CN103540745A - Method for preparing high-purity vanadium from heteropolyacid impurity in amine extraction mode - Google Patents
Method for preparing high-purity vanadium from heteropolyacid impurity in amine extraction mode Download PDFInfo
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Abstract
The invention relates to a method for preparing high-purity vanadium from heteropolyacid impurities in an amine extraction mode. Generally an ordinary vanadium solution is doped with impurities such as chromium, silicon, phosphorus, tungsten, molybdenum and arsenic, if acid is added into the solution, heteropolyacids such as phosphorus tungsten, phosphorus vanadium tungsten, silicon tungsten, phosphorus molybdenum tungsten, silicon molybdenum tungsten, molybdenum vanadium arsenic and tungsten arsenic can be formed, the impurities in the solution are removed by carrying out compounding synergic extraction on the heteropolyacids in the ordinary vanadium solution by using amines and a synergist so as to obtain a purified vanadium-containing raffinate, subsequently the vanadium-containing raffinate is evaporated and concentrated to be the concentration that each liter of the solution contains 40g vanadium, ammonium salt is further added into the concentrated liquid to obtain ammonium metavanadate solid, vanadium pentoxide with the purity greater than 99.9% is obtained through washing in pure water, drying and calcining in an oxygen atmosphere, the organic phase after the heteropolyacid is extracted is subjected to reverse extraction by using an alkali solution so as to form a heteropolyacid water phase, and the organic phase is recycled and circulated. The method has low requirement on equipment, and is simple to operate, key extraction agents are good in thermal stability and not sensitive in acid and alkali, and a recycling and circulating method is simple and easy to be industrialized.
Description
Technical field
The invention belongs to hydrometallurgy and metallurgical material preparation field, be specifically related to a kind of method that amine extracted heteropolyacid impurity is prepared high purity vanadium.
Background technology
Vanadium and rare earth, titanium etc. are listed in country-level strategic reserves resource, and purposes is very extensive, is called as " industrial monosodium glutamate ".Vanadium resource price is oscillated in quotations by the impact of steel market in recent years; relevant enterprise producer suffers untold misery; in order to walk out from this economic crisis, numerous producers turn to high-end product market by sight one after another, intend by improving the value-added content of product competitive power of winning the market.Common 98.5% Vanadium Pentoxide in FLAKES market value is at 7-8 ten thousand/ton at present, and 99.5% high purity vanadic anhydride price is more than 160,000/ton, and the Vanadium Pentoxide in FLAKES price that spectroscopically pure and content are 99.9% is 500 yuan/25g left and right.But because the processing requirement of spectroscopically pure Vanadium Pentoxide in FLAKES is high, the domestic manufacturer production that there is no; The basic dependence on import of high purity vanadium.The continuous expansion of vanadium cell, vananum and the vanadium catalyst market requirement, the requirement that further improves high purity vanadium, has brought opportunity to the development of high purity vanadium/spectroscopically pure Vanadium Pentoxide in FLAKES.
At present high purity vanadium is generally to buy from the market 98.5% common vanadium product, then obtains through precipitation removal of impurities crystallization repeatedly the high purity vanadium product that purity is greater than 99.5%, but this method vanadium loss is large, and precipitated crystal repeatedly, and preparation section is complicated.Patent CN102764897A has announced a kind of preparation method of high-purity vanadium powder, its objective is vanadium powder foreign matter content particularly O, the problem that N content is high of solving, meet the requirement of powder metallurgy technology aspect material purity, its preparation process comprises: first adopt alkali lye, distilled water and ethanol or acetone to carry out surface active to vanadium piece, packed again into encloses container and packed the above-mentioned encloses container that is placed with vanadium piece into hydrogenation suction hydrogen system, dry degasification is carried out hydrogenation by vanadium piece after degasification and is made high-purity Vanadium hydride particle under 200-500 degree Celsius; Bing Jianggai Vanadium hydride grinds, and puts into encloses container dehydrogenation, can make submicron order vanadium powder, and wherein Control for Oxygen Content is below 600ppm, and Control of Nitrogen Content is below 250ppm.In addition, also there is patent directly from reclaiming vanadium containing vanadium waste material, but do not make high purity vanadium vanadium product, such as the publication number patent that is CN101538652A proposes that alkali soaks, the combination process of alkali immersion liquid absorption, acidleach, ion-exchange, desorb vanadium removal, precipitation, can make common vanadium.Publication number is the patent of CN1073414, propose a kind of with chemical method from the method containing reclaiming vanadium chromium vanadium, chromium waste liquid, this technique only, to having practical significance containing chromium, dilute solution that vanadium is low, is more suitable for plant drainage and processes, and is not suitable for the regeneration of high dense tail washings.US Patent No. 4344924 adopt quaternary amine extraction agents under alkaline condition from water one step extracting vanadium chromium, then carry out separation with adjust pH washing method.This technical matters is fairly simple, and can obtain vanadium and the chromium product of higher degree, but due to extraction agent finite capacity, is difficult to obtain the vanadium liquid of high density.Application number 201210513214.X has announced a kind of precipitate and separate and the method reclaiming containing vanadium in vanadium chromium solution and chromium, and this method adopts acid ammonium salt precipitation, and the method for step-by-step reduction precipitation can be prepared the chromium product of higher concentration, but vanadium product is failed high purity utilization.Publication number is the patent of CN101121962A, a kind of vanadium, the chromium separation method that applicant proposes for the aqueous solution containing high vanadium concentrations and chromium, the highest 99.5% the vanadium that makes, this patented technology is to vanadium and chromium good separating effect, and industrial implementation and steady running have been carried out, but this technology is suitable for the newly-built technique of processing containing vanadium, chromium solution, be not too applicable to the transformation to existing technical process.
