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 PDFInfo
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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
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- 239000011609 ammonium molybdate Substances 0.000 title claims abstract description 46
- 235000018660 ammonium molybdate Nutrition 0.000 title claims abstract description 46
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 title claims abstract description 46
- 229940010552 ammonium molybdate Drugs 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 title claims abstract description 22
- 238000002386 leaching Methods 0.000 claims abstract description 89
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011733 molybdenum Substances 0.000 claims abstract description 76
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 239000012629 purifying agent Substances 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000012492 regenerant Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 7
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 5
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract description 23
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract description 15
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 14
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 238000000746 purification Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 239000007832 Na2SO4 Substances 0.000 description 6
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/28—Amines
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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
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.
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