CN111218571B - Method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime - Google Patents

Method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime Download PDF

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CN111218571B
CN111218571B CN202010031921.XA CN202010031921A CN111218571B CN 111218571 B CN111218571 B CN 111218571B CN 202010031921 A CN202010031921 A CN 202010031921A CN 111218571 B CN111218571 B CN 111218571B
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vanadium
roasting
vanadium slag
phosphorus
desiliconizing
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CN111218571A (en
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蒋霖
伍珍秀
李明
付自碧
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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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
    • C22B34/20—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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting 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
    • 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
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • 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

The invention belongs to the technical field of vanadium chemical metallurgy, and particularly relates to a method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime. The invention aims to solve the technical problem of providing a vanadium slag soda lime roasting pre-desiliconization phosphorus method which is short in process flow and capable of effectively removing impurities. The method comprises the following steps: a. mixing vanadium slag, alkali and a calcium-containing compound, and performing ball milling to obtain a raw material; b. roasting the raw materials to obtain clinker; c. and (5) soaking the crushed clinker in water, and filtering to obtain qualified vanadium liquid. The method of the invention omits the solution impurity removal process in the vanadium slag sodium salt extraction process, shortens the process flow and reduces the loss of vanadium.

Description

Method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime
Technical Field
The invention belongs to the technical field of vanadium chemical metallurgy, and particularly relates to a method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime.
Background
Vanadium is a rare metal, is widely applied to industries such as steel, aerospace, petrochemical industry and the like, and is an indispensable important strategic resource for developing modern industry, modern national defense and modern scientific technology. Vanadium slag, stone coal and vanadium-containing solid waste are main raw materials for extracting vanadium in the vanadium chemical industry of China, and the vanadium slag vanadium extraction occupies a leading position. The vanadium extraction process from the vanadium slag comprises sodium roasting, calcification roasting, pressurized acid leaching, a sub-molten salt method and the like, wherein the sodium roasting is a process which is developed earlier and is mainly used for producing vanadium pentoxide at present.
Enterprises which produce iron and vanadium products by taking vanadium titano-magnetite as a raw material adopt the traditional vanadium slag sodium salt roasting process to extract vanadium from vanadium slag, such as Pan steel and bearing steel in China, south Africa Hai Weird, New Zealand steel companies and the like. The basic principle of sodium roasting is Na2CO3As an additive, converting low-valence vanadium into water-soluble pentavalent vanadium sodium salt by high-temperature sodium salt roasting (750-850 ℃), leaching with water to obtain vanadium-containing leachate, removing impurities from the leachate to obtain qualified solution, adding ammonium salt to obtain ammonium polyvanadate precipitate, and reducing and roasting to obtain an oxide product of vanadium. The impurities in the alkaline leachate are mainly removed from impurities such as silicon, phosphorus and the like in the solution, the commonly adopted impurity removing agents comprise calcium salt, aluminum salt, magnesium salt and the like, impurity removing residues are difficult to filter and containThe subsequent treatment is needed when the amount of vanadium is large.