Summary of the invention
Technical problem to be solved by this invention is: for current vanadium industrial economy, glide, vanadium product purity is not high, cannot meet this reality that requires to vanadium product purity such as present stage vanadium flow battery, the catalyzer of having relatively high expectations, medical material, some luminescent material, provide a kind of amine extracted heteropolyacid impurity to prepare the method for high purity vanadium, can prepare high purity vanadic anhydride product by simple operation, low for equipment requirements, and crucial extraction medicament Heat stability is good, to acid, alkali is insensitive, regeneration is simple with circulation means, is easy to industrialization.
Technical solution of the present invention is: conventionally can be chromium-doped in the solution of common vanadium, silicon, phosphorus, tungsten, molybdenum, the impurity such as arsenic, in this solution, add acid, can form phosphorus tungsten, phosphorus tungsten vanadium, silicon tungsten, phosphorus molybdenum tungsten, silicon molybdenum tungsten, molybdenum vanadium arsenic, the heteropolyacids such as tungsten arsenic, adopt the heteropolyacid in amine and the common vanadium solution of the composite synergistic extraction of synergist to remove solution impurities, obtain purifying containing vanadium raffinate, then will be containing vanadium raffinate evaporation concentration to v element 40g/L, in concentrated solution, add again ammonium salt to obtain ammonium meta-vanadate solid, by pure water, wash again, dry, oxygen atmosphere calcining obtains the Vanadium Pentoxide in FLAKES that purity is greater than 99.9%, organic phase after extraction heteropolyacid adopts containing alkaline solution heteropolyacid back extraction is formed containing heteropolyacid water, and obtains reprocessing cycle containing heteropolyacid organic phase.
A kind of amine extracted heteropolyacid impurity provided by the invention is prepared the method for high purity vanadium, as shown in Figure 1, comprises the steps:
(1) be first the suitable extraction of preparation containing vanadium water and fresh organic phase
Before extraction, by adjusting pH value, make the impurity containing in vanadium water that contains impurity all generate heteropolyacid; Fresh organic phase is dissolved in nonpolar thinner after adopting amine and synergist composite in varing proportions, and is aided with long-chain alcohol as phase modifier.
(2) adopt the extraction heteropolyacid system of invention to extract according to certain condition, and load organic phase is carried out to back extraction regeneration, it is circulated, raffinate contains high-purity vanadium, can concentrate, more further prepare high purity vanadic anhydride by step (3), be specially:
By the ready fresh organic phase of step (1) 1. and containing vanadium water, 2. according to volume ratio, be mixed to steel basin at 1: 1 and stir stratification after certain hour, upper strata be rich heteropolyacid organic phase ③， lower floor be high purity vanadium water 4.; 4. 3. rich heteropolyacid organic phase separated with high purity vanadium water, 5. rich vanadium heteropolyacid organic phase can add in 3. containing buck makes heteropolyacid and alkali reaction form containing heteropolyacid water 6. and generate the organic phase of regenerating and 7. make rich heteropolyacid organic phase be regenerated mutually, containing heteropolyacid water, 6. can be impregnated on the carriers such as alumina balls in addition, be prepared into desulphurization denitration catalyzer; High purity vanadium water 4. can by evaporation concentration to the concentrated vanadium water of 40g/L 8..The visible accompanying drawing 2 of detailed process.
(3) the concentrated vanadium water of the higher degree making is carried out to the steps such as precipitation, washing, dry, calcining and prepares the high-purity vanadium pentoxide that purity is greater than 99.9%, be specially:
8. the concentrated vanadium water of step (2) gained is heated to after certain temperature, under agitation condition, add in batches a certain amount of ammonium salt that vanadium is precipitated with the formation of ammonium meta-vanadate, stir certain hour, after treating that most of vanadium avales, centrifugation solid-liquid two-phase, and to solid phase ammonium meta-vanadate wash, centrifugation operation, put the ammonium meta-vanadate obtaining into oven drying certain hour afterwards, put into again retort furnace, and calcining preparation purity surpasses 99.9% high purity vanadic anhydride.
