CN102251107A - Method for treating rhenium-containing raw material - Google Patents
Method for treating rhenium-containing raw material Download PDFInfo
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- CN102251107A CN102251107A CN2011101885865A CN201110188586A CN102251107A CN 102251107 A CN102251107 A CN 102251107A CN 2011101885865 A CN2011101885865 A CN 2011101885865A CN 201110188586 A CN201110188586 A CN 201110188586A CN 102251107 A CN102251107 A CN 102251107A
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Abstract
The invention provides a method for treating a rhenium-containing raw material, which comprises the following steps: (a) leaching: mixing the rhenium-containing raw material and an oxidant in an atmospheric-pressure alkaline environment, and filtering the reaction products after the reaction finishes; and (b) separation: adsorbing the filtering liquid obtained in the step (a) with strongly alkaline anion exchange resin, and resolving the strongly alkaline anion exchange resin, wherein the oxidant is a sodium nitrate/oxydol mixture. The method provided by the invention is convenient for industrial production, directly adopts an ion exchange technique without acidification, increases the molybdenum/rhenium separation speed, reduces the acid consumption in the acidification process, lowers the production cost, and is beneficial to environmental protection.
Description
Technical field
The present invention relates to a kind of treatment process of rhenium-containing raw material.
Background technology
Rhenium and alloy thereof have special performances, are the indispensable industrial raw material of the big production of contemporary societyization, are one of starting material important in the modern high-tech field such as national defence, space flight, electronic industry, petrochemical complex.Famous RePt/Al
2O
3Platinum-rhenium catalyst, rhenium-containing 0.1%～0.5% is used for the catalytic reforming of petroleum refinement, can produce high-octane gasoline, and it also is used to produce trichloromethane, aromatic hydrocarbons and vinyl cyanide, is that other catalyzer are difficult to match in excellence or beauty.Rhenium catalyst also is used for the reformation of steam conversion alcohol, is the good catalyst of producing optically-active alcohols and carboxylic acid.Rhenium catalyst also is used to handle automobile engine tail gas, diesel motor exhaust, is used for waste gas such as decomposing nitrogen oxide, is the environment-friendly highly efficient catalyzer.In addition, nanometer sulfuration rhenium is also as catalyzer, and countries such as the U.S. are also with rhenium catalyst production CNT (carbon nano-tube).Since the seventies in last century, the amount that is used as catalyzer at U.S.'s rhenium accounts for 80%～90% of total rhenium amount.
Many weeks, rhenium can improve the ductility and the mechanical property thereof of W-Re alloys and molybdenum rhenium alloys.Typical W-Re alloys rhenium-containing 41%～47.5% is widely used in electronic industry, air system and nuclear industry field.Typical molybdenum rhenium alloys has two kinds, a kind of rhenium-containing 3%～5%, and another kind of rhenium-containing 26% is used for electronic industry and does filament and thermopair.With the alloy that Fe, W form, hardness is very high, and resistance to abrasion and erosion resistance are very strong.
Because the fusing point of rhenium can at high temperature provide required intensity up to 2453 ℃, be the irreplaceable added ingredients of most of superalloy therefore.As lanthanum trioxide dispersion-strengthened molybdenum rhenium alloys, because its ultimate tensile strength than general molybdenum rhenium alloys height, is widely used in all kinds of hot industries field.Aircraft adopts rhenium as indispensable additive with nickel superalloy unidirectional solidification turbine vane.
The title complex of rhenium such as carboxylic acid rhenium etc. have antitumous effect, can be used in the radiopharmaceuticals.
Based on premium properties and the important application thereof that rhenium had, rhenium is always as the strategic reserves goods and materials of countries in the world.
Rhenate is the important intermediate of other rhenium goods of preparation, good rhenium powder of obtained performance or rhenium bar etc., must the high-purity rhenate of preparation.Wherein of paramount importance is the rehenic acid ammonium, and it can be used as the technology that good intermediate is used for producing various rhenium goods.
