CN115478178A - Method for efficiently extracting vanadium and manganese from vanadium precipitation mother liquor obtained by calcium roasting, acid leaching and vanadium extraction of vanadium slag - Google Patents
Method for efficiently extracting vanadium and manganese from vanadium precipitation mother liquor obtained by calcium roasting, acid leaching and vanadium extraction of vanadium slag Download PDFInfo
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- CN115478178A CN115478178A CN202211048581.7A CN202211048581A CN115478178A CN 115478178 A CN115478178 A CN 115478178A CN 202211048581 A CN202211048581 A CN 202211048581A CN 115478178 A CN115478178 A CN 115478178A
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- vanadium
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- residual water
- slag
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 202
- 238000000605 extraction Methods 0.000 title claims abstract description 142
- 239000011572 manganese Substances 0.000 title claims abstract description 97
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 86
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000001556 precipitation Methods 0.000 title claims abstract description 70
- 239000002893 slag Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000012452 mother liquor Substances 0.000 title claims abstract description 50
- 238000002386 leaching Methods 0.000 title claims abstract description 46
- 239000002253 acid Substances 0.000 title claims abstract description 34
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title abstract description 3
- 229910052791 calcium Inorganic materials 0.000 title abstract description 3
- 239000011575 calcium Substances 0.000 title abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 23
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 23
- 239000004571 lime Substances 0.000 claims abstract description 23
- 230000002308 calcification Effects 0.000 claims abstract description 20
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 vanadate anions Chemical class 0.000 claims abstract description 17
- 239000011550 stock solution Substances 0.000 claims abstract description 15
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 14
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 14
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 12
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 239000000284 extract Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 20
- 239000012074 organic phase Substances 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 239000003350 kerosene Substances 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- OKYDTGSQPZBYTF-UHFFFAOYSA-J calcium;magnesium;disulfate Chemical compound [Mg+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OKYDTGSQPZBYTF-UHFFFAOYSA-J 0.000 claims description 3
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 24
- 238000011084 recovery Methods 0.000 abstract description 11
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- 229910001456 vanadium ion Inorganic materials 0.000 description 2
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- RAQQJEFTDXAGKW-UHFFFAOYSA-M C([O-])([O-])=O.[Mg+].[NH4+] Chemical compound C([O-])([O-])=O.[Mg+].[NH4+] RAQQJEFTDXAGKW-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
-
- 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
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
Abstract
The invention discloses a method for extracting vanadium and manganese from vanadium precipitation mother liquor obtained by calcium roasting, acid leaching and vanadium extraction of vanadium slag. The method comprises the following steps: (1) Placing the calcified roasting clinker of the vanadium slag into manganese extraction residual water, adding dilute sulfuric acid to obtain acid leaching liquid, adding ammonium salt into the acid leaching liquid to obtain vanadium precipitation mother liquid, and adjusting the pH value of the vanadium precipitation mother liquid to 2.0-3.0 to obtain vanadium extraction raw liquid; (2) Extracting vanadate anions in the vanadium extraction stock solution to obtain vanadium extraction residual water; (3) adjusting the pH value of vanadium extraction residual water to 4.5-5.0 to obtain manganese extraction stock solution; (4) Carrying out countercurrent extraction on manganese ions in the manganese extraction stock solution to obtain manganese extraction residual water; (5) And (5) recycling the steps (1) to (4) to separate and extract vanadium and manganese in the vanadium and manganese extraction waste water until the concentration of magnesium ions in the manganese extraction waste water reaches 25g/L, neutralizing and precipitating the magnesium ions in the manganese extraction waste water by using lime, and returning the neutralized water to be used as a water source of acid leaching liquid of the vanadium slag calcification roasting clinker. The method has the advantages of greatly reducing the amount of slag, generating no waste water, realizing the high-efficiency recovery of vanadium and manganese, reducing the cost and the like.
Description
The technical field is as follows:
the invention relates to the technical field of chemical metallurgy, in particular to a method for efficiently extracting vanadium and manganese from vanadium precipitation mother liquor obtained by extracting vanadium from vanadium slag through calcification roasting and acid leaching.