Before described extraction, need to regulate the pH value of impure vanadium solution within the scope of 2-7, preferably pH value is adjustable as 3-7 scope, is particularly preferably 4-7.Described organic phase adopts organic amine and synergist mix with long-chain alcohol and are dissolved in nonpolar thinner, and selected amine extractant, synergist, long-chain alcohol, nonpolar thinner all have less solubleness in the aqueous solution.Preferably, described organic amine is that carbon atom quantity is more than or equal to 10 aliphatic amide, comprise the combination of a kind of in primary amine, secondary amine, tertiary amine, quaternary ammonium salt or at least two kinds, the preferably combination of a kind of in trimethylammonium alkanamine class, trialkyl tertiary amines, halo dimethyl tertiary amine class or at least two kinds, is particularly preferably the combination of a kind of in N236, N235, Alamine 336, Aliquat 336, N1923, Primene 81R, Primene JMT, 7203,7301 or at least two kinds; Described amine extractant boiling point is generally between 280-320 degree Celsius.Described synergist is preferably neutral phosphorus extractant, the neutral combination containing a kind of in oxygen extraction agent, neutral sulphur-containing extractants, chelating extractant or at least two kinds, be particularly preferably the combination of a kind of in trialkyl phosphorus class, ketone, sulfoxide type, oximes, hydroxyquinoline class or at least two kinds, be particularly preferably: the combination of TRPO, MIBK, dioctylsulfoxide(DOSO), 7-allylic alkylation-8 hydroxyquinoline, LIX64, LIX63, LIX65N, N530 a kind of or at least two kinds; Described long-chain alcohol is preferably the combination of a kind of in the unit alcohol of carbonatoms within the scope of 6-12, dibasic alcohol, trivalent alcohol or at least two kinds, is particularly preferably the combination of a kind of in n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, nonanol-, nonylcarbinol, 2-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 3-ethyl-2-enanthol, isooctyl alcohol or at least two kinds; Described synergist and long-chain alcohol can improve viscosity and the density of organic phase, are conducive to extract long-term circulation.Described nonpolar thinner is preferably the combination of a kind of in saturated fatty hydro carbons, arene, replacement hydrocarbons, kerosene or at least two kinds, is particularly preferably the combination of a kind of in hexanaphthene, normal hexane, normal heptane, toluene, o-Xylol, m-xylene, p-Xylol, chloroform, sulfonated kerosene or at least two kinds.In fresh organic phase, the volume percent in is 1. 0.5-10% to described amine extractant, and in fresh organic phase, the volume percent in is 1. 0.1-2.0% to synergist, and in fresh organic phase, the volume percent in is 1. 0.1-2.0% to long-chain alcohol; The volume percent that is particularly preferably amine extractant is 0.5-5%, and the volume percent of synergist is 0.1-1.0%, and the volume percent of long-chain alcohol is 0.1-1.0%.2. 1. and containing vanadium water described fresh organic phase be positioned in steel basin and stir 1-100 minute, is preferably and stirs 1-60 minute, is particularly preferably 1-30 minute; After described extraction, time of repose is 1-60 minute, is preferably 1-40 minute, is particularly preferably 1-20 minute.5. 3. with containing buck described rich heteropolyacid organic phase mixed and carried out back extraction according to volume ratio mutually at 1: 1, the back extraction time is 1-150 minute, is preferably 1-100 minute, is particularly preferably 1-50 minute, back extraction temperature, preferably at 25-50 degree Celsius, is particularly preferably 35-50 degree Celsius; Described alkali is preferably the combination of a kind of in potassium hydroxide, sodium hydroxide, ammoniacal liquor, sodium carbonate, sodium bicarbonate or at least two kinds, and described alkaline solution mass concentration scope is preferably 1-30%, is particularly preferably 1-20%; 4. described high purity vanadium water is preferred 80-120 degree Celsius by evaporation concentration to concentrated vanadium water temperature 8., is particularly preferably 95-105 degree Celsius.The temperature range that 8. solution that described step (2) obtains heat is 20-40 degree Celsius, is particularly preferably 25-35 degree Celsius; Described ammonium salt is preferably the combination of a kind of in ammonium chloride, ammonium sulfate, ammonium nitrate or at least two kinds, for concentrated vanadium water 8. in the vanadium solution of about 40g/L, 8. the dosage of described ammonium salt and concentrated vanadium solution solid-to-liquid ratio are 8. preferably 30-200 gram/mono-liter concentrated vanadium water, are particularly preferably 50-150 gram/mono-liter concentrated vanadium water 8.; In concentrated vanadium water 8. described ammonium salt adds in batches, adds batch to be preferably 2-4 time; Described churning time is preferably 60-200 minute, is particularly preferably 90-150 minute; The solid-to-liquid ratio scope of the ammonium meta-vanadate of described formation and washings is 25-45 gram/mono-liter washing water, and described washing water are high purity water.Described ammonium meta-vanadate is put into oven drying, is preferably dry 6-10 hour under 105 degrees Celsius, and described retort furnace calcining is that temperature is preferably 400-800 degree Celsius under oxygen atmosphere condition, is particularly preferably 500-700 degree Celsius; Described in retort furnace calcination time be preferably 3-8 hour, be particularly preferably 4-6 hour.
