WO2010057412A1 - Procédé de fabrication d’oxyde de vanadium utilisant une extraction - Google Patents

Procédé de fabrication d’oxyde de vanadium utilisant une extraction Download PDF

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Publication number
WO2010057412A1
WO2010057412A1 PCT/CN2009/074693 CN2009074693W WO2010057412A1 WO 2010057412 A1 WO2010057412 A1 WO 2010057412A1 CN 2009074693 W CN2009074693 W CN 2009074693W WO 2010057412 A1 WO2010057412 A1 WO 2010057412A1
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Prior art keywords
vanadium
extraction
vanadium oxide
production method
water
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PCT/CN2009/074693
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English (en)
Inventor
Yi Peng
Wu BIAN
Jing Wang
Xiaojiang Wang
Ping Pan
Yiping Zhou
Wuhan Liu
Fan Zhang
Daihua Liao
Chaohui Sun
Zongquan Zhou
Mingfu Peng
Ying Wang
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Pangang Group Research Institute Co. Ltd.
Panzhihua Iron & Steel (Group) Corporation
Panzhihua New Steel & Vanadium Co., Ltd.
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Application filed by Pangang Group Research Institute Co. Ltd., Panzhihua Iron & Steel (Group) Corporation, Panzhihua New Steel & Vanadium Co., Ltd. filed Critical Pangang Group Research Institute Co. Ltd.
Priority to NZ587968A priority Critical patent/NZ587968A/xx
Publication of WO2010057412A1 publication Critical patent/WO2010057412A1/fr
Priority to ZA2010/06529A priority patent/ZA201006529B/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present invention relates to production method of vanadium oxide using extraction, and belongs to the technical field of vanadium oxide extraction.
  • Conventional vanadium extraction process using sodium salt comprises: adopting common sodium salts, such as Na2CO3, Na 2 SO 4 , or NaCl, as additives, and roasting the sodium salt with vanadium-containing raw material at high temperature, wherein vanadium in the raw material is oxidized to V 5+ by oxygen in air, and then V 5+ bonds with sodium salt to generate sodium vanadate easily dissolvable in water; leaching the roasted product with water to dissolve sodium vanadate into solution, carrying out solid-liquid separation, removing major impurities such as P, Si and so on from the solution by using CaCl 2 , adding ammonium salts such as (NH 4 ) 2 SO 4 , NH 4 Cl, (NH 4 ) 2 CO 3 , OrNH 4 NO 3 etc.
  • common sodium salts such as Na2CO3, Na 2 SO 4 , or NaCl
  • ammonium salt has to be used in an amount much higher than theoretical amount during vanadium precipitation to give high quality vanadium product, such that wastewater after vanadium precipitation has high concentration of ammonia nitrogen and sodium salt and is most difficult to be treated, e.g., NH 4 + concentration usually is as high as 2,000-8,000 mg/L or even higher, and Na concentration can be above 20g/L. Therefore, wastewater treatment is the most difficult problem to be handled in the vanadium extraction process using sodium salt.
  • One scheme is to remove heavy metals, carry out ammonia removal and sodium removal treatments, and then discharge
  • the ammonia removal technique mainly comprises air stripping method, membrane separation method, magnesium ammonium phosphate precipitation method, chemical oxidation method, zeolite adsorption method, and biological nitrogen removal method
  • the sodium removal method mainly adopts concentration crystallization method.
  • the disadvantages of this scheme comprise that cost of ammonia removal treatment and sodium removal treatment is too high to be accepted by manufacturing plants, new pollution is likely to occur during the treatment, and the recovered sodium salt is sodium sulfate containing many impurities, which will release SO 2 to pollute environment upon roasting and thus is not suitable as roasting additive.
  • the other scheme is to remove heavy metals, carry out ammonia removal and sodium removal treatments, and return condensation water for circulation.
  • the difference from the first scheme is that the water of the first scheme does not circulate, but has to meet national industrial wastewater discharge standard ( ⁇ 15mg/L for ammonia nitrogen wastewater), so it is very difficult to meet the standard, and high cost is required; although the second scheme does not discharge wastewater, a large amount of energy has to be consumed to evaporate wastewater, which also has the disadvantage of high cost, and evaporated gaseous ammonia is usually not recovered.