Background art:
the vanadium titano-magnetite is an important mineral resource for extracting vanadium in China, and more than 80 percent of vanadium in China is extracted from the vanadium titano-magnetite. The Panxi area of Sichuan province has a large amount of vanadium-titanium magnetite, and V is obtained after the vanadium-titanium magnetite is prepared into steel by a pyrogenic process 2 O 5 The grade of the vanadium slag is about 20 percent, and V can be prepared by adopting a combined process of calcified roasting-sulfuric acid leaching-ammonium salt vanadium precipitation-calcining after the vanadium slag is ground 2 O 5 Flake vanadium with purity greater than 98%. But the vanadium precipitation process can generate vanadium precipitation mother liquor, metal ions in the vanadium precipitation mother liquor are removed by a lime neutralization method in production, a large amount of lime is added to precipitate metal in a hydroxide form, the purpose of removing metal impurity ions is achieved, and the neutralized wastewater is returned to leaching for use. Although the lime neutralization method has good effect on removing impurity ions in the vanadium precipitation mother liquor, the following problems still exist: (1) valuable metals in the vanadium precipitation mother liquor are not recovered. The vanadium precipitation mother liquor contains valuable metals such as V of about 0.2g/L, mn of 8-15 g/L, mg of about 1.4g/L and the like, and the metal ions are finally precipitated in the form of hydroxide and enter neutralization slag to be discarded. The lime neutralization method does not recover valuable metals, wastes resources and causes certain pollution to the environment. (2) The treatment cost is high. Although lime is cheap, the initial pH value of the vanadium precipitation mother liquor is about 1.3-1.5, the acidity is strong, the pH value of the solution needs to be adjusted to be more than 10 in order to completely precipitate manganese and magnesium plasmas, and a large amount of lime needs to be added, so that the wastewater treatment cost is increased. (3) The waste water after lime neutralization is alkaline, and the use amount of sulfuric acid is further increased when the waste water returns to leaching, so that the leaching cost is increased.
In general, although a vanadium plant adopts a calcification roasting acid leaching cleaning process to extract vanadium, the problem of recycling vanadium precipitation mother liquor is not treated in a high-valued way, and particularly, high-concentration manganese and a small amount of vanadium are lost in neutralized slag, so that metal resources are seriously wasted. Therefore, the key difficult problem that a vanadium plant needs to overcome urgently is to recover valuable metals from the vanadium precipitation mother liquor and solve the problem of recycling the vanadium precipitation mother liquor.
The university of Chongqing adopts an electrolytic manganese process (ZL 201310530382.4, a treatment method of industrial wastewater in vanadium oxide production) to recover metal manganese in the vanadium precipitation mother liquor, and provides an electrolytic manganese anolyte ammonium carbonate magnesium removal technology (ZL 201010503168.6, a method for reducing the concentration of magnesium ions in electrolytic manganese anolyte), and adopts ammonium carbonate, ammonium fluoride and aluminum sulfate to remove Mg accumulated in the electrolytic manganese anolyte 2+ ，Mg 2+ The removal rate was about 50%. However, anode mud generated by the 'vanadium precipitation mother liquor electrolytic manganese-ammonium carbonate magnesium removal anolyte circulating leaching' process of Chongqing university contains heavy metal Pb, and belongs to hazardous waste; the slag of magnesium carbonate and aluminum ammonium sulfate contains F, mn and other elements, and belongs to hazardous waste; and vanadium ions in the vanadium precipitation wastewater are lost in the purification slag, and vanadium is not recovered.
The invention content is as follows:
the invention solves the problems of recovery of valuable metals in vanadium precipitation mother liquor of vanadium slag calcification roasting acid leaching vanadium extraction and recycling of vanadium precipitation mother liquor in the prior art, and provides a method for efficiently extracting vanadium and manganese from vanadium precipitation mother liquor of vanadium slag calcification roasting acid leaching vanadium extraction.