Usually rhenium and molybdenum exist with class matter homophase in the molybdenum glance, and mainly exist with the form of sulfide, and the sulfuration rhenium is oxidized in roasting process, but the molybdenum that cures again in process of cooling is reduced into rhenium at a low price, is difficult to leach.Thereby desire with the roasting molybdenum glance and flue dust in the low price rhenium leach, it must be oxidized to the high price rhenium.
According to the literature, the technical process for preparing the rehenic acid ammonium of present domestic processing molybdenum glance calcination fume mainly contains following two kinds:
1, the logical oxonium base of flue dust → High Temperature High Pressure soaks → the heavy molybdenum of acidifying → primary amine collection rhenium → back extraction → thick rehenic acid ammonium;
2, hydrogen peroxide or Manganse Dioxide leaching → acidifying acid adjustment degree → resin anion(R.A) absorption → parsing → rehenic acid ammonium under flue dust → acidic conditions.
Yet have following problem in the correlation technique: high-temperature and high-pressure conditions is very high to equipment requirements, have bigger potential safety hazard, and production cost is higher, and if under acidic conditions, leach, can etching apparatus, and easily cause environmental pollution.
Summary of the invention
The object of the invention is to provide a kind of treatment process of rhenium-containing raw material, and is high and easily cause environmental pollution problems to solve in the correlation technique production cost.
For addressing the above problem, the invention provides a kind of treatment process of rhenium-containing raw material, comprising: a) leach step, the raw material that will contain rhenium under the normal pressure alkaline environment mixes with oxygenant, and question response filters reactant after finishing; B) separating step, after will adsorbing by strongly basic anion exchange resin through the filtered liquid that step a) obtains, this strongly basic anion exchange resin is resolved, wherein, above-mentioned oxygenant is the mixture of Sodium Nitrite and hydrogen peroxide, and the mass ratio of Sodium Nitrite and hydrogen peroxide is in 5: 3.5～5: 2.5 scopes.Further, in above-mentioned steps a) and further comprise acidification step between the step b), to carry out acidification through the filtered liquid that described step a) obtains, make the pH value of the filtered liquid after the acidification be adjusted to 8～10, and the interpolation hydrogen peroxide, the addition of hydrogen peroxide be the filtered liquid after the acidification quality 3%～8%.
Preferably, the alkaline environment of above-mentioned steps in a) is the mixing solutions that sodium hydroxide and yellow soda ash and water form, and wherein, the mass ratio of above-mentioned sodium hydroxide and yellow soda ash is in 6: 1～10: 1 scope.
Preferably, the mass ratio of above-mentioned Sodium Nitrite and hydrogen peroxide is in 5: 3.5～5: 2.5 scopes.
Preferably, the mass ratio of above-mentioned oxygenant and above-mentioned rhenium-containing raw material is 20%～80%.
Preferably, at above-mentioned steps b) in, before above-mentioned strongly basic anion exchange resin is resolved, adopt ammoniacal liquor as the above-mentioned strongly basic anion exchange resin of eluent drip washing.
Further, at above-mentioned steps b) further comprise step c) afterwards, to through above-mentioned steps b) and add ammonium ion in the desorbed solution that obtains, carry out crystallization treatment, obtain the rehenic acid ammonium.
The present invention has following beneficial effect:
The method according to this invention carries out alkaline oxygenated leaching under normal pressure, solved to adopt acidic oxidation to leach the pollution to environment of the deep-etching of equipment and acid mist.The method according to this invention is convenient to industrial production, need not acidifying and directly adopts the pressurization ion exchange technique of heating, and has accelerated the velocity of separation of molybdenum rhenium, and the usage quantity of acid has reduced production cost when having reduced acidifying, and helps environmental protection.
Except purpose described above, feature and advantage, the present invention also has other purpose, feature and advantage.With reference to embodiment, the present invention is further detailed explanation below.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is elaborated, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
Related normal pressure alkaline environment can be by following content-defined among the present invention: normal pressure is meant a normal atmosphere, i.e. the gaseous tension that this atmospheric layer of our usual life produces.According to differences such as residing geographical position, various places, sea level elevation, temperature, its actual normal atmosphere and standard atmospheric pressure are also unequal, but for simplicity, can be similar to and think that normal pressure is exactly a standard atmospheric pressure, i.e. 100KPa.
