammonium molybdate acidic wastewater according to claim 8, which is characterized in that: in the step (7), after the molybdenum-containing organic phase in the step (6) is washed by water, the loaded organic phase enters a back extraction process, and the washing liquid enters a water treatment process; the temperature of washing is controlled to be 20-30 ℃, the flow ratio O/A is 1-7:1, the flow ratio O/A is 1-2:1, the water phase is continuous, and the washing stages are 2-5 stages.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020094564A1 (en) * | 2000-07-17 | 2002-07-18 | Banfield Jillian F. | Method for extracting and separating metals |
| RU2195510C2 (en) * | 2001-02-23 | 2002-12-27 | Уфимцев Виталий Павлович | Method for extracting molybdenum from acid solutions |
| CN101225471A (en) * | 2007-12-17 | 2008-07-23 | 金堆城钼业股份有限公司 | Method for recovering molybdenum from water-washing molybdenum calcine wastewater |
| CN101760652A (en) * | 2009-12-29 | 2010-06-30 | 广东省矿产应用研究所 | Technological method for treating refractory complex molybdenum ore by combined dressing and smelting process |
| JP2013007107A (en) * | 2011-06-27 | 2013-01-10 | Sumitomo Metal Mining Co Ltd | Recovering method of molybdenum and extraction solvent of molybdenum |
| CN106507814B (en) * | 2011-07-05 | 2014-01-08 | 核工业北京化工冶金研究院 | A kind of process for reclaiming uranium molybdenum from uranium molybdenum ore and uranium-bearing molybdenum ore |
| CN105714113A (en) * | 2016-04-21 | 2016-06-29 | 湖南稀土金属材料研究院 | Method for separating tungsten and molybdenum from tungsten sulfide and molybdenum sulfide concentrates |
-
2021
- 2021-12-17 CN CN202111554262.9A patent/CN114350983A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020094564A1 (en) * | 2000-07-17 | 2002-07-18 | Banfield Jillian F. | Method for extracting and separating metals |
| RU2195510C2 (en) * | 2001-02-23 | 2002-12-27 | Уфимцев Виталий Павлович | Method for extracting molybdenum from acid solutions |
| CN101225471A (en) * | 2007-12-17 | 2008-07-23 | 金堆城钼业股份有限公司 | Method for recovering molybdenum from water-washing molybdenum calcine wastewater |
| CN101760652A (en) * | 2009-12-29 | 2010-06-30 | 广东省矿产应用研究所 | Technological method for treating refractory complex molybdenum ore by combined dressing and smelting process |
| JP2013007107A (en) * | 2011-06-27 | 2013-01-10 | Sumitomo Metal Mining Co Ltd | Recovering method of molybdenum and extraction solvent of molybdenum |
| CN106507814B (en) * | 2011-07-05 | 2014-01-08 | 核工业北京化工冶金研究院 | A kind of process for reclaiming uranium molybdenum from uranium molybdenum ore and uranium-bearing molybdenum ore |
| CN106507809B (en) * | 2011-07-05 | 2014-01-08 | 核工业北京化工冶金研究院 | A kind of process for improving uranium molybdenum ore leaching rate and separating U from Mo |
| CN105714113A (en) * | 2016-04-21 | 2016-06-29 | 湖南稀土金属材料研究院 | Method for separating tungsten and molybdenum from tungsten sulfide and molybdenum sulfide concentrates |
Non-Patent Citations (2)
| Title |
|---|
| 李波;: "酸性体系中钼的溶剂萃取研究进展" * |
| 王玉芳;刘三平;王海北;: "钼精矿酸性介质加压氧化生产钼酸铵" * |
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