  • vanadium extraction process using lime or limestone as roasting additive has been studied, which targets at some inherit shortcomings of vanadium extraction process using sodium salt, including (1) strict restriction on CaO content (less than 1.5%) in vanadium slag, because vanadium recovery yield drops 4.7-9% as CaO content in the slag increases 1%; (2) high cost due to large consumption amount of sodium salt and ammonium salt; and (3) environment pollution caused by large amount of sodium salt and ammonium salt in wastewater.
  • the roasted material of vanadium extraction process using calcium salt can be leached with sulfuric aid, or with carbonate or bicarbonate. Germany Patent Application No. 2324737 and British Patent Application No.
  • Tula Vanadium Plant of former Soviet Union constructed the world first (also the only one) vanadium manufacture plant adopting calcifying roasting-sulfuric acid leaching- vanadium hydrolysis precipitation process, which can give V 2 O 5 product with purity of 88-94% (92% on average) and containing main impurities of Mn, Mg, and Ca, and then V 2 O 5 product is smelted into vanadium iron also containing many impurities; therefore the manufacturer is non-competitive on international market, and mainly supplies product to domestic market, that is the main reason that other vanadium plants do not adopt this process.
  • Russian patent application Nos To improve product competivity on market, Russian patent application Nos.
  • 2001127026/02 and 96106854/02 disclosed method for producing high quality vanadium oxide from hydrolysis precipitate containing Mn, Ca, and Mg impurities.
  • the method comprises adopting NaOH to dissolve hydrolysis precipitate, then adding ammonium salt like ammonium sulfate while heating, precipitating ammonium polyvanadate, and calcining to give high quality vanadium oxide with V 2 O 5 content higher than 98%.
  • the method reduces total amount of ammonia-containing wastewater, but still requires wastewater treatment including ammonia removal and sodium removal; therefore the technical and economic difficulties of high cost and difficult ammonia nitrogen wastewater treatment still exist, additionally, vanadium recovery rate is lowered to some extent due to long treatment process and complicated procedures.
  • the object of the present invention is to provide a vanadium oxide production method which can not only obtain high quality vanadium product but also circulate and reuse vanadium extraction wastewater.
  • the vanadium oxide production method in the present invention comprises following steps including: a. mixing vanadium -containing material with additive to give mixed material, wherein the additive is CaO or limestone, and the amount of the additive makes the CaOAV 2 Os weight ratio in the mixed material be 0.5-1.4 : 1; b. roasting the mixed material at 860 ° C-950 ° C in oxidizing atmosphere for 60-240min to give roasted material; c. adding water into the roasted material to give slurry, stirring, and slowly adding sulfuric acid solution to leach the slurry while controlling pH at 2.5-3.5; d.
  • step f removing P, Mn, and Mg impurities in the wastewater generated in step f to make Mn 2+ and Mg 2+ concentrations lower than 5g/L respectively, and P concentration lower than 0.005g/L to give circulation water, and returning the circulation water to step c for preparing slurry and to step d for washing the residue, wherein the solid raw material used in the above steps has total alkali metal amount not more than 0.3wt%, and total amount of Cl and NO 3 not more than 0.1 wt%; and the liquid raw material used in the above steps has total alkali metal amount not more than 0.1 g/L, and total amount of Cl and NO 3 not more than 0.1 g/L.
  • wastewater can be circulated and reused; and in addition, as the inventive method adopts calcifying roasting and sulfuric acid leaching to give vanadium solution substantially free of alkali metal ions, and various raw materials (including supplement water) are substantially free of easily soluble ions of alkali metal, halogen, and nitrate, balance of the easily soluble ions can be maintained during circulation process, wastewater can be circulated and reused after treatment, and thus problems of wastewater treatment of conventional vanadium extraction process using sodium salt are avoided.
  • the vanadium -containing material can be various vanadium-containing raw materials useful for preparing vanadium oxide, such as vanadium slag or other vanadium -containing raw materials (such as vanadium-containing magnetite, and vanadium lead zinc ore, etc.), preferably vanadium slag.
  • the mixed material is pulverized to particle size of 0.1mm or less, to make vanadium be easily oxidized into V to generate vanadate.
  • the oxidizing atmosphere can be pure oxygen, air, or mixture of oxygen and inert gas.
  • the inert gas is preferably nitrogen gas.
  • appropriate roasting temperature and time can be selected within the range in the present invention, for example when the roasting temperature is high (such as 950 " C), the roasting time can be shortened (such as 60min), and when the roasting temperature is low (such as 860 "C), the roasting time can be prolonged (about 240min).