The present invention's advantage is compared with prior art:
(1) the present invention adopts extraction process to extract heteropolyacid from the vanadium solution that contains impurity, makes impurity at utmost to remove, and prepares high purity vanadium product, can improve value-added content of product, have distinct economic.
(2) the present invention is low for equipment requirements, simple to operate, crucial extraction medicament Heat stability is good, and insensitive to acid, alkali, regeneration is simple with circulation means, is easy to industrialization.
Accompanying drawing explanation
Fig. 1 is the schema of the inventive method;
Fig. 2 is the method flow diagram of the amine extracted heteropolyacid in the present invention.
Embodiment
Be accompanied by specific embodiment below and introduce in detail the present invention.But following embodiment only limits to explain the present invention, and protection scope of the present invention should comprise the full content of claim, is not limited only to the present embodiment.
Embodiment 1:
Take containing the feed liquid after chrome alum slag leach liquor deep impurity-removing as containing vanadium solution, solution composition is: the vanadium of 16 grams per liters, 0.5 grams per liter chromium, 0.5 grams per liter tungsten, 0.05 grams per liter silicon, 0.05 grams per liter phosphorus, 0.5 grams per liter molybdenum, 0.1 grams per liter arsenic, with primary amine N1923, oximes extraction agent LIX63, n-Octanol and kerosene are made into organic phase, carry out extracting and separating test, adjusting material liquid pH value is 6.00, extraction agent primary amine concentration of volume percent is chosen as 3%, LIX63 concentration of volume percent is 0.8%, n-Octanol concentration of volume percent is 0.8%, extraction temperature is 25 ℃ of room temperatures, water and organic phase are mixed in steel basin, stir extraction 15 minutes, take off vibrator stratification 20 minutes, make organic phase obtain regeneration the sodium hydroxide back extraction of load organic phase employing 5%, raffinate is heated to 105 degree, be evaporated to about 40g/L, the solid-to-liquid ratio of the vanadium solution after the dosage of ammonium chloride and evaporation is 50 grams/mono-liter solution, add at twice, precipitation temperature is 30 degrees Celsius, stir precipitation 120 minutes, wash three times, the solid-to-liquid ratio scope of ammonium meta-vanadate and total washings is 35 grams/mono-liter washing water, in baking oven, be dried 7 hours, be positioned over retort furnace and be warming up to 600 degree, under oxygen atmosphere, be dried 5 hours.Gained Vanadium Pentoxide in FLAKES is 99.958% through XRF analysis.
Embodiment 2:
Take containing the feed liquid after chrome alum slag leach liquor deep impurity-removing as containing vanadium solution, solution composition is: the vanadium of 16 grams per liters, 0.5 grams per liter chromium, 0.5 grams per liter tungsten, 0.05 grams per liter silicon, 0.05 grams per liter phosphorus, 0.5 grams per liter molybdenum, 0.1 grams per liter arsenic, with quaternary ammonium salt N263, trialkyl phosphorus TRPO, n-hexyl alcohol and toluene are made into organic phase, carry out extracting and separating test, adjusting material liquid pH value is 6.50, extraction agent primary amine concentration of volume percent is chosen as 4%, LIX63 concentration of volume percent is 1.0%, n-Octanol concentration of volume percent is 1.0%, extraction temperature is 25 ℃ of room temperatures, water and organic phase are mixed in steel basin, stir extraction 20 minutes, take off vibrator stratification 10 minutes, make organic phase obtain regeneration the potassium hydroxide back extraction of load organic phase employing 5%, raffinate is heated to 105 degree, be evaporated to about 40g/L, the solid-to-liquid ratio of the vanadium solution after the dosage of ammonium chloride and evaporation is 55 grams/mono-liter solution, add at twice, precipitation temperature is 30 degrees Celsius, stir precipitation 100 minutes, wash three times, the solid-to-liquid ratio scope of ammonium meta-vanadate and total washings is 40 grams/mono-liter washing water, in baking oven, be dried 7 hours, be positioned over retort furnace and be warming up to 500 degree, under oxygen atmosphere, be dried 6 hours.Gained Vanadium Pentoxide in FLAKES is 99.97% through XRF analysis.
Embodiment 3:
Take containing the feed liquid after chrome alum slag leach liquor deep impurity-removing as containing vanadium solution, solution composition is: the vanadium of 16 grams per liters, 0.5 grams per liter chromium, 0.5 grams per liter tungsten, 0.05 grams per liter silicon, 0.05 grams per liter phosphorus, 0.5 grams per liter molybdenum, 0.1 grams per liter arsenic, with tertiary amine Alamine336, dioctylsulfoxide(DOSO), 4 methyl 1 amylalcohols and o-Xylol are made into organic phase, carry out extracting and separating test, adjusting material liquid pH value is 4.5, extraction agent primary amine concentration of volume percent is chosen as 3.0%, LIX63 concentration of volume percent is 0.3%, n-Octanol concentration of volume percent is 0.3%, extraction temperature is 25 ℃ of room temperatures, water and organic phase are mixed in steel basin, stir extraction 20 minutes, take off vibrator stratification 10 minutes, make organic phase obtain regeneration the potassium hydroxide back extraction of load organic phase employing 15%, raffinate is heated to 105 degree, be evaporated to about 40g/L, the solid-to-liquid ratio of the vanadium solution after the dosage of ammonium nitrate and evaporation is 80 grams/mono-liter solution, add at twice, precipitation temperature is 25 degrees Celsius, stir precipitation 120 minutes, wash three times, the solid-to-liquid ratio scope of ammonium meta-vanadate and total washings is 45 grams/mono-liter washing water, in baking oven, be dried 8 hours, be positioned over retort furnace and be warming up to 700 degree, under oxygen atmosphere, be dried 5 hours.Gained Vanadium Pentoxide in FLAKES is 99.93% through XRF analysis.