The invention aims to provide a method for efficiently extracting vanadium and manganese from vanadium precipitation mother liquor obtained by extracting vanadium from vanadium slag through calcification roasting and acid leaching, which comprises the following steps:
(1) Putting the calcified roasting clinker of the vanadium slag into manganese extraction residual water, adding dilute sulfuric acid to obtain acid leaching solution containing vanadium, manganese and magnesium, adding ammonium salt into the acid leaching solution to obtain vanadium precipitation mother liquor, and adjusting the pH value of the vanadium precipitation mother liquor to 2.0-3.0 by using calcium carbonate to obtain vanadium extraction stock solution;
(2) Extracting vanadate anions containing pentavalent vanadium in vanadium extraction stock solution by using an extraction system consisting of secondary carbon primary amine N1923 with the volume fraction of 10% and sulfonated kerosene with the volume fraction of 90% to obtain vanadium extraction residual water;
(3) Adjusting the pH value of vanadium extraction residual water to 4.5-5.0 by using calcium carbonate to obtain manganese extraction stock solution;
(4) The manganese ions in the manganese stock solution are extracted by four-stage countercurrent extraction system consisting of 30 volume percent of P204 and 70 volume percent of sulfonated kerosene, the pH value of the manganese ion extraction process is controlled by ammonium bicarbonate or ammonium carbonate, the first-stage extraction pH value of the manganese ions is controlled to be 4.1-4.5, the second-stage extraction pH value is controlled to be 3.7-4.0, the third-stage extraction pH value is controlled to be 3.3-3.5, and the fourth-stage extraction pH value is controlled to be 2.9-3.0. Obtaining manganese extraction residual water, and returning the manganese extraction residual water to the step (1) to be used as a water source of acid leaching liquid of the vanadium slag calcification roasting clinker;
(5) Circulating the processes of the steps (1) to (4) to separate and extract vanadium and manganese in the manganese-extracted residual water until the concentration of magnesium ions in the manganese-extracted residual water in the step (4) reaches 25g/L, and neutralizing and precipitating the magnesium ions in the manganese-extracted residual water by using lime;
(6) And (5) after magnesium ions in the manganese extraction residual water are neutralized and precipitated by lime, the obtained ammonia gas is returned to the step (1) to be used as ammonium salt to realize vanadium precipitation, the manganese extraction residual water after magnesium ions are neutralized is subjected to solid-liquid separation to obtain neutralized water and calcium-magnesium sulfate slag, and the neutralized water is returned to the step (1) to be used as a water source of acid leaching liquid of the vanadium slag calcification roasting clinker.
The manganese extraction residual water (Mn extraction residual water) provided by the invention does not need to be neutralized every time, but the Mn extraction residual water is circularly leached out of the calcified roasted clinker until the total ion concentration in the Mn extraction residual water influences the leaching of V; in the whole process of Mn extraction residual water circulation leaching, the pH value in the Mn extraction process is controlled by an ammonium neutralizer, so that the high-efficiency separation and extraction of Mn ions are realized. And NH 4 + The ammonium salt of the circulating leachate is consumed in time in the vanadium precipitation process, and accumulation is avoided. The ammonium salt is firstly used for controlling the pH value in the manganese extraction process to realize Mn 2+ High efficiency extraction of NH 4 + And the vanadium is precipitated again, thereby achieving two purposes and reducing the cost. Only Mg exists in the whole cycle leaching process 2+ Accumulation occurs when Mg in manganese extraction residual water 2+ Neutralizing, precipitating and removing magnesium only when the vanadium slag is accumulated to a certain concentration, and circularly leaching the vanadium slag calcification roasting clinker by using water after neutralization.
The method provided by the invention comprehensively extracts vanadium and manganese in the vanadium precipitation mother liquor by the processes of vanadium precipitation mother liquor extraction vanadium extraction, pH control of the extraction process, efficient extraction manganese extraction and manganese extraction residual water circulating leaching, and realizes the minimization and harmlessness of slag amount, no wastewater generation and cost minimization of the whole process. The amount of slag generated by the vanadium precipitation wastewater treated by the method provided by the invention is less than that generated by the 'vanadium precipitation mother liquor electrolytic manganese-ammonium carbonate magnesium removal anolyte circulating leaching' process provided by Chongqing university and that generated by the 'lime direct neutralization vanadium precipitation mother liquor' process adopted in enterprise production. The method realizes the recovery of valuable metals from the vanadium precipitation mother liquor, solves the problem of recycling the vanadium precipitation mother liquor, solves the key problem of comprehensive utilization of the vanadium precipitation mother liquor in a vanadium plant, and has wide application prospect.