  • the roasted material is cooled and pulverized to 0.18mm or less to facilitate leaching before being prepared into slurry.
  • the slurry is prepared by stirring the roasted material with water 1.5-4 times by weight.
  • the adopted water is the washing water resulted from the residue washing, and if the washing water is insufficient, circulation water is adopted for supplement.
  • the sulfuric acid solution for leaching has concentration of 10-75%, the leaching temperature is between room temperature and 58 ° C, and the leaching time is 30-90min. More preferably, pH of the slurry is regulated to 2.8-3.3 with 32-65wt% sulfuric acid solution.
  • the washing times are preferably 5-7, the amount of water used for each washing is preferably 20-35wt% of the residue on dry basis, to maintain water balance in circulation process.
  • P-removal reagent can be adopted for P-removal treatment, as long as TWP ⁇ 1000 is satisfied.
  • Ca-removal reagent can be adopted for Ca-removal treatment, as long as [Ca 2+ ] ⁇ 0.05g/L is satisfied.
  • the extraction agent may be organic substance being capable of extracting Mn 2 ⁇ Mg 2+ and Fe 3+ at pH of 2-5, and is preferably at least one of bis-(2-ethylhexyl) phosphate, mono-(2-ethylhexyl) 2-ethylhexylphosphonate, and bis-(2,4,4-trimethylpentyl) hypophosphorous acid.
  • the extraction agent may be diluted by any common diluent such as 260# solvent oil or sulfonated kerosene prior to use.
  • the extraction agent is previously saponified by ammonia to convert most exchangeable groups in the extraction agent into NH 4 + while the remaining keeps to be H + .
  • the extraction agent is previously saponified by ammonia such that the raffinate has pH of 2.8-3.8.
  • Alkaline of alkali metals such as sodium hydroxide or potassium hydroxide can not be used for saponification.
  • the organic phase containing Mn ,Mg and Fe can be subjected to reverse extraction using 2-3M sulfuric acid solution to reverse extract the Mn + ,Mg + impurity into the sulfuric acid solution such that the organic phase is regenerated and can be reused.
  • the solution resulted from the reverse extraction can be used for reverse extraction of Mn and can be used for Mn recovery Mn with wastewater neutralization residue after the reverse extraction ability decreases.
  • the wastewater can be treated according to various routine methods to remove P, Mn, and Mg, for example, lime milk is adopted to neutralize wastewater to pH 9-11, the wastewater is filtered to remove main impurities such as Mn, P, and Mg while obtaining wastewater neutralization residue useful as raw material for Mn recovery; or Mn can be individually recovered with other reagents, and then impurities like Mn, P and Mg are removed.
  • the returned circulation water may contain a certain amount OfNH 4+ , if the weight ratio of NHVMn in the P-removed and Ca-removed leachate already satisfies above requirement, extraction is not added, and vanadium precipitation is directly carried out.
  • the present invention has following beneficial effects:
  • the inventive method adopts calcifying roasting and sulfuric acid leaching technique to give vanadium solution substantially free of alkali metal ions, and various raw materials (including supplement water) are substantially free of easily soluble ions of alkali metal, halogen, and nitrate, so that balance of the easily soluble ions can be maintained during circulation, and problems of wastewater treatment of conventional vanadium extraction process using sodium salt are avoided.
  • Extraction is adopted to substitute impurities like Mn, P and Mg with NH 4 + to refine the vanadium-containing solution so as to prepare high quality vanadium oxide product, so that technical problem that conventional calcifying roasting-sulfuric acid leaching process can not produce high quality vanadium product is solved.
  • Weight ratio of NH 3 /Mn is controlled to control the extent of the extraction, when the ratio in the leachate is lower than the value specified in the present invention, extraction is performed to regulate the ratio to the specified value, and then the vanadium precipitation is carried out; when the ratio in the leachate has already reached the specified value in the present invention, extraction is not needed, and vanadium precipitation is directly carried out, and part of NH 4 is discharged along with ammonium polyvanadate precipitate, so that NH 4 concentration in the system will not continuously increase to enable circulation and reuse.
  • the circulation water containing sulfate salt such as (NH 4 ) 2 SO 4 is adopted for leaching; within the leaching condition range in the present invention, NH 4 + will not cause adverse influence, and SO 4 " is beneficial for increasing leaching rate of calcified roasted material, so that water circulation and reuse can be finally realized. 5.