Embodiment 4:
Take containing the feed liquid after chrome alum slag leach liquor deep impurity-removing as containing vanadium solution, solution composition is: the vanadium of 16 grams per liters, 0.5 grams per liter chromium, 0.5 grams per liter tungsten, 0.05 grams per liter silicon, 0.05 grams per liter phosphorus, 0.5 grams per liter molybdenum, 0.1 grams per liter arsenic, with Primene 81R, 7-allylic alkylation-oxine, 2 methyl isophthalic acid amylalcohols and m-xylene are made into organic phase, carry out extracting and separating test, adjusting material liquid pH value is 4.0, extraction agent primary amine concentration of volume percent is chosen as 2.0%, LIX65N concentration of volume percent is 0.4%, n-Octanol concentration of volume percent is 0.4%, extraction temperature is 25 ℃ of room temperatures, water and organic phase are mixed in steel basin, stir extraction 30 minutes, take off vibrator stratification 5 minutes, make organic phase obtain regeneration the potassium hydroxide back extraction of load organic phase employing 10%, raffinate is heated to 105 degree, be evaporated to about 40g/L, the solid-to-liquid ratio of the vanadium solution after the dosage of ammonium sulfate and evaporation is 105 grams/mono-liter solution, add at twice, precipitation temperature is 35 degrees Celsius, stir precipitation 150 minutes, wash three times, the solid-to-liquid ratio scope of ammonium meta-vanadate and total washings is 40 grams/mono-liter washing water, in baking oven, be dried 10 hours, be positioned over retort furnace and be warming up to 500 degree, under oxygen atmosphere, be dried 6 hours.Gained Vanadium Pentoxide in FLAKES is 99.96% through XRF analysis.
Embodiment 5:
Take containing the feed liquid after chrome alum slag leach liquor deep impurity-removing as containing vanadium solution, solution composition is: the vanadium of 16 grams per liters, 0.5 grams per liter chromium, 0.5 grams per liter tungsten, 0.05 grams per liter silicon, 0.05 grams per liter phosphorus, 0.5 grams per liter molybdenum, 0.1 grams per liter arsenic, with Primene81R, 7-allylic alkylation-oxine, 2 methyl isophthalic acid amylalcohols and m-xylene are made into organic phase, carry out extracting and separating test, adjusting material liquid pH value is 7.0, extraction agent primary amine concentration of volume percent is chosen as 4.0%, N530 concentration of volume percent is 0.8%, n-Octanol concentration of volume percent is 0.6%, extraction temperature is 25 ℃ of room temperatures, water and organic phase are mixed in steel basin, stir extraction 10 minutes, take off vibrator stratification 20 minutes, make organic phase obtain regeneration the potassium hydroxide back extraction of load organic phase employing 5%, raffinate is heated to 105 degree, be evaporated to about 40g/L, the solid-to-liquid ratio of the vanadium solution after the dosage of ammonium sulfate and evaporation is 105 grams/mono-liter solution, add at twice, precipitation temperature is 30 degrees Celsius, stir precipitation 120 minutes, wash three times, the solid-to-liquid ratio scope of ammonium meta-vanadate and total washings is 35 grams/mono-liter washing water, in baking oven, be dried 9 hours, be positioned over retort furnace and be warming up to 600 degree, under oxygen atmosphere, be dried 4 hours.Gained Vanadium Pentoxide in FLAKES is 99.95% through XRF analysis.
In a word, the present invention can adopt extraction process to extract heteropolyacid from the vanadium solution that contains impurity, makes impurity at utmost to remove, and prepares high purity vanadium product, and this invention can improve value-added content of product, have distinct economic.
It should be noted that, according to the various embodiments described above of the present invention, those skilled in the art are the four corners that can realize independent claim of the present invention and appurtenance completely, implementation procedure and method same the various embodiments described above; And non-elaborated part of the present invention belongs to techniques well known.
The above; be only part embodiment of the present invention, but protection scope of the present invention is not limited to this, in the technical scope that any those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.