Preferably, the initial concentrations of vanadium, manganese and magnesium in the acid leaching solution in the step (1) are respectively 24-26 g/L, 6-8 g/L and 1.2-1.4 g/L. When the pH value of the vanadium precipitation mother liquor is about 2.2, vanadium precipitation occurs on ammonium salt and vanadium ions, and Mn and Mg cannot be precipitated. The concentration of V in the vanadium precipitation mother liquor is 0.2-0.6 g/L.
Preferably, the extraction system in the step (2) consists of 10 volume percent of secondary carbon primary amine N1923 and 90 volume percent of sulfonated kerosene.
Preferably, the extraction in the step (2) is four-stage countercurrent extraction, the volume ratio of the aqueous phase to the organic phase in the extraction system is 4.
Preferably, the vanadium is reversely extracted from the vanadium-loaded organic phase obtained in the step (2) by using an ammonium carbonate aqueous solution, the organic phase is regenerated to be recycled, and the vanadium-rich liquid returns to the step (1) of precipitating vanadium from the acid leaching liquid ammonium salt of the vanadium slag calcification roasting clinker to precipitate vanadium.
Preferably, the extraction system described in step (4) consists of 30% by volume of P204 and 70% by volume of sulfonated kerosene.
Preferably, the volume ratio of the aqueous phase to the organic phase in the extraction system in the step (4) is 1. The manganese-loaded organic phase in the step (4) is subjected to four-stage countercurrent back extraction by using a sulfuric acid solution, and the organic phase is regenerated to realizeThe back extraction solution is a high-purity manganese sulfate solution. NH in manganese extraction residual water in step (4) 4 + ≤9.0g/L，NH 4 + NH for precipitating vanadium as ammonium salt in acid leaching solution of vanadium slag calcified roasting clinker 4 + The source of (2) was used.
Preferably, the number of cycles of steps (1) to (4) is 20, and steps (1) to (4) are performed all the time in a cycle. Valuable metal vanadium (V) and manganese (Mn) ions in the vanadium precipitation mother liquor are extracted in each circulation, and Mg is remained 2+ Accumulated in the solution until Mg in manganese extraction residual water 2+ The accumulated concentration is less than or equal to 25g/L, ions in the wastewater are removed by neutralization and precipitation, and the neutralized water is recycled to leach the calcified roasted clinker.
Compared with the prior art, the invention has the following advantages: in the method for separating and extracting metal vanadium and manganese from vanadium precipitation mother liquor, ammonium neutralizer is adopted to control the pH value in the manganese extraction process, so that the high-efficiency separation and extraction of manganese ions are realized, and NH in the ammonium neutralizer is used 4 + The vanadium precipitation process of the acid leaching solution is reused, and manganese ions and ammonium ions can not be accumulated, so that the vanadium slag calcified roasting clinker can be leached out by manganese extraction residual water in a circulating manner. Mg in manganese extraction residual water 2+ Neutralizing, precipitating and removing magnesium only when the vanadium slag is accumulated to a certain concentration, and circularly leaching the vanadium slag calcification roasting clinker by using water after neutralization. The method for separating and extracting vanadium and manganese from the vanadium precipitation mother liquor has the advantages of greatly reducing the slag amount, generating no wastewater, realizing the high-efficiency recovery of vanadium and manganese, reducing the cost and the like.
The specific implementation mode is as follows:
the following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Unless otherwise indicated, the experimental materials and reagents used herein are all conventional commercial products in the art.