Related normal pressure alkaline environment can be by following content-defined among the present invention: alkalescence is meant that a kind of material provides the not ability of share electron pair to other material in solvent, the alkalescence that whether has a kind of material depends on that unpaired electron accepts the ability of proton, as OH in the aqueous solution
-Ion can be accepted H
+, NH
+ 4Plasma, thereby the alkalescence of showing, mineral alkali commonly used has: NaOH, KOH, Ca (OH)
2, NaNH
2, NH
3H
2O etc., organic bases commonly used mainly is quaternary ammonium bases (R
4NOH).
Above-mentioned rhenium-containing raw material among the present invention is meant: rhenium content can be the calcination fume of molybdenum glance, copper mine or the waste material of other rhenium-containings etc. greater than 0.01% material.Rhenium-containing raw material among the present invention preferably makes calcination fume by the low-temperature bake molybdenum glance.
The oxygenant that uses among the present invention can be: manganese oxide, hydrogen peroxide, Sodium Nitrite, chlorine etc. or its mixture, the mixture of wherein preferred Sodium Nitrite and hydrogen peroxide.
The method according to this invention, its flow process is as follows:
Flue dust (raw material that contains rhenium, low-temperature bake molybdenum glance and make) → alkali soaks (adding oxygenant simultaneously) → ion-exchange absorption rhenium → parsing.
Reaction equation in the said process can be expressed as follows:
4R
eS
2+4R
e2S
7+57O
2+84OH
-＝12R
eO
4 -+36SO
3 2-+6H
2O (1)
Treatment process according to rhenium-containing raw material of the present invention comprises: a) leach step, will contain the rhenium raw material and mix with oxygenant under the normal pressure alkaline environment, question response filters reactant after finishing; B) separating step after will adsorbing by strongly basic anion exchange resin through the filtered liquid that step a) obtains, is resolved this strongly basic anion exchange resin, and wherein, described oxygenant is the mixture of Sodium Nitrite and hydrogen peroxide.
Further, in above-mentioned steps a) and further comprise acidification step between the step b), to carry out acidification through the filtered liquid that described step a) obtains, make the pH value of the filtered liquid after the acidification be adjusted to 8～10, and the interpolation hydrogen peroxide, the addition of hydrogen peroxide be the filtered liquid after the acidification quality 3%～8%.By strong acid such as interpolation sulfuric acid, reaction is removed and is filtered unnecessary alkali in the reaction solution that obtains.In addition, there is certain low price sulphur in the molybdenum glance calcination fume, causes the molybdenum in the above-mentioned reaction solution to be reduced into molybdenum blue (Mo
8O
288H
2O: PLSCONFM and Mo
4O
11H
2O).And molybdenum blue easily becomes colloidal state to be adsorbed on the resin in the separating step, hinders ReO
4 -Be adsorbed, make in the above-mentioned reaction solution rhenium absorption not exclusively, thereby above-mentioned reaction solution is carried out pre-treatment (adding an amount of hydrogen peroxide) herein, molybdenum blue is oxidized to molybdenum at high price.
Preferably, the alkaline environment of above-mentioned steps in a) is the mixing solutions that sodium hydroxide and yellow soda ash and water form, wherein, described sodium hydroxide and yellow soda ash in 6: 1～10: 1 scope.
Preferably, above-mentioned Sodium Nitrite and hydrogen peroxide in 5: 3.5～5: 2.5 scopes.Hydrogen peroxide can be oxidized to perrhenic acid with the rhenium of sulphided state, but heat release during hydrogen peroxide oxidation, system temperature raises fast, easily make the rhenium volatilization, Sodium Nitrite can be opened the molybdenum rhenium sulfide oxidation that exists with the sosoloid form, improves the leaching yield of rhenium, both combine, improve the limitation of single-oxidizer, improve the leaching yield of whole system, guarantee that rhenium exists in solution.
Preferably, the mass ratio of above-mentioned oxygenant and above-mentioned rhenium-containing raw material is 20%～80%.