Claims (8)
1. amine extracted heteropolyacid impurity is prepared a method for high purity vanadium, it is characterized in that comprising the steps:
(1) be first the suitable extraction of preparation containing vanadium water and fresh organic phase
Before extraction, by regulating pH value within the scope of 2-7, make the impurity containing in vanadium water that contains impurity all generate heteropolyacid; Fresh organic phase is dissolved in nonpolar thinner after adopting organic amine and synergist composite in varing proportions, and is aided with long-chain alcohol as phase modifier;
(2) adopt the extraction heteropolyacid system of invention to extract according to certain condition, and load organic phase is carried out to back extraction regeneration, it is circulated, raffinate contains high-purity vanadium, can concentrate, more further prepare high purity vanadic anhydride by step (3), be specially:
Containing vanadium water and fresh organic phase, according to volume ratio, be mixed to steel basin at 1: 1 and stir stratification after certain hour step (1) is ready, the organic phase of heteropolyacid that upper strata has been load, lower floor is high purity vanadium water; Both are separated, in rich heteropolyacid organic phase, add containing buck mutual-assistance heteropolyacid and alkali reaction and form containing heteropolyacid water, and rich heteropolyacid organic phase is regenerated; High purity vanadium water is the concentrated vanadium water to 40g/L by evaporation concentration;
(3) concentrated vanadium solution step (2) being made carries out precipitation, washing, dry, calcining step is prepared highly purified Vanadium Pentoxide in FLAKES, is specially:
The concentrated vanadium water of step (2) gained is heated to after certain temperature, under agitation condition, add in batches a certain amount of ammonium salt that vanadium is precipitated with the form of ammonium meta-vanadate, stir certain hour, after treating that most of vanadium avales, centrifugation solid-liquid two-phase, and to solid phase ammonium meta-vanadate wash, centrifugation operation, put the ammonium meta-vanadate obtaining into oven drying certain hour afterwards, put into again retort furnace, and the high purity vanadic anhydride that calcining preparation purity is greater than 99.9% in oxygen atmosphere.
2. a kind of amine extracted heteropolyacid impurity according to claim 1 is prepared the method for high purity vanadium, it is characterized in that: before described extraction, need to regulate the pH value of impure vanadium solution being 3-7 scope, be preferably 4-7.
3. a kind of amine extracted heteropolyacid impurity according to claim 1 is prepared the method for high purity vanadium, it is characterized in that: described organic amine is that carbon atom quantity is more than or equal to 10 aliphatic amide, comprise the combination of a kind of in primary amine, secondary amine, tertiary amine, quaternary ammonium salt or at least two kinds; The preferably combination of a kind of in trimethylammonium alkanamine class, trialkyl tertiary amines, halo dimethyl tertiary amine class or at least two kinds, is particularly preferably the combination of a kind of in N236, N235, Alamine 336, Aliquat 336, N1923, Primene 81R, Primene JMT, 7203,7301 or at least two kinds.
4. a kind of amine extracted heteropolyacid impurity according to claim 1 is prepared the method for high purity vanadium, it is characterized in that: described synergist is neutral phosphorus extractant, the neutral combination containing a kind of in oxygen extraction agent, neutral sulphur-containing extractants, chelating extractant or at least two kinds; Be preferably the combination of a kind of in trialkyl phosphorus class, ketone, sulfoxide type, oximes, hydroxyquinoline class or at least two kinds, be particularly preferably: the combination of TRPO, MIBK, dioctylsulfoxide(DOSO), 7-allylic alkylation-8 hydroxyquinoline, LIX64, LIX63, LIX65N, N530 a kind of or at least two kinds.
5. a kind of amine extracted heteropolyacid impurity according to claim 1 is prepared the method for high purity vanadium, it is characterized in that: described long-chain alcohol is preferably the combination of a kind of in the unit alcohol of carbonatoms within the scope of 6-12, dibasic alcohol, trivalent alcohol or at least two kinds; Be preferably the combination of a kind of in n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, nonanol-, nonylcarbinol, 2-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 3-ethyl-2-enanthol, isooctyl alcohol or at least two kinds.
6. a kind of amine extracted heteropolyacid impurity according to claim 1 is prepared the method for high purity vanadium, it is characterized in that: described nonpolar thinner is the combination of a kind of in saturated fatty hydro carbons, arene, replacement hydrocarbons, kerosene or at least two kinds; Be preferably the combination of a kind of in hexanaphthene, normal hexane, normal heptane, toluene, o-Xylol, m-xylene, p-Xylol, chloroform, sulfonated kerosene or at least two kinds.
7. a kind of amine extracted heteropolyacid impurity according to claim 1 is prepared the method for high purity vanadium, it is characterized in that: the volume percent of described amine extractant in fresh organic phase is 0.5-10%, the volume percent of synergist in fresh organic phase is 0.1-2.0%, and the volume percent of long-chain alcohol in fresh organic phase is 0.1-2.0%; The volume percent that is particularly preferably amine extractant is 0.5-5%, and the volume percent of synergist is 0.1-1.0%, and the volume percent of long-chain alcohol is 0.1-1.0%.