A method for efficiently extracting vanadium and manganese from vanadium precipitation mother liquor obtained by extracting vanadium from vanadium slag through calcification roasting and acid leaching comprises the following steps:
(1) Placing the calcified roasting clinker of the vanadium slag into manganese extraction residual water, adding dilute sulfuric acid to obtain acid leaching liquid containing vanadium, manganese and magnesium, adding ammonium salt into the acid leaching liquid to obtain vanadium precipitation mother liquor, and adjusting the pH value of the vanadium precipitation mother liquor to 2.0-3.0 by using calcium carbonate to obtain vanadium extraction stock liquor;
(2) Extracting vanadate anions containing pentavalent vanadium in vanadium extraction stock solution by using an extraction system consisting of 8-12% of secondary carbon primary amine N1923 and 88-92% of sulfonated kerosene to obtain vanadium extraction residual water;
(3) Adjusting the pH value of vanadium extraction residual water to 4.5-5.0 by using calcium carbonate to obtain manganese extraction stock solution;
(4) Extracting manganese ions in the manganese raw liquor by using an extraction system consisting of 25-35% of P204 in volume fraction and 65-75% of sulfonated kerosene in volume fraction, controlling the pH value in the manganese ion extraction process by using ammonium bicarbonate or ammonium carbonate, controlling the primary extraction pH value of the manganese ions to 4.1-4.5, the secondary extraction pH value to 3.7-4.0, the tertiary extraction pH value to 3.3-3.5 and the quaternary extraction pH value to 2.9-3.0 to obtain manganese extraction residual water, and returning the manganese extraction residual water to the step (1) to be used as a water source of an acid leaching solution of the vanadium slag calcification roasting clinker;
(5) Circulating the processes of the steps (1) to (4) to separate and extract vanadium and manganese in the manganese-extracted residual water until the concentration of magnesium ions in the manganese-extracted residual water in the step (4) reaches 25g/L, and neutralizing and precipitating the magnesium ions in the manganese-extracted residual water by using lime;
(6) And (5) after magnesium ions in the manganese extraction residual water are neutralized and precipitated by lime, the obtained ammonia gas is returned to the step (1) to be used as ammonium salt to realize vanadium precipitation, the manganese extraction residual water after magnesium ions are neutralized is subjected to solid-liquid separation to obtain neutralized water and calcium-magnesium sulfate slag, and the neutralized water is returned to the step (1) to be used as a water source of acid leaching liquid of the vanadium slag calcification roasting clinker.
Example 1
The chemical composition of the vanadium precipitation mother liquor treated in this example is shown in table 1:
TABLE 1 chemical composition of vanadium precipitation mother liquor (g. L) of certain vanadium plant -1 )
A method for recovering vanadium and manganese from vanadium precipitation mother liquor comprises the following steps:
(1) Adjusting the pH value of the vanadium precipitation mother liquor from 1.42 to 2.0-3.0 by using calcium carbonate to prepare vanadium extraction stock solution;
(2) Extracting the vanadate anions containing pentavalent vanadium in vanadium extraction stock solution by using an extraction system consisting of 10% secondary carbon primary amine N1923 and 90% sulfonated kerosene (both in volume concentration), wherein the volume ratio of a water phase to an organic phase is 4, the extraction time is 15 minutes, four-stage countercurrent extraction is carried out, and the vanadium extraction rate reaches 96.8%; the vanadium is reversely extracted from the obtained vanadium-loaded organic phase by adopting an ammonium carbonate aqueous solution, the reverse extraction rate of the vanadium reaches 100 percent, the organic phase is regenerated to realize the reutilization, and the vanadium-rich liquid returns to the procedure of precipitating vanadium from the vanadium slag calcification roasting clinker pickle liquor ammonium salt for precipitating vanadium;
(3) Adjusting the pH value of vanadium extraction residual water to 4.5-5.0 by using calcium carbonate to prepare manganese extraction stock solution;