The vanadium extraction of the vanadium slag is carried out for pre-desiliconizing phosphorus, which mainly refers to desiliconization, and the subsequent vanadium precipitation process is not influenced because the phosphorus content is lower sometimes. Patent document CN 108130425 a discloses a method for vanadium slag pretreatment desilication and medium circulation, which comprises mixing coarse vanadium-breaking slag with calcium-containing material and alkaline medium, performing wet ball milling, and separating vanadium slag from iron particles after ball milling; carrying out flotation desilication treatment on the vanadium slag slurry after iron separation to obtain desilicated slurry; naturally settling the desiliconized slurry, separating to obtain an alkaline medium and refined vanadium slag, and returning the alkaline medium to the first step.
Disclosure of Invention
The invention aims to solve the technical problem of providing a vanadium slag soda lime roasting pre-desiliconization phosphorus method which is short in process flow and capable of effectively removing impurities.
The invention solves the technical problems by adopting the technical scheme that a method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime is provided. The method comprises the following steps:
a. mixing vanadium slag, alkali and a calcium-containing compound, and performing ball milling to obtain a raw material;
b. roasting the raw materials to obtain clinker;
c. and (5) soaking the crushed clinker in water, and filtering to obtain qualified vanadium liquid.
In the method for pre-desiliconizing and dephosphorizing vanadium slag by soda lime roasting, in the step a, the vanadium slag, alkali and a calciferous substance are mixed according to the mass ratio of 100: 20-30: 1-5.
Further, in the step a, the alkali is NaOH or Na2CO3Or NaHCO3At least one of (1). Preferably, the base is Na2CO3。
Further, in step a, the calcareous compound is CaO or CaCO3Or Ca (OH)2At least one of (1).
Preferably, the calcareous compound is CaCO3。
Further, in the step a, the ball milling is dry ball milling.
In the method for pre-desiliconizing and dephosphorizing vanadium slag by soda lime roasting, in the step b, the roasting temperature is 800-1200 ℃; the roasting time is 60-180 min.
Further, in the step b, a muffle furnace is adopted for roasting, and an oxidizing atmosphere is introduced into the muffle furnace during roasting.
Further, the oxidizing atmosphere is air or oxygen.
In the method for pre-desiliconizing and dephosphorizing vanadium slag by soda lime roasting, in the step c, the liquid-solid ratio of water leaching is 2-4 mL:1 g.
Further, in the step c, the water immersion temperature is 30-90 ℃; the water immersion time is 10-60 min.
The vanadium slag comprises the following components in percentage by mass: v3% -12%, Cr 0.3% -5%, SiO210％～20％、CaO 1％～3％、MgO 1％～5％、MnO 5％～10％、Fe 28％～38％、P 0.01％～1％、S 0.01％～0.5％。
The invention has the beneficial effects that:
the method of the invention comprises the steps of roasting the raw material consisting of vanadium slag, alkali and lime at high temperature to convert vanadium into sodium vanadate which is easy to dissolve in water, respectively converting silicon and phosphorus into calcium silicate and calcium phosphate which are insoluble in water, and directly obtaining qualified vanadium liquid with lower impurity content by water immersion. Compared with the existing vanadium slag sodium salt extraction process, the solution impurity removal process in the vanadium slag sodium salt extraction process is omitted, the process flow is shortened, and the cost is reduced. The method of the invention simultaneously realizes impurity removal in the leaching process, directly obtains the leaching slag and saves the subsequent treatment of the impurity-removed slag. Compared with the conventional roasting-impurity removal process, the vanadium loss can be reduced by 2-3%.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
Specifically, the invention provides a method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime. The method comprises the following steps:
a. mixing vanadium slag, alkali and a calcium-containing compound according to a mass ratio of 100: 20-30: 1-5, and performing ball milling to obtain a raw material;
b. placing the raw material in a muffle furnace, roasting for 60-180 min at 800-1200 ℃, and introducing air or oxygen into the muffle furnace during roasting to obtain clinker;
c. and crushing the clinker, soaking in 1g of water according to the liquid-solid ratio of 2-4 mL, and filtering to obtain qualified vanadium liquid.
The invention carries out high-temperature roasting on the raw material consisting of vanadium slag, alkali and lime to ensure that vanadium generates sodium vanadate which is easy to dissolve in water, impurities of silicon and phosphorus respectively generate calcium silicate and calcium phosphate which are insoluble in water and are remained in leached slag, and then qualified vanadium liquid with lower impurity content is obtained by water leaching, thus omitting the solution impurity removal process in the vanadium slag sodium salt vanadium extraction process.
