CN106517336B - A kind of purification from ammonium paratungstate is except the method for rhenium - Google Patents
A kind of purification from ammonium paratungstate is except the method for rhenium Download PDFInfo
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- CN106517336B CN106517336B CN201611033672.8A CN201611033672A CN106517336B CN 106517336 B CN106517336 B CN 106517336B CN 201611033672 A CN201611033672 A CN 201611033672A CN 106517336 B CN106517336 B CN 106517336B
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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Abstract
The invention discloses a kind of purification from ammonium paratungstate except the method for rhenium, this method are：First, dissolve：Ammonium paratungstate of the rhenium content more than 15ppm is dissolved with sodium hydroxide solution first, obtains the aqueous slkali of sodium tungstate；2nd, adsorb：The aqueous slkali of sodium tungstate is subjected to dynamic ion-exchange, after adsorption saturation, stops ion exchange；3rd, desorb：With 10g/L NH4Cl+1mol/L NH3·H2O solution elutes, then with 5mol/L NH4Cl+2mol/L NH3·H2O solution is desorbed, and obtains pure ammonium tungstate solution；4th, crystallize：Pure ammonium tungstate solution is evaporated crystallization, control percent crystallization in massecuite is not more than 80%, obtains the order of ammoniumparatungstate crystal that rhenium content is less than 5ppm.The ammonium paratungstate that the present invention realizes the impurity containing trace rhenium purifies to obtain the preparation of the ammonium paratungstate containing higher purity, so as to meet requirement of some special materials to low rhenium content in tungsten.
Description
Technical field
The invention belongs to technical field of metallurgical purification, and in particular to a kind of purification from ammonium paratungstate is except the method for rhenium.
Background technology
Tungsten has highest fusing point and boiling point in metallic element, while also again with high density, high intensity, higher sound
Fast, superior corrosion stability and capability of resistance to radiation, and good hot property and relatively low sputtering yield strength, and be widely used in
The industry such as Ferrous Metallurgy, national defence and Aero-Space, electronics.
Impurity content is gradually recognized tungsten material and the affecting laws of tungsten alloy performance by people.High purity tungsten (quality
Content is 99.999%) or ultra-high pure tungsten (mass content 99.9999%) is with the high conductance to electron transfer, high-temperature stable
Property and the characteristics of stable silicide can be formed, be used as grid, connection and obstacle metal in the form of a film in the electronics industry,
Also serve as the distribution material of semiconductor.Some impurity elements also show that important influence, example in the performance of specific tungsten material
Such as, P elements are (1 × 10-7)~(1 × 10-6) in the range of change that some tungsten materials and alloy property will all produced will be significant
Change.
With the exploitation and extensive use of High Performance W material, purity or some impurity of each industrial circle to ammonium paratungstate
The requirement of content will more and more higher.At present GB_T 3459-2006 tungsten rods only to wherein Pb, Bi, Sn, Sb, As, Fe, Ni, Al,
Si, Ca, Mg, Mo, P, C, O, N have content requirement.China APT produces according to 0 grade of product of national standard at present, even if 23 as contained by standard
The impurity element upper limit calculates, and its purity is only 99.9% or so, the also not requirement to rhenium content of its standard.Rhenium as with tungsten
The much like rare refractory metal of property, usually association is in molybdenum ore, and the molybdenum content more and more higher in current tungsten ore, simultaneously
The national standard of tungsten product does not have at present is required to the content of rhenium, and the concern to rhenium is lacked in tungsten product production process, may
Rhenium can be caused to enter final product, so that tungsten product possibly can not meet the requirement higher to trace element of some materials.
The method of W-Re separation at present mainly has ion-exchange, volatility process, the potassium perrhenate precipitation method.Wherein ion exchange
Method is mainly using some resins (such as AB-17 × 16 Γ resins) to ReO4 -Absorption property be much larger than H2W12O40 5-, therefore ReO4 -
It is preferentially adsorbed so as to reach the effect of W-Re separation.Volatility process utilizes the oxide of rhenium mainly for the treatment of tungsten-rhenium alloy etc.