Preferably, at above-mentioned steps b) in, before above-mentioned strongly basic anion exchange resin is resolved, adopt ammoniacal liquor as the above-mentioned strongly basic anion exchange resin of eluent drip washing.Adopt the above-mentioned ion exchange resin of ammoniacal liquor drip washing, to remove absorption impurity such as molybdenum ion thereon.Because the molybdenum rhenium is different with the binding ability of asking the basic anion resin, molybdenum is easier to be got off by drip washing.Eluent can be the sodium hydroxide solution or the ammonia soln of lower concentration.Can be D296 or D301 macroreticular weakly base resin, R-518 resin or P350 extration resin etc.
Further, at above-mentioned steps b) further comprise step c) afterwards, to through above-mentioned steps b) and add ammonium ion in the desorbed solution that obtains, carry out crystallization treatment, obtain the rehenic acid ammonium.
Because rhenate (rehenic acid ammonium) is the important intermediate of other rhenium goods of preparation, good rhenium powder of obtained performance or rhenium bar etc., must the high-purity rhenate (rehenic acid ammonium) of preparation.
One, the method according to this invention prepares the rehenic acid ammonium
Embodiment 1
1) leach step:
Soak material: use the enamel reaction still (can also use the reactive tank or the irony reactor of polypropylene material) that is provided with agitator, side valve or bottom valve.At first check each pipeline, pump, valve, cell body, whether power supplys etc. are in standard state, toward the interior water that adds prescribed volume of groove, add and calculate good sodium hydroxide and yellow soda ash, the raw material (flue dust) that slowly adds load weighted rhenium-containing then, solid-to-liquid ratio S: L=1: 3, the volumetric molar concentration of sodium hydroxide is 4mol/L, the mass ratio of sodium hydroxide and soda ash is 6: 1, oxygenant is that Sodium Nitrite and hydrogen peroxide mix, the add-on of this oxygenant is 40% of a raw materials quality, rate of addition control is not to emit groove to be advisable, and the volumetric molar concentration of oxygenant is 2mol/L, and Sodium Nitrite and hydrogen peroxide mass ratio are 5: 3; 80～90 ℃ of temperature of reaction, the reaction times is 3 hours.
Filter: after reaction mass is cooled to room temperature, use the plate-and-frame filter press press filtration, slag adds the water flushing.
Acidifying: the filtrate after the press filtration, carry out acidifying with sulfuric acid, transferring pH value is 8～10, add hydrogen peroxide simultaneously and prevent that molybdenum from becoming the molybdenum orchid, the addition of hydrogen peroxide be the filtered liquid after the acidification quality 3%～8%.If precipitation is arranged, then must filter.The concentration of sampling analysis rhenium, molybdenum.
2) separating step:
Absorption: the feed liquid good acidifying pumps into header tank, measures volume, Open valve, adopt strongly basic anion exchange resin (being gel-type 201 * 7 resins in the present embodiment), the control flow velocity, when just beginning to adsorb, speed can be hurried up, be controlled at 0.4cm/min, the content that guarantees rhenium in the tail washings is less than 0.005g/L, along with resin more and more near saturated, the contents increased of rhenium in the tail washings, slowly reduce rate of adsorption, make resin fully saturated.When rhenium content reaches 0.005g/L in the tail washings, stop absorption.
Drip washing: for removing the molybdenum that adsorbs on the resin, the ammoniacal liquor that adopts 6～10% concentration will prepare eluent as eluent before the operation, the drip washing speed control is below 0.2cm/min, elution volume is at 2～4 times of column volumes, and the molybdenum content of drip washing tail washings is reduced to below the 0.05g/L, stops drip washing.
Resolve: adopt 10% perchloric acid+2N nitric acid as resolving agent, will prepare the parsing agent before the operation, the drip washing speed control is below 0.1cm/min, and elution volume is at 2 times of column volumes, Fractional Collections by volume when collecting desorbed solution, branch sampling analysis.