  • the inventive method can greatly increase total recovery rate (up to 82-85%) of vanadium oxide from vanadium slag, while the recovery rate of the conventional vanadium extraction process using sodium salt is about 80%; therefore the inventive method has increased the recovery rate by 2-5% on average compared with conventional vanadium extraction process using sodium salt, and the obtained vanadium product has good quality, and meets Chinese National Standard No. GB3283-87.
  • the inexpensive lime material is adopted to replace expensive sodium carbonate, the consumption amount of sulfuric acid is similar to that in the vanadium extraction process using sodium salt, and consumption and cost of other auxiliary materials are low; therefore, consumption and cost of various auxiliary and raw materials are significantly decreased.
  • Fig. 1 shows flow chart of one preferred embodiment of the method in the present invention.
  • the mixed material is calcified and roasted (equivalent to step b);
  • Sulfuric acid solution is adopted to leach the roasted material at constant pH (equivalent to step c);
  • the leachate is subjected to extraction (equivalent to step e);
  • Vanadium precipitation is performed, and ammonium polyvanadate obtained from vanadium precipitation is calcined or reduced to give high quality vanadium oxide (equivalent to step f);
  • the wastewater obtained from vanadium precipitation is added with lime milk for neutralization, the obtained circulation water is returned to prepare slurry or wash residue, and
  • Mn is recovered from the neutralization residue (equivalent to step g).
  • Example 1 Roasted material prepared according to step (1) is adopted, 51 cycles of wastewater circulation test are carried out according to the inventive method, and each cycle includes steps (2)-(6).
  • Common vanadium slag with composition shown in Table 1 is ground to less than 0.098mm, 28kg of ground vanadium slag powder is mixed with 1.96kg of lime (ground to below 0.1mm) containing CaO>98%, and then the mixture is roasted at 860 ° C in air for 240min, cooled, and ground to less than 0.18mm.
  • 2,000ml of water resulted from residue washing of last cycle (clear water is used for the first cycle) is added to 50Og of the ground roasted material to prepare slurry, 10-32wt% sulfuric acid solution is slowly added continuously while stirring, pH is controlled at 2.8-3.3 during leaching process while the slurry temperature is held at a temperature between room temperature and 58 ° C, the reaction is carried out for 60min.
  • the resultant is filtered to give leachate, the residue is washed with circulation water (clear water is used for the first cycle) for 6-7 times, water used for each time is 120ml, the washing water is combined for preparing slurry for leaching of next cycle, and the residue is dried and weighed to determine TV (total vanadium) content and calculate vanadium leaching rate.
  • the leachate is subjected to P-removal treatment and Ca-removal treatment to make P satisfy TV/P ⁇ IOOO and [Ca + ] ⁇ 0.05g/L, and then extraction is carried out.
  • Extraction 10-20volume% kerosene solution of P204 is saponified by ammonia.
  • the saponified organic phase is mixed with leachate to perform one-stage extraction at room temperature for 5min under stirring.
  • the mixture is kept standing for the phase separation, and the organic substances remained in the aqueous phase are removed
  • the weight ratio of NH 3 /Mn in the aqueous phase solution is controlled to be 0.6-50 : 1 by controlling saponification ratio and the extraction phase ratio .
  • P204 represents bis-(2-ethylhexyl) phosphate.
  • a small amount of sulfuric acid is used to regulate pH of the oil-removed aqueous phase to 1.5-2.5, then the resultant is heated to above 90 ° C, held for 60-120min, and filtered, the precipitate is washed with tap water containing [Na+K] ⁇ 0. lg/L for 3 times and water used for each time is 30ml, and the washing wastewater is combined with supernatant of vanadium precipitation to give wastewater of vanadium precipitation.
  • Ammonium polyvanadate precipitate is dried, calcined and melted at 500 ° C-800 ° C to give V 2 O 5 , and the composition of the obtained V 2 O 5 is analyzed.
  • Lime milk with low water content is prepared, added into the wastewater of vanadium precipitation to regulate pH of the solution to 9.0-10.0, and filtered.
  • the filtrate is regulated to pH of 5-7 with diluted sulfuric acid to give circulation water as residue washing water for leaching in the next cycle.