(4) Extracting manganese ions in the manganese raw solution by four-stage countercurrent extraction of an extraction system consisting of 30 percent of P204 and 70 percent of sulfonated kerosene (both volume concentration), controlling the pH value in the manganese ion extraction process by adopting ammonium bicarbonate or ammonium carbonate, controlling the pH value of the first-stage extraction to be 4.1-4.5, controlling the pH value of the second-stage extraction to be 3.7-4.0, controlling the pH value of the third-stage extraction to be 3.3-3.5 and controlling the pH value of the fourth-stage extraction to be 2.9-3.0; the volume ratio of the water phase to the organic phase is 1, the extraction time is 10 minutes, the extraction rate of manganese reaches 95.8%, the manganese-loaded organic phase is subjected to four-stage countercurrent back extraction by using 1.5mol/L sulfuric acid solution, the volume ratio of the organic phase to the water phase in the back extraction process is 5;
(5) Returning the manganese extraction residual water to dilute sulfuric acid leaching of the vanadium slag calcification roasting clinker, and extracting NH in the manganese extraction residual water 4 + 8.96g/L, this fraction NH 4 + Can be used as NH in the vanadium precipitation process of the ammonium salt in the acid leaching solution of the vanadium slag calcified roasting clinker 4 + The source of (2) is used;
(6) And (4) separating and extracting vanadium and manganese in the vanadium-precipitation mother liquor obtained after vanadium extraction of the acid leaching liquor in the step (5) by adopting the processes of the steps (1) to (5), circulating for 20 times in such a way until the concentration of magnesium ions in manganese extraction residual water reaches 25g/L, neutralizing and precipitating the magnesium ions in the manganese extraction residual water rich in magnesium ions by adopting lime, and returning the neutralized water to dilute acid leaching of the vanadium slag calcification roasting clinker.
The calculation shows that Mn extraction residual water is circularly leached for 20 times and then neutralized, and the average total dry slag amount generated in the whole process is 29.80kg/m 3 Wastewater treatment of 45 km 3 The amount of dry slag generated by the wastewater is 1.34 ten thousand tons, and 45 ten thousand meters of dry slag is treated by the original process (the process of directly neutralizing the vanadium precipitation wastewater by using lime) of a certain vanadium plant 3 The dry slag amount generated by directly neutralizing the waste water lime is 2.5 ten thousand tons, and compared with the original process of a certain vanadium plant, the dry slag amount is reduced by 1.16 ten thousand tons, and the slag amount is reduced by 46.4%. And the recovery rate of vanadium in the vanadium precipitation mother liquor reaches 96%, and the recovery rate of manganese reaches 95%.
According to the method, the vanadium and manganese in the vanadium precipitation mother liquor are efficiently recovered, and the generated slag amount is reduced by 46% compared with the slag amount generated by the existing vanadium precipitation wastewater lime direct neutralization process of enterprises. The technology of the invention treats 1.0m 3 The vanadium precipitation mother liquor will produce about 152.82 yuan. Therefore, the method solves the key problem of comprehensive utilization of vanadium precipitation mother liquor in a vanadium plant, has wide application prospect, and has the advantages that water in the whole process of manganese extraction residual water circulating leaching is always recycled, no wastewater is generated, the slag amount is greatly reduced, the high-efficiency recovery of vanadium and manganese in vanadium precipitation wastewater can be realized, the cost is reduced, and the like.
Example 2
The same as in example 1, except that: the extraction system in the step (2) consists of secondary carbon primary amine N1923 with the volume fraction of 8% and sulfonated kerosene with the volume fraction of 92%, and the volume ratio of the water phase to the organic phase is 5; and (4) the extraction system consists of 25% of P204 in volume fraction and 75% of sulfonated kerosene in volume fraction.
The results obtained were: the extraction rate of vanadium reaches 96.2 percent, and the extraction rate of manganese reaches 95.1 percent.
Mn extraction residual water is circularly leached for 20 times and then neutralized, and the average total dry slag amount generated in the whole process is 29.00kg/m 3 Wastewater treatment of 45 km 3 Waste water producing dryingThe slag amount is 1.305 ten thousand tons, and the slag amount is 45 ten thousand meters compared with the original process (the process of directly neutralizing vanadium precipitation waste water by using lime) of a certain vanadium plant 3 2.5 ten thousand tons of dry slag generated by directly neutralizing the waste water with lime are reduced by 1.195 ten thousand tons, and the slag amount is reduced by 47.8 percent. And the recovery rate of vanadium in the vanadium precipitation mother liquor reaches 95.8 percent, and the recovery rate of manganese reaches 94.6 percent.