3) purification step:
Concentrate: the qualified desorbed solution of Fractional Collections, add the ammonium ion of calculated amount, the beaker splendid attire with 5000 milliliters places on the electric furnace, and heating when volume is concentrated into original 1/4th when following, stops heating, naturally cooling, slow stirring is separated out to crystal.
Suction filtration: when percent crystallization in massecuite is reached 80% left and right sides, it is carried out suction filtration, and pure water drip washing a little, the impurity that flush away is carried secretly.
Recrystallization: the crystal behind the suction filtration is dissolved with pure water, the step that repeats concentrated and suction filtration, 3～4 times repeatedly.
Install the crystal of having drained with clean porcelain dish, place in the baking oven, temperature 100 degree, 8 hours, get high-purity rehenic acid ammonium after the cooling, outward appearance is the white crystals body, and it is packed on request.
4) record the result
Adopt ICP-AES (inductive coupling plasma emission spectrograph has used French JY-2000 type product in the present embodiment) to detect, Re content is 69.40%, and the purity of rehenic acid ammonium reaches 99.99%.Impurity summation≤100ppm, (unit: ppm) as follows: K is 2.0, Na is 11.0, Ca is 2.0, Fe is 5.0, W is 5.0, Pb is 1.5, Cu is 3.5, Sn is 2.0, Ba is 2.5, Mn is 2.0, Be＜1.0, Pt＜1.0, Co are 1.0, Cd＜1.0, Cr＜1.0, Mg are 2.5, Zn is 2.5, Sb is 2.0, Al is 3.0, Mo is 32.0, Ni is 1.0, Ti is 2.0 for impurity element and content thereof.
Embodiment 2:
1) leach step:
Soak material: use the enamel reaction still (can also use the reactive tank or the irony reactor of polypropylene material) that is provided with agitator, side valve or bottom valve.At first check each pipeline, pump, valve, cell body, whether power supplys etc. are in standard state, toward the interior water that adds prescribed volume of groove, add and calculate good sodium hydroxide and yellow soda ash, slowly add the load weighted raw material (flue dust) that contains rhenium then, solid-to-liquid ratio S: L=1: 3.5, the volumetric molar concentration of sodium hydroxide is 4.5mol/L, the mass ratio of sodium hydroxide and soda ash is 6: 1, oxygenant is that Sodium Nitrite and hydrogen peroxide mix, the add-on of this oxygenant is 20% of a raw materials quality, rate of addition control is not to emit groove to be advisable, and the volumetric molar concentration of oxygenant is 2.5mol/L, and Sodium Nitrite and hydrogen peroxide mass ratio are 5: 3; 80～90 ℃ of temperature of reaction, the reaction times is 4 hours.
Filter: after reaction mass is cooled to room temperature, use the plate-and-frame filter press press filtration, slag adds the water flushing.
Acidifying: the filtrate after the press filtration, carry out acidifying with sulfuric acid, transferring pH value is 8～10, add hydrogen peroxide simultaneously and prevent that molybdenum from becoming the molybdenum orchid, the addition of hydrogen peroxide be the filtered liquid after the acidification quality 3%～8%.If precipitation is arranged, then must filter.The concentration of sampling analysis rhenium, molybdenum.
2) separating step:
Identical with embodiment 1.
3) purification step:
Identical with embodiment 1.
4) record the result
Adopt ICP-AES (inductive coupling plasma emission spectrograph has used French JY-2000 type product in the present embodiment) to detect, Re content is 69.38%, and the purity of rehenic acid ammonium reaches 99.99%.Impurity summation≤100ppm, (unit: ppm) as follows: K is 2.5, Na is 15.0, Ca is 1.0, Fe is 5.0, W is 6.0, Pb is 2.0, Cu is 3.0, Sn is 2.0, Ba is 2.5, Mn is 1.0, Be＜1.0, Pt＜1.0, Co are 1.0, Cd＜1.0, Cr＜1.0, Mg are 2.5, Zn is 2.5, Sb is 1.0, Al is 3.0, Mo is 38.0, Ni is 1.0, Ti is 2.0 for impurity element and content thereof.