  • the neutralization residue obtained from the filtration is used as raw material for Mn recovery.
  • the organic phase containing cation such as Mn 2+ (carried organic phase) is reused after being reverse extracted by 2.5M sulfuric acid solution. After 10 cycles, the organic phase is reverse extracted by 6N hydrochloric acid besides the 2.5M sulfuric acid solution, and washed by dilute sulfuric acid to remove the Cl " , and then the extraction agent returns to the system. The solution resulted from the hydrochloric acid reverse extraction and the solution resulted from the sulfuric acid solution reverse extraction are separately treated. When Mn in the reverse-extraction solution accumulates to an extent, the reverse-extraction solution reacts with wastewater neutralization residue to recover Mn.
  • steps (2)-(6) are repeated, 50Og of roasted material is used for each cycle, liquid solid ratio for each cycle is 4:1, vanadium precipitation is not carried out after leaching in the first cycle, the leachate is used for slurry preparation of the second cycle to increase vanadium concentration of the leachate; then during leaching in each of the rest cycles, residue washing water of last cycle is used in step (2), and the insufficient part is supplemented by circulation water; circulation water is used for washing the residue, and the insufficient part is supplemented by clear water. 51 cycles are carried out, and no wastewater containing ammonia nitrogen is discharged from the system.
  • the maximum value, the minimum value, and the average value of the recovery rate of the rest cycles are shown in Table 2; the maximum value, the minimum value, and the average value of the chemical compositions of the V 2 O 5 product of the rest cycles are shown in Table 3, and the Table 3 also shows compositions of the metallurgical No. 98 and No. 99 of Chinese National Standard No. GB3283-87; and the maximum value, the minimum value, and the average value of the composition of the circulation water after circulation treatment for the rest cycles are shown in Table 4.
  • the procedure of raw material pretreatment includes pulverization of bulk coarse vanadium slag, grinding, and iron removal, and a small amount of vanadium is lost in this process.
  • the table 3 shows that the vanadium product obtained by the process has good product quality, and meets Chinese National Standard No. GB3283-87.
  • Example 2 Roasted material prepared according to step (1) is adopted, 51 cycles of wastewater circulation test are carried out according to the inventive method, and each cycle includes steps (2)-(6).
  • the vanadium slag shown in Table 5 is ground to less than 0.098mm.
  • the resultant is filtered to give leachate, the residue is washed with circulation water (clear water is used for the first cycle) for 6 times, water used for each time is 120ml, the washing water is combined for preparing slurry for leaching of next cycle, and the residue is dried and weighed to determine TV (total vanadium) content and calculate vanadium leaching rate.
  • the leachate is subjected to P-removal treatment and Ca-removal treatment to make P satisfy TV/P ⁇ IOOO and [Ca + ] ⁇ 0.05g/L, and then extraction is carried out.
  • 10-30volume% kerosene solution of P507 is saponified by ammonia.
  • the saponified organic phase is mixed with leachate to perform one-stage extraction at room temperature for 5min under stirring.
  • the mixture is kept standing for the phase separation, and the organic substances remained in the aqueous phase are removed
  • the weight ratio of NH 3 /Mn in the aqueous phase solution is controlled to be 10-200 : 1 by controlling saponification ratio and the extraction phase ratio.
  • P507 represents mono-(2-ethylhexyl) 2-ethylhexylphosphonate. (4) Vanadium precipitation and V 2 O 5 production by calcination
  • a small amount of sulfuric acid is used to regulate pH of the aqueous phase solution to 1.5-2.5, then the resultant is heated to above 90 ° C, held for 60-120min, and filtered, the precipitate is washed with tap water containing [Na+K] ⁇ 0.1g/L for 3 times and water used for each time is 30ml, and the washing wastewater is combined with supernatant of vanadium precipitation to give wastewater of vanadium precipitation.
  • Ammonium polyvanadate precipitate is dried, calcined and melted at 500 ° C-800 ° C to give V 2 O 5 , and the composition of the obtained V 2 O 5 is analyzed. (5) Wastewater treatment
  • Lime milk with low water content is prepared, added into the wastewater of vanadium precipitation to regulate pH of the solution to 9.5-10.00, and filtered.
  • the filtrate is regulated to pH of 5-7 with diluted sulfuric acid to give circulation water as residue washing water for leaching in the next cycle.