Re2O7Low boiling point (361 DEG C), tungsten-rhenium alloy is placed in hot conditions so that rhenium is oxidized to Re2O7Volatilization separates with tungsten.High rhenium
Sour potassium precipitation rule is to be separated using potassium tungstate with potassium perrhenate dissolubility difference, KReO4 at 0 DEG C in 100g water most
High meltage is 0.358g, and the solubility of potassium tungstate is very big.But the method for these W-Res separation at present is all mainly processing
Material when W-Re ratio is quite or W-Re content is larger, separating for rhenium can not be carried out to the material containing Determination of Trace Rhenium in tungsten
Remove.
The content of the invention
The technical problems to be solved by the invention are to be directed to above-mentioned the deficiencies in the prior art, there is provided a kind of from para-tungstic acid
Purification is except the method for rhenium in ammonium.The purification method is simple, controllable, using using Cl-The resin of type 201 × 7 carries out Dynamic ion friendship
Absorption is changed, the WO of high concentration can be maximally utilised4 2-Replace the impurity anions ReO being adsorbed4 2-, so as to reach
Except the effect of rhenium, control the percent crystallization in massecuite of ammonium paratungstate to be not more than 80%, obtain the high-purity ammonium paratungstate that rhenium content is less than 5ppm.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of purification from ammonium paratungstate is except rhenium
Method, it is characterised in that this method comprises the following steps：
Step 1: dissolving：Ammonium paratungstate of the rhenium content more than 15ppm is dissolved with sodium hydroxide solution first, obtains tungsten
The aqueous slkali of sour sodium；NaOH mass concentration is 4g/L~8g/L, WO in the aqueous slkali of the sodium tungstate3Mass concentration be
15g/L~25g/L；
Step 2: absorption：By the aqueous slkali of sodium tungstate described in step 1 by being filled with Cl-The resin of type 201 × 7 from
Sub- exchange column carries out dynamic ion-exchange, as WO in the efflux of ion exchange column3Mass concentration and influent in WO3Matter
When amount concentration is identical, Cl-The resin adsorption saturation of type 201 × 7, then stop ion exchange；
Step 3: desorption：After the ion exchange absorption process of step 2 terminates, with 10g/L NH4Cl+1mol/L
NH3·H2O solution, to the Cl in ion exchange column-The resin of type 201 × 7 is eluted, then with 5mol/L NH4Cl+2mol/L
NH3·H2O solution is to the Cl in ion exchange column-The resin of type 201 × 7 is desorbed, and obtains pure ammonium tungstate solution；
Step 4: crystallization：The pure ammonium tungstate solution for desorbing to obtain in step 3 is evaporated crystallization, controls secondary tungsten
The percent crystallization in massecuite of sour ammonium is not more than 80%, obtains the order of ammoniumparatungstate crystal that rhenium content is less than 5ppm.
A kind of above-mentioned purification from ammonium paratungstate is except the method for rhenium, it is characterised in that Dynamic ion described in step 2
The linear flow rate of exchange is 4cm/min.
A kind of above-mentioned purification from ammonium paratungstate is except the method for rhenium, it is characterised in that Dynamic ion described in step 2
The temperature of the aqueous slkali of sodium tungstate is 15 DEG C~35 DEG C in exchange process.
A kind of above-mentioned purification from ammonium paratungstate is except the method for rhenium, it is characterised in that ammonium tungstate is molten described in step 4
The temperature of the evaporative crystallization of liquid is 95 DEG C.