Embodiment 3:
1) leach step:
Soak material: use the enamel reaction still (can also use the reactive tank or the irony reactor of polypropylene material) that is provided with agitator, side valve or bottom valve.At first check each pipeline, pump, valve, cell body, whether power supplys etc. are in standard state, toward the interior water that adds prescribed volume of groove, add and calculate good sodium hydroxide and yellow soda ash, slowly add the load weighted raw material (flue dust) that contains rhenium then, solid-to-liquid ratio S: L=1: 4, the volumetric molar concentration of sodium hydroxide is 4.5mol/L, the mass ratio of sodium hydroxide and soda ash is 8: 1, oxygenant is that Sodium Nitrite and hydrogen peroxide mix, the add-on of this oxygenant is 80% of a raw materials quality, rate of addition control is not to emit groove to be advisable, and the volumetric molar concentration of oxygenant is 3.0mol/L, and Sodium Nitrite and hydrogen peroxide mass ratio are 5: 2; 80～95 ℃ of temperature of reaction, the reaction times is 4 hours.
Filter: after reaction mass is cooled to room temperature, use the plate-and-frame filter press press filtration, slag adds the water flushing.
Acidifying: the filtrate after the press filtration, carry out acidifying with sulfuric acid, transferring pH value is 8～10, add hydrogen peroxide simultaneously and prevent that molybdenum from becoming the molybdenum orchid, the addition of hydrogen peroxide be the filtered liquid after the acidification quality 3%～8%.。If precipitation is arranged, then must filter.The concentration of sampling analysis rhenium, molybdenum.
2) separating step:
Identical with embodiment 1.
3) purification step:
Identical with embodiment 1.
4) record the result
Adopt ICP-AES (inductive coupling plasma emission spectrograph has used French JY-2000 type product in the present embodiment) to detect, Re content is 69.4%, and the purity of rehenic acid ammonium reaches 99.95%.Impurity summation≤500ppm, (unit: ppm) as follows: K is 12.0, Na is 12.5, Ca is 1.5, Fe is 4.0, W is 15.0, Pb is 1.0, Cu is 4.0, Sn is 1.0, Ba is 3.0, Mn is 1.0, Be＜1.0, Pt＜1.0, Co are 1.0, Cd＜1.0, Cr＜1.0, Mg are 12.0, Zn is 1.5, Sb is 1.5, Al is 3.5, Mo is 285.0, Ni is 1.0, Ti is 2.5 for impurity element and content thereof.
Two, prepare the rehenic acid ammonium according to method of the prior art
Comparative example 1
1) leach step:
Soak material: use the enamel reaction still (can also use the reactive tank or the irony reactor of polypropylene material) that is provided with agitator, side valve or bottom valve.Check at first whether each pipeline, pump, valve, cell body, power supply etc. are in standard state, toward the interior water that adds prescribed volume of groove, add and calculate good sulfuric acid, the raw material (flue dust) that slowly adds load weighted rhenium-containing then, solid-to-liquid ratio S: L=1: 4, the initial volumetric molar concentration of vitriolic is 3mol/L, oxygenant is the hydrogen peroxide of concentration 30%, the add-on of hydrogen peroxide is 40% of a raw materials quality, rate of addition control is not to emit groove to be advisable, temperature of reaction is controlled at 60～70 ℃, and the reaction times is 3 hours.
Filter: after reaction mass is cooled to room temperature, use the plate-and-frame filter press press filtration, slag adds the water flushing.
Transfer PH: the filtrate after the press filtration, transferring pH value with yellow soda ash is 8～10, add hydrogen peroxide simultaneously and prevent that molybdenum from becoming the molybdenum orchid, the addition of hydrogen peroxide be the filtered liquid after the acidification quality 3%～8%.If precipitation is arranged, then must filter.The concentration of sampling analysis rhenium, molybdenum.
2) separating step:
Absorption: the feed liquid that mixes up pH value is pumped into header tank, measure volume, Open valve, control flow velocity, when just beginning to adsorb, speed can be hurried up, and is controlled at 0.4cm/min, and the content that guarantees rhenium in the tail washings is less than 0.005g/L, along with resin is more and more approaching saturated, the contents increased of rhenium in the tail washings slowly reduces rate of adsorption, makes strong basicity 201 * 7 type anionite-exchange resin fully saturated.When rhenium content reaches 0.005g/L in the tail washings, stop absorption.