8. a kind of amine extracted heteropolyacid impurity according to claim 1 is prepared the method for high purity vanadium, it is characterized in that: described alkali is preferably the combination of a kind of in potassium hydroxide, sodium hydroxide, ammoniacal liquor, sodium carbonate, sodium bicarbonate or at least two kinds, the described alkaline solution mass concentration scope that contains is preferably 1-30%, is particularly preferably 1-20%; Described high purity vanadium solution is preferred 80-120 degree Celsius by evaporation concentration to the temperature that concentrates vanadium solution, is particularly preferably 95-105 degree Celsius.
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| CN103937998A (en) * | 2014-04-21 | 2014-07-23 | 中国科学院过程工程研究所 | Method for preparing low-silicon vanadium pentoxide from solution containing vanadium, chromium and silicon |
| CN103937981A (en) * | 2014-04-21 | 2014-07-23 | 中国科学院过程工程研究所 | Method for preparing high-purity vanadium and heteropolyacid catalyst |
| CN104018011A (en) * | 2014-06-23 | 2014-09-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Production method of vanadic oxide |
| CN104178632A (en) * | 2014-08-12 | 2014-12-03 | 东北大学 | Method for comprehensively utilizing titanium white waste acid |
| CN104762475A (en) * | 2014-12-03 | 2015-07-08 | 核工业北京化工冶金研究院 | Vanadium extracting method capable of dynamically adjusting acid |
| CN105369036A (en) * | 2015-11-20 | 2016-03-02 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing high-concentration hydrochloric acid solution |
| CN106947864A (en) * | 2016-01-07 | 2017-07-14 | 中国科学院过程工程研究所 | A kind of system and its processing method that heavy metal is reclaimed from discarded SCR catalyst |
| CN107117652A (en) * | 2016-02-25 | 2017-09-01 | 中国科学院过程工程研究所 | It is a kind of from alkalescence containing the method that ammonium metavanadate is obtained in vanadium solution |
| CN107964592A (en) * | 2016-10-19 | 2018-04-27 | 中国科学院过程工程研究所 | A kind of method of Separation by Complexation chromium and vanadium in self-contained chrome alum Acidic Liquid |
| WO2018129868A1 (en) | 2017-01-11 | 2018-07-19 | 中国科学院过程工程研究所 | System for extracting vanadium from leaching solution containing vanadium chromium silicon and for preparing vanadium pentoxide and processing method therefor |
| CN108358792A (en) * | 2017-06-23 | 2018-08-03 | 中国科学院过程工程研究所 | The method that solid complex is extracted from the aqueous solution of the oxygen-containing acid group containing vanadium, obtained solid complex and application thereof |
| CN108866356A (en) * | 2018-04-03 | 2018-11-23 | 东北大学 | A method of the extraction vanadium extraction from vanadium slag high acidic oils liquid |
| CN110423890A (en) * | 2019-08-28 | 2019-11-08 | 重庆大学 | A method of the deep phosphorous removal in acid vanadium extraction solution |
| CN110629049A (en) * | 2018-06-25 | 2019-12-31 | 中国科学院过程工程研究所 | Method for extracting and separating chromium from chromium-containing ammonium metavanadate solution |
| CN110629051A (en) * | 2018-06-25 | 2019-12-31 | 中国科学院过程工程研究所 | Method for extracting and separating chromium from alkaline vanadium-chromium-containing solution |
| CN111235409A (en) * | 2020-03-09 | 2020-06-05 | 广西大学 | Method for extracting vanadium from vanadium-containing sodium carbonate leaching solution |
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| CN114517264A (en) * | 2022-02-21 | 2022-05-20 | 江西理工大学 | Cooperative metallurgy method for extracting tungsten and removing arsenic based on arsenic-tungsten heteropoly acid |
| CN116814990A (en) * | 2023-08-31 | 2023-09-29 | 中国科学院过程工程研究所 | Method for extracting and separating vanadium in vanadium-arsenic solution by utilizing hydrophobic eutectic solvent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451199A (en) * | 2008-12-16 | 2009-06-10 | 中色（宁夏）东方集团有限公司 | Method for extracting vanadic anhydride from stone coal vanadium ore |
| CN101928830A (en) * | 2010-09-25 | 2010-12-29 | 吉首大学 | Method for extracting vanadium from vanadium-containing liquid |
| CN102154550A (en) * | 2011-03-25 | 2011-08-17 | 北京能泰高科环保技术有限公司 | Vanadium extracting method based on extraction-back extraction system |
-
2013
- 2013-08-26 CN CN201310377023.XA patent/CN103540745B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451199A (en) * | 2008-12-16 | 2009-06-10 | 中色（宁夏）东方集团有限公司 | Method for extracting vanadic anhydride from stone coal vanadium ore |
| CN101928830A (en) * | 2010-09-25 | 2010-12-29 | 吉首大学 | Method for extracting vanadium from vanadium-containing liquid |
| CN102154550A (en) * | 2011-03-25 | 2011-08-17 | 北京能泰高科环保技术有限公司 | Vanadium extracting method based on extraction-back extraction system |