The present invention has advantages below compared with prior art：
1st, operation principle of the invention is：When the aqueous slkali of sodium tungstate flows through Cl-It is right during type strongly basic anionic resin layer
Strong-base anion-exchange resin affinity is more than Cl-Will be adsorbed on resin, it may occur that following ion exchange reaction：
2R4NCl+WO4 2-=(R4N)2WO4+2Cl-1
2R4NCl+CrO4 2-=(R4N)2CrO4+2Cl-1
2R4NCl+SiO3 2-=(R4N)2SiO3+2Cl-1
R4NCl+ReO4 -=(R4N)2ReO4 -+Cl-1
When absorption is constantly carried out, when sodium tungstate solution constantly flows into exchange column, some impurity being adsorbed onto on resin
Anion, will be by the higher WO of concentration4 2-Replace and be gradually transferred in the lower-layer resin of exchange column, finally gradually from tree
It is set to change the liquid into after handing over and realize the separation of tungsten and impurity in lipid layer.(R4N)2SiO3+WO4 2-=(R4N)2WO4+SiO3 2-
2R4N ReO4 -+WO4 2-=(R4N)2WO4+2ReO4 -
2nd, the present invention uses Cl-The resin of type 201 × 7 carries out dynamic ion-exchange absorption, advantages of good adsorption effect, and the present invention
The method adsorbed using saturation, i.e., as WO in the efflux of ion exchange column3Mass concentration and influent in WO3Quality it is dense
When spending identical, Cl-The resin adsorption saturation of type 201 × 7, then stop ion exchange, utilizes the WO of high concentration to greatest extent4 2-Put
Change the impurity anions ReO being adsorbed4 2-, so as to reach the effect for removing rhenium, while ammonium tungstate converts in crystallization process
For ammonium para-tungstate crystal, the solubility of ammonium paratungstate is much smaller than ammonium perrhenate and ammonium tungstate, also there is certain point in crystallization process
From effect.
3rd, the present invention can purify the rhenium removed in ammonium paratungstate and obtain the ammonium paratungstate of higher purity, so as to meet some spies
Different requirement of the material to low rhenium content in tungsten, realizes the purification of the ammonium paratungstate containing trace rhenium.
Technical scheme is described in further detail below by embodiment.
Embodiment
Embodiment 1
Purified from the ammonium paratungstate that rhenium content is 18ppm except the method for rhenium is：
Step 1: dissolving：Take 57g sodium hydroxides (analysis is pure) to be dissolved in 4.425L water, obtain sodium hydroxide solution, then
The ammonium paratungstate that 100g rheniums content is 18ppm is dissolved in sodium hydroxide solution, and reacted with sodium hydroxide, finally
To the aqueous slkali of sodium tungstate；NaOH mass concentration is 6g/L, WO in the aqueous slkali of the sodium tungstate3Mass concentration be 20g/
L；
Step 2: absorption：By the aqueous slkali of sodium tungstate described in step 1 by being filled with Cl-The resin of type 201 × 7 from
Sub- exchange column carries out dynamic ion-exchange, as WO in the efflux of ion exchange column3Mass concentration and influent in WO3Matter
When amount concentration is identical, Cl-The resin adsorption saturation of type 201 × 7, then stop ion exchange；Sodium tungstate in the ion exchange process
The exchange velocity of aqueous slkali be 4cm/min；The temperature of the aqueous slkali of sodium tungstate is 25 DEG C in the dynamic ion-exchange process；
Step 3: desorption：After the ion exchange absorption process of step 2 terminates, with 10g/L NH4Cl+1mol/L
NH3·H2O solution, to the Cl in ion exchange column-The resin of type 201 × 7 is eluted, then with 5mol/L NH4Cl+2mol/L
NH3·H2O solution is to the Cl in ion exchange column-The resin of type 201 × 7 is desorbed, and obtains pure ammonium tungstate solution；
Step 4: crystallization：By the pure ammonium tungstate solution for desorbing to obtain in step 3 under conditions of temperature is 95 DEG C
Crystallization is evaporated, when the percent crystallization in massecuite of ammonium paratungstate is 80%, obtains the order of ammoniumparatungstate crystal that rhenium content is 5ppm.