Drip washing: for removing the molybdenum that adsorbs on the resin, the ammoniacal liquor that adopts 6～10% concentration will prepare eluent as eluent before the operation, the drip washing speed control is below 0.2cm/min, elution volume is at 2～4 times of column volumes, and the molybdenum content of drip washing tail washings is reduced to below the 0.05g/L, stops drip washing.
Resolve: adopt 10% perchloric acid+2N nitric acid as resolving agent, will prepare the parsing agent before the operation, the drip washing speed control is below 0.1cm/min, and elution volume is at 2 times of column volumes, Fractional Collections by volume when collecting desorbed solution, branch sampling analysis.
3) purification step:
Concentrate: the qualified desorbed solution of Fractional Collections, add the ammonium ion of calculated amount, the beaker splendid attire with 5000 milliliters places on the electric furnace, and heating when volume is concentrated into original 1/4th when following, stops heating, naturally cooling, slow stirring is separated out to crystal.
Suction filtration: when percent crystallization in massecuite is reached 80% left and right sides, it is carried out suction filtration, and pure water drip washing a little, the impurity that flush away is carried secretly.
Recrystallization: the crystal behind the suction filtration is dissolved with pure water, the step that repeats concentrated and suction filtration, 3～4 times repeatedly.
Install the crystal of having drained with clean porcelain dish, place in the baking oven, temperature 100 degree, 8 hours, get high-purity rehenic acid ammonium after the cooling, outward appearance is the white crystals body, and it is packed on request.
4) record the result
Adopt French JY-2000ICP-AES (inductive coupling plasma emission spectrograph) to detect, Re content is 68.89%, the purity of rehenic acid ammonium reaches 99.12%, impurity summation≤2000ppm, (unit: ppm) as follows: K is 20, Na is 32, Ca is 25, Fe is 35, W is 155, Pb is 8, Cu is 36, Sn is 45, Ba is 55, Mn is 56, Be is 10, Pt is 8, Co is 15, Cd is 12, Cr is 18, Mg is 45, Zn is 75, Sb is 65, Al is 165, Mo is 782, Ni is 58, Ti is 42 for impurity element and content thereof.
Comparative example 2:
1) leach step:
Soak material: use the enamel reaction still (can also use the reactive tank or the irony reactor of polypropylene material) that is provided with agitator, side valve or bottom valve.Check at first whether each pipeline, pump, valve, cell body, power supply etc. are in standard state, toward the interior water that adds prescribed volume of groove, add and calculate good sulfuric acid, the raw material (flue dust) that slowly adds load weighted rhenium-containing then, solid-to-liquid ratio S: L=1: 8, the initial volumetric molar concentration of vitriolic is 6mol/L, and oxygenant is a Manganse Dioxide, and the add-on of oxygenant is heavy by 20% for material; Temperature of reaction is controlled at 80～90 ℃, and the reaction times is 4 hours.About reaction end of a period acidity control sulfuric acid content 1.2mol/L.
Filter: after reaction mass is cooled to room temperature, use the plate-and-frame filter press press filtration, slag adds the water flushing.
2) separating step:
Remove molybdenum: the filtrate after the press filtration, neutralize with lime, pH value is 8～10, and the molybdenum in the solution precipitates with the form of calcium molybdate and separates with rhenium, and the concentration of sampling analysis rhenium, molybdenum when the concentration of molybdenum is controlled at 0.05g/L, is filtered.
3) purification step:
Concentrate: neutralization is filtered back solution with 5000 milliliters beaker splendid attire, adds the ammonium ion of calculated amount, places on the electric furnace, heats, when volume is concentrated into density and is 1.1g/cm3, stop heating, adopt freezing plant to be cooled to 10 degree, ageing 4 hours is separated out to crystal.