  • the neutralization residue obtained from the filtration is used as raw material for Mn recovery. (6) Regeneration of the organic phase
  • the organic phase containing cation such as Mn 2+ is reused after being reverse extracted by 2.5M sulfuric acid solution. After 10 cycles, the organic phase is reverse extracted by 6N hydrochloric acid besides the 2.5M sulfuric acid solution, and washed by dilute sulfuric acid to remove the Cl " , and then the extraction agent returns to the system.
  • the solution resulted from the hydrochloric acid reverse extraction and the solution resulted from the sulfuric acid solution reverse extraction are separately treated.
  • Mn in the reverse-extraction solution accumulates to an extent, the reverse-extraction solution reacts with wastewater neutralization residue to recover Mn.
  • steps (2)-(6) are repeated, 50Og of roasted material is used for each cycle, liquid solid ratio for each cycle is 2.5:1, vanadium precipitation is not carried out after leaching in the first cycle, the leachate is used for slurry preparation of the second cycle to increase vanadium concentration of the leachate; then during leaching in each of the rest cycles, residue washing water of last cycle is used in step (2), and the insufficient part is supplemented by circulation water; circulation water is used for washing the residue, and the insufficient part is supplemented by clear water. 51 cycles are carried out, and no wastewater containing ammonia nitrogen is discharged from the system.
  • the table 7 shows that the vanadium product obtained by the process has good product quality, and meets Chinese National Standard No. GB3283-87.
  • roasted material prepared according to step (1) is adopted, 100 cycles of wastewater circulation test are carried out according to the inventive method, and each cycle includes steps (2)-(6).
  • Preparation of roasted material 110kg of vanadium slag with composition shown in Table 9 is ground to less than 0.098mm, the ground vanadium slag powder is mixed with 7.7kg of lime (ground to below 0.1mm) containing 98% CaO, and then the mixture is roasted at 920 ° C in air for 150min, cooled, and ground to less than 0.18mm.
  • 2,000ml of water resulted from residue washing of last cycle (clear water is used for the first cycle) is added to 1,00Og of ground roasted material to prepare slurry, 50-75wt% sulfuric acid solution is slowly added continuously while stirring, pH is controlled at 2.8-3.3 during leaching process while the slurry temperature is held at a temperature between room temperature and 58 ° C, the reaction is carried out for 60min.
  • the resultant is filtered to give leachate, the residue is washed with circulation water (clear water is used for the first cycle) for 5-6 times, water used for each time is 250ml, the washing water is combined for preparing slurry for leaching of next cycle, and the residue is dried and weighed to determine TV (total vanadium) content and calculate vanadium leaching rate.
  • the leachate is subjected to P-removal treatment and Ca-removal treatment to make P satisfy TV/P ⁇ IOOO and [Ca + ] ⁇ 0.05g/L, and then extraction is carried out.
  • Cyanex represents bis-(2,4,4-trimethylpentyl) hypophosphorous acid.
  • a small amount of sulfuric acid is used to regulate pH of the aqueous phase solution to 1.5-2.5, then the resultant is heated to above 90 ° C, held for 60-120min, and filtered, the precipitate is washed with tap water containing [Na+K] ⁇ 0.1g/L for 3 times and water used for each time is 30ml, and the washing wastewater is combined with supernatant of vanadium precipitation to give wastewater of vanadium precipitation.
  • Ammonium polyvanadate precipitate is dried, calcined and melted at 500 ° C-800 ° C to give V2O5, and the composition of the obtained V2O5 is analyzed.
  • Lime milk with low water content is prepared, added into the wastewater of vanadium precipitation to regulate pH of the solution to 9.5-11, and filtered.
  • the filtrate is regulated to pH of 5-7 with diluted sulfuric acid to give circulation water as residue washing water for leaching in the next cycle.
  • the neutralization residue obtained from the filtration is used as raw material for Mn recovery.
  • the organic phase containing cation such as Mn 2+ is reused after being reverse extracted by 2.5M sulfuric acid solution. After 10 cycles, the organic phase is reverse extracted by 6N hydrochloric acid besides the 2.5M sulfuric acid solution, and washed by dilute sulfuric acid to remove the Cl " , and then the extraction agent returns to the system.
  • the solution resulted from the hydrochloric acid reverse extraction and the solution resulted from the sulfuric acid solution reverse extraction are separately treated.