In step a, ball milling is carried out by adopting a dry method in order to improve the mixing degree of the raw materials and play a role of mechanical activation. According to the method, vanadium slag, alkali and a calcium-containing compound are creatively controlled to be 100: 20-30: 1-5 in a mass ratio, so that the vanadium is generated into sodium vanadate to facilitate subsequent water leaching, and the silicon and the phosphorus are respectively formed into calcium silicate and calcium phosphate to be left in leaching slag.
In the step b, in order to ensure the vanadium yield and avoid sintering, the roasting temperature is controlled to be 800-1200 ℃.
In the step c, the clinker is crushed and then immersed in water according to the liquid-solid ratio of 2-4 mL:1g so as to control the concentration of vanadium in the qualified vanadium liquid to be 15-30 g/L and facilitate subsequent vanadium precipitation.
For the conventional roasting-impurity removal working procedure, the leaching rate of the obtained vanadium is about 95 percent, the impurity removal yield is about 95 percent, and the total yield of the vanadium is about 90.25 percent; in the invention, although the leaching rate of vanadium is reduced to about 93 percent, the impurity removal process is omitted, and the total yield of vanadium is improved.
The present invention will be further illustrated by the following specific examples.
The main components of the vanadium slag adopted in the following comparative examples and examples are as follows (%):
Figure BDA0002364623580000031
comparative example
100g of vanadium slag fine powder is added with Na2CO320g, and mixing and grinding to obtain raw materials; then placing the mixture in a muffle furnace for roasting at 800 ℃ for 180min to obtain clinker; crushing the clinker, and then soaking the crushed clinker in water, wherein the solid-to-solid ratio of the soaking solution is 2:1(mL/g), the leaching temperature is 60 ℃, and the leaching time is 30min, so as to obtain a vanadium leaching solution. The V content in the tailings is 0.83 percent, and c (P) and c (Si) in the vanadium leaching solution are 0.018g/L and 0.672g/L respectively. And removing impurities from the vanadium leaching solution to obtain qualified vanadium solution, wherein c (P) is 0.013g/L, c (Si) is 0.102g/L, and the vanadium yield is 89.35% from the vanadium slag to the qualified vanadium solution.
Example 1
100g of vanadium slag fine powder is added with Na2CO3 20g、CaCO31g, mixing and grinding to obtain raw materials; then placing the mixture in a muffle furnace for roasting at 800 ℃ for 180min to obtain clinker; crushing the clinker, then soaking the crushed clinker in water, wherein the solid-to-solid ratio of the soaking solution is 2:1(mL/g), the leaching temperature is 60 ℃, the leaching time is 30min, and filtering to obtain qualified vanadium solution. The V content in the tailings is 0.92 percent, and the qualified vanadium liquid c (P)<0.01g/L, and c (Si) 0.103 g/L. The vanadium yield from the vanadium slag to the qualified vanadium liquid is 92.17%.
Example 2
200g of vanadium slag fine powder is added with Na2CO3 50g、CaCO36g, mixing and grinding to obtain raw materials; then placing the mixture in a muffle furnace for roasting, wherein the sintering temperature is 1000 ℃, and the sintering time is 120min, so as to obtain clinker; crushing the clinker, then soaking the crushed clinker in water, wherein the solid-to-solid ratio of the soaking solution is 3:1(mL/g), the leaching temperature is 90 ℃, the leaching time is 10min, and filtering to obtain qualified vanadium solution. The V content in the tailings is 0.95 percent, and the qualified vanadium liquid c (P)<0.01g/L, and c (si) 0.125 g/L. The vanadium yield from the vanadium slag to the qualified vanadium liquid is 91.85 percent.
Example 3
500g of vanadium slag fine powder is added with Na2CO3 150g、CaCO325g, and mixing and grinding to obtain raw materials; then is arranged at the rearRoasting in a muffle furnace at the sintering temperature of 1200 ℃ for 60min to obtain clinker; crushing the clinker, then soaking the crushed clinker in water, wherein the solid-to-solid ratio of the soaking solution is 4:1(mL/g), the leaching temperature is 30 ℃, the leaching time is 60min, and filtering to obtain qualified vanadium solution. The V content in the tailings is 0.96 percent, and the qualified vanadium liquid c (P)<0.01g/L, and c (si) 0.118 g/L. The vanadium yield from the vanadium slag to the qualified vanadium liquid is 91.23%.