Suction filtration: crystal and mother liquor are carried out suction filtration, and pure water drip washing a little, the impurity that flush away is carried secretly.
Recrystallization: the crystal behind the suction filtration is dissolved with pure water, repeat the step of concentrated and suction filtration again, 3～4 times repeatedly.
Install the crystal of having drained with clean porcelain dish, place in the baking oven, temperature 100 degree, 8 hours, must purer rehenic acid potassium after the cooling, outward appearance is the white crystals body, and it is packed on request.
4) record the result
Adopt French JY-2000ICP-AES (inductive coupling plasma emission spectrograph) to detect, Re content is 63.32%, and the purity of rehenic acid ammonium reaches 98.38%.Impurity summation≤5000ppm, (unit: ppm) as follows: K is 20, Na is 58, Ca is 2548, Fe is 153, W is 165, Pb is 8, Cu is 35, Sn is 23, Ba is 84, Mn is 63, Be is 12, Pt is 14, Co is 26, Cd is 13, Cr is 14, Mg is 36, Zn is 45, Sb is 24, Al is 78, Mo is 1536, Ni is 136, Ti is 79 for impurity impurity element and content thereof.
Three, the result data (table 1) of embodiment 1-3 and comparative example 1-2
Table 1
As can be seen from Table 1, the rehenic acid ammonium purity height of prepared in accordance with the method for the present invention, and total recovery height, foreign matter content is low.
In sum,, under normal pressure, carry out alkaline oxygenated leaching rhenium, solved and adopted acidic oxidation to leach the pollution of the deep-etching of equipment and acid mist to environment according to the treatment process of rhenium-containing raw material of the present invention.The method according to this invention is convenient to industrial production, need not acidifying and directly adopts ion exchange technique, has accelerated the velocity of separation of molybdenum rhenium, and the usage quantity of acid has reduced production cost when having reduced acidifying, and helps environmental protection.What is more important the method according to this invention can make high purity rehenic acid ammonium, compares with adopting method of the prior art, and its yield obviously improves.And the rehenic acid ammonium can be used as the technology that good intermediate is used for producing various rhenium goods.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the treatment process of a rhenium-containing raw material is characterized in that, comprising:
A) leach step, under the normal pressure alkaline environment described rhenium-containing raw material is mixed with oxygenant, question response filters reactant after finishing;
B) separating step after will adsorbing by strongly basic anion exchange resin through the filtered liquid that described step a) obtains, is resolved described strongly basic anion exchange resin,
Wherein, described oxygenant is the mixture of Sodium Nitrite and hydrogen peroxide.
2. treatment process according to claim 1, it is characterized in that, between described step a) and step b), further comprise acidification step, to carry out acidification through the filtered liquid that described step a) obtains, make the pH value of the filtered liquid after the acidification be adjusted to 8～10, and the interpolation hydrogen peroxide, the addition of described hydrogen peroxide be the filtered liquid after the described acidification quality 3%～8%.
3. treatment process according to claim 1, it is characterized in that, the mixing solutions that alkaline environment in the described step a) is formed by sodium hydroxide and yellow soda ash and water makes up and forms, and wherein, the mass ratio of described sodium hydroxide and yellow soda ash is in 6: 1～10: 1 scope.
4. treatment process according to claim 1 is characterized in that, the mass ratio of described Sodium Nitrite and hydrogen peroxide is in 5: 3.5～5: 2.5 scopes.
5. treatment process according to claim 1 is characterized in that, the mass ratio of described oxygenant and described rhenium-containing raw material is 20%～80%.
6. treatment process according to claim 1 is characterized in that, in described step b), before described strongly basic anion exchange resin is resolved, adopts ammoniacal liquor as the described strongly basic anion exchange resin of eluent drip washing.
7. treatment process according to claim 1 is characterized in that, further comprises step c) after described step b), adds ammonium ion in the desorbed solution that obtains through described step b), carries out crystallization treatment, obtains the rehenic acid ammonium.
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| CN102628111A (en) * | 2012-04-06 | 2012-08-08 | 阳谷祥光铜业有限公司 | Method for extracting rhenium from rhenium-rich concentrates |
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