  • Mn in the reverse-extraction solution accumulates to an extent, the reverse-extraction solution reacts with wastewater neutralization residue to recover Mn.
  • steps (2)-(6) are repeated, lOOOg of roasted material is used for each cycle, liquid solid ratio for each cycle is 2:1, vanadium precipitation is not carried out after leaching in the first cycle, the leachate is used for slurry preparation of the second cycle to increase vanadium concentration of the leachate; then during leaching in each of the rest cycles, residue washing water of last cycle is used in step (2), and the insufficient part is supplemented by circulation water; circulation water is used for washing the residue, and the insufficient part is supplemented by clear water. 51 cycles are carried out, and no wastewater containing ammonia nitrogen is discharged from the system.
  • the table 11 shows that the vanadium product obtained by the process has good product quality, and meets Chinese National Standard No. GB3283-87.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

La présente invention concerne un procédé de fabrication d’oxyde de vanadium qui utilise une extraction, et qui appartient au domaine technique de l’extraction d’oxyde de vanadium. Le problème technique à résoudre dans le cadre de la présente invention est de proposer un procédé propre de fabrication d’oxyde de vanadium qui permet non seulement d’obtenir un produit vanadium de grande qualité, mais également de mettre en circulation et de réutiliser l’eau usée de l’extraction du vanadium. Le procédé selon l’invention comprend la préparation d’une matière première à griller, un grillage calcifiant, une lixiviation, une séparation solide-liquide, une extraction, une précipitation de vanadium, et une élimination d’ammoniac par calcination ou réduction pour préparer de l’oxyde de vanadium. Selon l’invention, l’eau usée de l’extraction du vanadium est remise en circulation dans le système et réutilisée après un traitement de neutralisation avec du lait de chaux, et aucun déchargement d’eau usée n’est réalisé. L’invention améliore le taux de récupération du vanadium et le rend supérieur à celui des procédés disponibles, et réduit également les coûts de fabrication. En l’associant à d’autres techniques, le procédé permet également de transformer les déchets résultants de l’extraction en ressources secondaires pouvant être réutilisées, afin de réaliser une fabrication propre.
PCT/CN2009/074693 2008-11-18 2009-10-29 Procédé de fabrication d’oxyde de vanadium utilisant une extraction WO2010057412A1 (fr)

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NZ587968A NZ587968A (en) 2008-11-18 2009-10-29 A production method of vanadium oxide using extraction
ZA2010/06529A ZA201006529B (en) 2008-11-18 2010-09-13 A production method of vanadium oxide using extraction

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CN2008103056037A CN101412540B (zh) 2008-11-18 2008-11-18 一种利用萃取技术生产氧化钒的方法
CN200810305603.7 2008-11-18

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Cited By (5)

* Cited by examiner, † Cited by third party
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WO2015161660A1 (fr) * 2014-04-21 2015-10-29 中国科学院过程工程研究所 Procédé de préparation de pentoxyde de vanadium à faible teneur en silicium à partir d'une solution contenant du vanadium, du chrome et du silicium
WO2019127305A1 (fr) * 2017-12-29 2019-07-04 焱鑫环保科技有限公司 Procédé de traitement destiné à produire un produit de sulfite de sodium par absorption de gaz de combustion so2 et par purification par élimination de l'arsenic à l'aide d'une solution de lixiviation de résidu industriel alcalin contenant de l'arsenic
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US10844458B2 (en) * 2015-07-15 2020-11-24 National University Corporation Gunma University Vanadium recovery method, method for producing electrolytic solution for redox flow batteries, vanadium recovery device, and device for producing electrolytic solution for redox flow batteries
WO2019127305A1 (fr) * 2017-12-29 2019-07-04 焱鑫环保科技有限公司 Procédé de traitement destiné à produire un produit de sulfite de sodium par absorption de gaz de combustion so2 et par purification par élimination de l'arsenic à l'aide d'une solution de lixiviation de résidu industriel alcalin contenant de l'arsenic
CN115247234A (zh) * 2020-10-17 2022-10-28 刘辉 一种钒渣直接硫酸氧化酸解制备偏钒酸铵的方法
CN114620859A (zh) * 2022-02-25 2022-06-14 中南大学 一种皂化p507废水中溶解态p507的去除方法
CN114620859B (zh) * 2022-02-25 2023-10-27 中南大学 一种皂化p507废水中溶解态p507的去除方法

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