Embodiment 2
Purified from the ammonium paratungstate that rhenium content is 15ppm except the method for rhenium is：
Step 1: dissolving：Take 44.6g sodium hydroxides (analysis is pure) to be dissolved in 3.54L water, obtain sodium hydroxide solution,
The ammonium paratungstate that 100g rheniums content is 15ppm is dissolved in sodium hydroxide solution again, and reacted with sodium hydroxide, finally
Obtain the aqueous slkali of sodium tungstate；NaOH mass concentration is 4g/L, WO in the aqueous slkali of the sodium tungstate3Mass concentration be
25g/L；
Step 2: absorption：By the aqueous slkali of sodium tungstate described in step 1 by being filled with Cl-The resin of type 201 × 7 from
Sub- exchange column carries out dynamic ion-exchange, as WO in the efflux of ion exchange column3Mass concentration and influent in WO3Matter
When amount concentration is identical, Cl-The resin adsorption saturation of type 201 × 7, then stop ion exchange；Sodium tungstate in the ion exchange process
The exchange velocity of aqueous slkali be 4cm/min；The temperature of the aqueous slkali of sodium tungstate is 15 DEG C in the dynamic ion-exchange process；
Step 3: desorption：After the ion exchange absorption process of step 2 terminates, with 10g/L NH4Cl+1mol/L
NH3·H2O solution, to the Cl in ion exchange column-The resin of type 201 × 7 is eluted, then with 5mol/L NH4Cl+2mol/L
NH3·H2O solution is to the Cl in ion exchange column-The resin of type 201 × 7 is desorbed, and obtains pure ammonium tungstate solution；
Step 4: crystallization：By the pure ammonium tungstate solution for desorbing to obtain in step 3 under conditions of temperature is 95 DEG C
Crystallization is evaporated, the percent crystallization in massecuite for controlling ammonium paratungstate is 60%, obtains the order of ammoniumparatungstate crystal that rhenium content is 3ppm.
Embodiment 3
Purified from the ammonium paratungstate that rhenium content is 22ppm except the method for rhenium is：
Step 1: dissolving：Take 58.8g sodium hydroxides (analysis is pure) to be dissolved in 3.54L water, obtain sodium hydroxide solution,
The ammonium paratungstate that 100g rheniums content is 22ppm is dissolved in sodium hydroxide solution again, and reacted with sodium hydroxide, finally
Obtain the aqueous slkali of sodium tungstate；NaOH mass concentration is 8g/L, WO in the aqueous slkali of the sodium tungstate3Mass concentration be
25g/L；
Step 2: absorption：By the aqueous slkali of sodium tungstate described in step 1 by being filled with Cl-The resin of type 201 × 7 from
Sub- exchange column carries out dynamic ion-exchange, as WO in the efflux of ion exchange column3Mass concentration and influent in WO3Matter
When amount concentration is identical, Cl-The resin adsorption saturation of type 201 × 7, then stop ion exchange；Sodium tungstate in the ion exchange process
The exchange velocity of aqueous slkali be 4cm/min；The temperature of the aqueous slkali of sodium tungstate is 35 DEG C in the dynamic ion-exchange process；
Step 3: desorption：After the ion exchange absorption process of step 2 terminates, with 10g/L NH4Cl+1mol/L
NH3·H2O solution, to the Cl in ion exchange column-The resin of type 201 × 7 is eluted, then with 5mol/L NH4Cl+2mol/L
NH3·H2O solution is to the Cl in ion exchange column-The resin of type 201 × 7 is desorbed, and obtains pure ammonium tungstate solution；
Step 4: crystallization：By the pure ammonium tungstate solution for desorbing to obtain in step 3 under conditions of temperature is 95 DEG C
Crystallization is evaporated, the percent crystallization in massecuite for controlling ammonium paratungstate is 70%, obtains the order of ammoniumparatungstate crystal that rhenium content is less than 4ppm.