Example 3
The same as in example 1, except that: the extraction system in the step (2) consists of secondary carbon primary amine N1923 with the volume fraction of 12% and sulfonated kerosene with the volume fraction of 88%; the extraction system in the step (4) consists of 35% of P204 in volume fraction and 65% of sulfonated kerosene in volume fraction.
The results obtained were: the extraction rate of vanadium reaches 97.5 percent, and the extraction rate of manganese reaches 97.2 percent.
Mn extraction residual water is circularly leached for 20 times and then neutralized, and the average total dry slag amount generated in each full process is 29.50kg/m 3 Wastewater treatment of 45 km 3 The amount of dry slag generated by the wastewater is 1.327 ten thousand tons, and is 45 ten thousand meters after being compared with the original process (the vanadium precipitation wastewater is directly neutralized by lime) of a certain vanadium plant 3 The amount of dry slag generated by directly neutralizing the waste water with lime is reduced by 1.173 ten thousand tons for 2.5 ten thousand tons, and the amount of slag is reduced by 46.92 percent. And the recovery rate of vanadium in the vanadium precipitation mother liquor reaches 96.2 percent, and the recovery rate of manganese reaches 96.8 percent.
The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (7)
1. A method for efficiently extracting vanadium and manganese from vanadium precipitation mother liquor obtained by extracting vanadium from vanadium slag through calcification roasting and acid leaching is characterized by comprising the following steps:
(1) Putting the calcified roasting clinker of the vanadium slag into manganese extraction residual water, adding dilute sulfuric acid to obtain acid leaching solution containing vanadium, manganese and magnesium, adding ammonium salt into the acid leaching solution to obtain vanadium precipitation mother liquor, and adjusting the pH value of the vanadium precipitation mother liquor to 2.0-3.0 by using calcium carbonate to obtain vanadium extraction stock solution;
(2) Extracting vanadate anions containing pentavalent vanadium in vanadium extraction stock solution by using an extraction system consisting of 8-12% of secondary carbon primary amine N1923 and 88-92% of sulfonated kerosene to obtain vanadium extraction residual water;
(3) Adjusting the pH value of vanadium extraction residual water to 4.5-5.0 by using calcium carbonate to obtain manganese extraction stock solution;
(4) Extracting manganese ions in the manganese raw liquor by using an extraction system consisting of 25-35% of P204 in volume fraction and 65-75% of sulfonated kerosene in volume fraction, controlling the pH value in the manganese ion extraction process by using ammonium bicarbonate or ammonium carbonate, controlling the primary extraction pH value of the manganese ions to 4.1-4.5, the secondary extraction pH value to 3.7-4.0, the tertiary extraction pH value to 3.3-3.5 and the quaternary extraction pH value to 2.9-3.0 to obtain manganese extraction residual water, and returning the manganese extraction residual water to the step (1) to be used as a water source of an acid leaching solution of the vanadium slag calcification roasting clinker;
(5) Circulating the processes of the steps (1) to (4) to separate and extract vanadium and manganese in the manganese-extracted residual water until the concentration of magnesium ions in the manganese-extracted residual water in the step (4) reaches 25g/L, and neutralizing and precipitating the magnesium ions in the manganese-extracted residual water by using lime;
(6) And (5) after magnesium ions in the manganese extraction residual water are neutralized and precipitated by lime, the obtained ammonia gas is returned to the step (1) to be used as ammonium salt to realize vanadium precipitation, the manganese extraction residual water after magnesium ions are neutralized is subjected to solid-liquid separation to obtain neutralized water and calcium-magnesium sulfate slag, and the neutralized water is returned to the step (1) to be used as a water source of acid leaching liquid of the vanadium slag calcification roasting clinker.