Claims (6)

1. The method for pre-desiliconizing and dephosphorizing vanadium slag by soda lime roasting is characterized by comprising the following steps of: the method comprises the following steps:
a. mixing vanadium slag, alkali and a calcium-containing compound, and performing ball milling to obtain a raw material; the alkali is NaOH and Na2CO3Or NaHCO3At least one of; the calcium-containing substance is CaO and CaCO3Or Ca (OH)2At least one of; mixing the vanadium slag, the alkali and the calcium-containing compound according to a mass ratio of 100: 20-30: 1-5; the vanadium slag comprises the following components in percentage by mass: v3% -12%, Cr 0.3% -5%, SiO2 10%～20%、CaO 1%～3%、MgO 1%～5%、MnO 5%～10%、Fe 28%～38%、P 0.01%～1%、S 0.01%～0.5%；
b. Roasting the raw materials to obtain clinker; the roasting temperature is 800-1200 ℃; roasting for 60-180 min; a muffle furnace is adopted for roasting, and an oxidizing atmosphere is introduced into the muffle furnace during roasting;
c. and (5) soaking the crushed clinker in water, and filtering to obtain qualified vanadium liquid.
2. The method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime as claimed in claim 1, is characterized in that: in step a, the alkali is Na2CO3。
3. The vanadium slag soda lime roasting method for pre-desiliconizing phosphorus according to claim 1 or 2, characterized in that: in step a, the calcareous compound is CaCO3。
4. The method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime as claimed in claim 1, is characterized in that: in the step a, the ball milling is dry ball milling.
5. The method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime as claimed in claim 1, is characterized in that: in the step c, the liquid-solid ratio of the water immersion is 2-4 mL:1 g.
6. The method for pre-desiliconizing phosphorus by roasting vanadium slag soda lime as claimed in claim 1, is characterized in that: in the step c, the water immersion temperature is 30-90 ℃; the water immersion time is 10-60 min.
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Citations (4)

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CN102154559A (en) * 2011-04-12 2011-08-17 郴州市金龙铁合金有限公司 Process for extracting vanadium from vanadium slag containing phosphorus at low temperature
CN104152672A (en) * 2014-07-31 2014-11-19 攀钢集团攀枝花钢铁研究院有限公司 Sodium salt roasting method of vanadium and phosphorus-containing material
CN104357652A (en) * 2014-11-20 2015-02-18 重庆大学 Method for directly extracting vanadium from high-calcium vanadium slag by roasting-alkali leaching
CN107164643A (en) * 2017-05-22 2017-09-15 重庆大学 A kind of method of vanadium-bearing slag of high calcium and high phosphor dephosphorization vanadium extraction

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JP4768116B2 (en) * 2000-12-15 2011-09-07 千代田化工建設株式会社 Method for producing high purity vanadium compound from carbonaceous residue containing vanadium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102154559A (en) * 2011-04-12 2011-08-17 郴州市金龙铁合金有限公司 Process for extracting vanadium from vanadium slag containing phosphorus at low temperature
CN104152672A (en) * 2014-07-31 2014-11-19 攀钢集团攀枝花钢铁研究院有限公司 Sodium salt roasting method of vanadium and phosphorus-containing material
CN104357652A (en) * 2014-11-20 2015-02-18 重庆大学 Method for directly extracting vanadium from high-calcium vanadium slag by roasting-alkali leaching
CN107164643A (en) * 2017-05-22 2017-09-15 重庆大学 A kind of method of vanadium-bearing slag of high calcium and high phosphor dephosphorization vanadium extraction

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