Embodiment 4
Purified from the ammonium paratungstate that rhenium content is 25ppm except the method for rhenium is：
Step 1: dissolving：Take 54g sodium hydroxides (analysis is pure) to be dissolved in 5.9L water, obtain sodium hydroxide solution, then will
100g rheniums content is that 25ppm ammonium paratungstate is dissolved in sodium hydroxide solution, and is reacted with sodium hydroxide, is finally obtained
The aqueous slkali of sodium tungstate；NaOH mass concentration is 4g/L, WO in the aqueous slkali of the sodium tungstate3Mass concentration be 15g/L；
Step 2: absorption：By the aqueous slkali of sodium tungstate described in step 1 by being filled with Cl-The resin of type 201 × 7 from
Sub- exchange column carries out dynamic ion-exchange, as WO in the efflux of ion exchange column3Mass concentration and influent in WO3Matter
When amount concentration is identical, Cl-The resin adsorption saturation of type 201 × 7, then stop ion exchange；Sodium tungstate in the ion exchange process
The exchange velocity of aqueous slkali be 4cm/min；The temperature of the aqueous slkali of sodium tungstate is 25 DEG C in the dynamic ion-exchange process；
Step 3: desorption：After the ion exchange absorption process of step 2 terminates, with 10g/L NH4Cl+1mol/L
NH3·H2O solution, to the Cl in ion exchange column-The resin of type 201 × 7 is eluted, then with 5mol/L NH4Cl+2mol/L
NH3·H2O solution is to the Cl in ion exchange column-The resin of type 201 × 7 is desorbed, and obtains pure ammonium tungstate solution；
Step 4: crystallization：By the pure ammonium tungstate solution for desorbing to obtain in step 3 under conditions of temperature is 95 DEG C
Crystallization is evaporated, when the percent crystallization in massecuite of ammonium paratungstate is 80%, obtains the order of ammoniumparatungstate crystal that rhenium content is 5ppm.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (3)
1. a kind of purification from ammonium paratungstate is except the method for rhenium, it is characterised in that this method comprises the following steps：
Step 1: dissolving：Ammonium paratungstate of the rhenium content more than 15ppm is dissolved with sodium hydroxide solution first and reacted, obtains tungsten
The aqueous slkali of sour sodium；NaOH mass concentration is 4g/L~8g/L, WO in the aqueous slkali of the sodium tungstate3Mass concentration be
15g/L~25g/L；
Step 2: absorption：By the aqueous slkali of sodium tungstate described in step 1 by being filled with Cl-The ion of the resin of type 201 × 7 is handed over
Change post and carry out dynamic ion-exchange, as WO in the efflux of ion exchange column3Mass concentration and influent in WO3Quality it is dense
When spending identical, Cl-The resin adsorption saturation of type 201 × 7, stop ion exchange；The linear flow rate of the dynamic ion-exchange is
4cm/min；
Step 3: desorption：After the ion exchange of step 2 terminates, with 10g/L NH4Cl+1mol/L NH3·H2O solution, it is right
Cl in ion exchange column-The resin of type 201 × 7 is eluted, then with 5mol/L NH4Cl+2mol/L NH3·H2O solution to from
Cl in sub- exchange column-The resin of type 201 × 7 is desorbed, and obtains pure ammonium tungstate solution；
Step 4: crystallization：The pure ammonium tungstate solution for desorbing to obtain in step 3 is evaporated crystallization, controls ammonium paratungstate
Percent crystallization in massecuite be not more than 80%, obtain rhenium content be less than 5ppm order of ammoniumparatungstate crystal.
2. a kind of purification from ammonium paratungstate according to claim 1 is except the method for rhenium, it is characterised in that institute in step 2
The temperature for stating the aqueous slkali of sodium tungstate in dynamic ion-exchange process is 15 DEG C~35 DEG C.
3. a kind of purification from ammonium paratungstate according to claim 1 is except the method for rhenium, it is characterised in that institute in step 4
The temperature for stating the evaporative crystallization of ammonium tungstate solution is 95 DEG C.
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| US7572379B2 (en) * | 2005-09-02 | 2009-08-11 | Sachem, Inc. | Removal of metal ions from onium hydroxides and onium salt solutions |
| CN104176784B (en) * | 2014-08-16 | 2016-03-16 | 厦门世达膜科技有限公司 | A kind of method preparing ammonium perrhenate |
| CN105197997B (en) * | 2015-09-11 | 2017-01-04 | 中国有色集团（广西）平桂飞碟股份有限公司 | The method of ammonium paratungstate degree of depth clarification |
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