2. The process of claim 1, wherein the initial concentrations of vanadium, manganese and magnesium in the acid leachate of step (1) are 24 to 26g/L, 6 to 8g/L and 1.2 to 1.4g/L, respectively.
3. The method according to claim 1 or 2, wherein the extraction system in step (2) consists of 10 volume percent of primary secondary carbon amine N1923 and 90 volume percent of sulfonated kerosene.
4. The method according to claim 1 or 2, wherein the extraction in the step (2) is four-stage countercurrent extraction, the volume ratio of the aqueous phase to the organic phase in the extraction system is 4.
5. The method as claimed in claim 1, wherein the vanadium-loaded organic phase obtained in step (2) is subjected to back extraction of vanadium by using an ammonium carbonate aqueous solution, the organic phase is regenerated for recycling, and the vanadium-rich solution is returned to the step (1) of acid leaching solution ammonium salt vanadium precipitation of the calcified roasting clinker of the vanadium slag for vanadium precipitation.
6. The method of claim 1, wherein the extraction system in step (4) is composed of 30% by volume of P204 and 70% by volume of sulfonated kerosene.
7. The method according to claim 1, wherein the volume ratio of the aqueous phase to the organic phase in the extraction system in step (4) is 1.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988224A (en) * | 1974-12-18 | 1976-10-26 | Commissariat A L'energie Atomique | Method of extraction of metallic elements from submarine nodules |
| CN103981364A (en) * | 2014-05-23 | 2014-08-13 | 中广核铀业发展有限公司 | Uranium-vanadium separation method |
| CN104388679A (en) * | 2014-09-30 | 2015-03-04 | 边悟 | Method for extracting vanadium from vanadium-containing raw material |
| CN109097599A (en) * | 2018-09-27 | 2018-12-28 | 中南大学 | A kind of method of synergic solvent extraction separation manganese and calcium, magnesium |
| CN109706316A (en) * | 2019-02-11 | 2019-05-03 | 广东省稀有金属研究所 | A method of recycling valuable metal from deposition vanadium mother liquid |
| CN110016548A (en) * | 2019-05-22 | 2019-07-16 | 攀枝花学院 | The method of vanadium titano-magnetite concentrate roasting extraction vanadium extraction |
| CN113528819A (en) * | 2021-07-12 | 2021-10-22 | 安徽思凯瑞环保科技有限公司 | Method for tungsten-vanadium alkaline extraction and realizing alkali liquor recycling |
| CN114350965A (en) * | 2021-11-30 | 2022-04-15 | 攀钢集团研究院有限公司 | Method for extracting vanadium, manganese and recycling wastewater by using vanadium slag calcified roasting clinker |
-
2022
- 2022-08-30 CN CN202211048581.7A patent/CN115478178A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988224A (en) * | 1974-12-18 | 1976-10-26 | Commissariat A L'energie Atomique | Method of extraction of metallic elements from submarine nodules |
| CN103981364A (en) * | 2014-05-23 | 2014-08-13 | 中广核铀业发展有限公司 | Uranium-vanadium separation method |
| CN104388679A (en) * | 2014-09-30 | 2015-03-04 | 边悟 | Method for extracting vanadium from vanadium-containing raw material |
| CN109097599A (en) * | 2018-09-27 | 2018-12-28 | 中南大学 | A kind of method of synergic solvent extraction separation manganese and calcium, magnesium |
| CN109706316A (en) * | 2019-02-11 | 2019-05-03 | 广东省稀有金属研究所 | A method of recycling valuable metal from deposition vanadium mother liquid |
| CN110016548A (en) * | 2019-05-22 | 2019-07-16 | 攀枝花学院 | The method of vanadium titano-magnetite concentrate roasting extraction vanadium extraction |
| CN113528819A (en) * | 2021-07-12 | 2021-10-22 | 安徽思凯瑞环保科技有限公司 | Method for tungsten-vanadium alkaline extraction and realizing alkali liquor recycling |
| CN114350965A (en) * | 2021-11-30 | 2022-04-15 | 攀钢集团研究院有限公司 | Method for extracting vanadium, manganese and recycling wastewater by using vanadium slag calcified roasting clinker |
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