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| CN103937998A (en) * | 2014-04-21 | 2014-07-23 | 中国科学院过程工程研究所 | Method for preparing low-silicon vanadium pentoxide from solution containing vanadium, chromium and silicon |
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| CN104018011A (en) * | 2014-06-23 | 2014-09-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Production method of vanadic oxide |
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| CN104762475A (en) * | 2014-12-03 | 2015-07-08 | 核工业北京化工冶金研究院 | Vanadium extracting method capable of dynamically adjusting acid |
| CN105369036A (en) * | 2015-11-20 | 2016-03-02 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing high-concentration hydrochloric acid solution |
| CN106947864B (en) * | 2016-01-07 | 2019-06-04 | 中国科学院过程工程研究所 | A kind of system and its processing method recycling heavy metal from discarded SCR catalyst |
| CN106947864A (en) * | 2016-01-07 | 2017-07-14 | 中国科学院过程工程研究所 | A kind of system and its processing method that heavy metal is reclaimed from discarded SCR catalyst |
| CN107117652A (en) * | 2016-02-25 | 2017-09-01 | 中国科学院过程工程研究所 | It is a kind of from alkalescence containing the method that ammonium metavanadate is obtained in vanadium solution |
| CN107117652B (en) * | 2016-02-25 | 2019-04-23 | 中国科学院过程工程研究所 | A method of from alkalinity containing obtaining ammonium metavanadate in vanadium solution |
| CN107964592A (en) * | 2016-10-19 | 2018-04-27 | 中国科学院过程工程研究所 | A kind of method of Separation by Complexation chromium and vanadium in self-contained chrome alum Acidic Liquid |
| CN107964592B (en) * | 2016-10-19 | 2019-06-14 | 中国科学院过程工程研究所 | A kind of method of Separation by Complexation chromium and vanadium in self-contained chrome alum Acidic Liquid |
| WO2018129868A1 (en) | 2017-01-11 | 2018-07-19 | 中国科学院过程工程研究所 | System for extracting vanadium from leaching solution containing vanadium chromium silicon and for preparing vanadium pentoxide and processing method therefor |
| CN108358792A (en) * | 2017-06-23 | 2018-08-03 | 中国科学院过程工程研究所 | The method that solid complex is extracted from the aqueous solution of the oxygen-containing acid group containing vanadium, obtained solid complex and application thereof |
| CN108358792B (en) * | 2017-06-23 | 2021-03-12 | 中国科学院过程工程研究所 | Method for extracting solid complex from aqueous solution containing vanadium and oxygen acid radical, obtained solid complex and application thereof |
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| CN110629049B (en) * | 2018-06-25 | 2020-12-04 | 中国科学院过程工程研究所 | Method for extracting and separating chromium from chromium-containing ammonium metavanadate solution |
| CN110629049A (en) * | 2018-06-25 | 2019-12-31 | 中国科学院过程工程研究所 | Method for extracting and separating chromium from chromium-containing ammonium metavanadate solution |
| CN110629051A (en) * | 2018-06-25 | 2019-12-31 | 中国科学院过程工程研究所 | Method for extracting and separating chromium from alkaline vanadium-chromium-containing solution |
| CN110629051B (en) * | 2018-06-25 | 2021-02-26 | 中国科学院过程工程研究所 | Method for extracting and separating chromium from alkaline vanadium-chromium-containing solution |
| CN110423890A (en) * | 2019-08-28 | 2019-11-08 | 重庆大学 | A method of the deep phosphorous removal in acid vanadium extraction solution |
| CN110423890B (en) * | 2019-08-28 | 2021-06-18 | 重庆大学 | Method for deeply removing phosphorus in acidic vanadium extraction solution |
| CN111235409A (en) * | 2020-03-09 | 2020-06-05 | 广西大学 | Method for extracting vanadium from vanadium-containing sodium carbonate leaching solution |
| CN112210678A (en) * | 2020-09-14 | 2021-01-12 | 广东芳源环保股份有限公司 | Method for removing impurities of phosphorus and silicon from nickel solution by complexing extraction |
| CN112226629A (en) * | 2020-09-14 | 2021-01-15 | 广东芳源环保股份有限公司 | Method for removing impurities from nickel solution by using reusable polymetallic salt as complexing agent |
| CN113058289A (en) * | 2021-02-19 | 2021-07-02 | 江钨世泰科钨品有限公司 | Extraction system of sodium tungstate solution transformation |
| CN113201657A (en) * | 2021-05-07 | 2021-08-03 | 中南大学 | Method for separating vanadium and chromium from vanadium and chromium-containing solution through co-extraction-selective back extraction |
| CN114517264A (en) * | 2022-02-21 | 2022-05-20 | 江西理工大学 | Cooperative metallurgy method for extracting tungsten and removing arsenic based on arsenic-tungsten heteropoly acid |
| CN114438347A (en) * | 2022-04-12 | 2022-05-06 | 中国恩菲工程技术有限公司 | Method for extracting and preparing high-purity vanadium oxide from high-chlorine vanadium-containing solution |
| CN116814990A (en) * | 2023-08-31 | 2023-09-29 | 中国科学院过程工程研究所 | Method for extracting and separating vanadium in vanadium-arsenic solution by utilizing hydrophobic eutectic solvent |
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